National Library of Energy BETA

Sample records for oxides carbon monoxide

  1. Device for staged carbon monoxide oxidation

    DOE Patents [OSTI]

    Vanderborgh, Nicholas E.; Nguyen, Trung V.; Guante, Jr., Joseph

    1993-01-01

    A method and apparatus for selectively oxidizing carbon monoxide in a hydrogen rich feed stream. The method comprises mixing a feed stream consisting essentially of hydrogen, carbon dioxide, water and carbon monoxide with a first predetermined quantity of oxygen (air). The temperature of the mixed feed/oxygen stream is adjusted in a first the heat exchanger assembly (20) to a first temperature. The mixed feed/oxygen stream is sent to reaction chambers (30,32) having an oxidation catalyst contained therein. The carbon monoxide of the feed stream preferentially absorbs on the catalyst at the first temperature to react with the oxygen in the chambers (30,32) with minimal simultaneous reaction of the hydrogen to form an intermediate hydrogen rich process stream having a lower carbon monoxide content than the feed stream. The elevated outlet temperature of the process stream is carefully controlled in a second heat exchanger assembly (42) to a second temperature above the first temperature. The process stream is then mixed with a second predetermined quantity of oxygen (air). The carbon monoxide of the process stream preferentially reacts with the second quantity of oxygen in a second stage reaction chamber (56) with minimal simultaneous reaction of the hydrogen in the process stream. The reaction produces a hydrogen rich product stream having a lower carbon monoxide content than the process stream. The product stream is then cooled in a third heat exchanger assembly (72) to a third predetermined temperature. Three or more stages may be desirable, each with metered oxygen injection.

  2. Composite catalyst for carbon monoxide and hydrocarbon oxidation

    DOE Patents [OSTI]

    Liu, W.; Flytzani-Stephanopoulos, M.

    1996-03-19

    A method and composition are disclosed for the complete oxidation of carbon monoxide and/or hydrocarbon compounds. The method involves reacting the carbon monoxide and/or hydrocarbons with an oxidizing agent in the presence of a metal oxide composite catalyst. The catalyst is prepared by combining fluorite-type oxygen ion conductors with active transition metals. The fluorite oxide, selected from the group consisting of cerium oxide, zirconium oxide, thorium oxide, hafnium oxide, and uranium oxide, and may be doped by alkaline earth and rare earth oxides. The transition metals, selected from the group consisting of molybdenum, copper, cobalt, manganese, nickel, and silver, are used as additives. The atomic ratio of transition metal to fluorite oxide is less than one.

  3. Composite catalyst for carbon monoxide and hydrocarbon oxidation

    DOE Patents [OSTI]

    Liu, Wei; Flytzani-Stephanopoulos, Maria

    1996-01-01

    A method and composition for the complete oxidation of carbon monoxide and/or hydrocarbon compounds. The method involves reacting the carbon monoxide and/or hydrocarbons with an oxidizing agent in the presence of a metal oxide composite catalyst. The catalyst is prepared by combining fluorite-type oxygen ion conductors with active transition metals. The fluorite oxide, selected from the group consisting of cerium oxide, zirconium oxide, thorium oxide, hafnium oxide, and uranium oxide, and may be doped by alkaline earth and rare earth oxides. The transition metals, selected from the group consisting of molybdnum, copper, cobalt, maganese, nickel, and silver, are used as additives. The atomic ratio of transition metal to fluorite oxide is less than one.

  4. Size Effect of Ruthenium Nanoparticles in Catalytic Carbon Monoxide Oxidation

    SciTech Connect (OSTI)

    Joo, Sang Hoon; Park, Jeong Y.; Renzas, J. Russell; Butcher, Derek R.; Huang, Wenyu; Somorjai, Gabor A.

    2010-04-04

    Carbon monoxide oxidation over ruthenium catalysts has shown an unusual catalytic behavior. Here we report a particle size effect on CO oxidation over Ru nanoparticle (NP) catalysts. Uniform Ru NPs with a tunable particle size from 2 to 6 nm were synthesized by a polyol reduction of Ru(acac){sub 3} precursor in the presence of poly(vinylpyrrolidone) stabilizer. The measurement of catalytic activity of CO oxidation over two-dimensional Ru NPs arrays under oxidizing reaction conditions (40 Torr CO and 100 Torr O{sub 2}) showed an activity dependence on the Ru NP size. The CO oxidation activity increases with NP size, and the 6 nm Ru NP catalyst shows 8-fold higher activity than the 2 nm catalysts. The results gained from this study will provide the scientific basis for future design of Ru-based oxidation catalysts.

  5. Composite catalyst for carbon monoxide and hydrocarbon oxidation...

    Office of Scientific and Technical Information (OSTI)

    The atomic ratio of transition metal to fluorite oxide is less than one. Inventors: Liu, Wei 1 ; Flytzani-Stephanopoulos, Maria 2 + Show Author Affiliations (Cambridge, MA) ...

  6. Reaction of uranium oxides with chlorine and carbon or carbon monoxide to prepare uranium chlorides

    SciTech Connect (OSTI)

    Haas, P.A.; Lee, D.D.; Mailen, J.C.

    1991-11-01

    The preferred preparation concept of uranium metal for feed to an AVLIS uranium enrichment process requires preparation of uranium tetrachloride (UCI{sub 4}) by reacting uranium oxides (UO{sub 2}/UO{sub 3}) and chlorine (Cl{sub 2}) in a molten chloride salt medium. UO{sub 2} is a very stable metal oxide; thus, the chemical conversion requires both a chlorinating agent and a reducing agent that gives an oxide product which is much more stable than the corresponding chloride. Experimental studies in a quartz reactor of 4-cm ID have demonstrated the practically of some chemical flow sheets. Experimentation has illustrated a sequence of results concerning the chemical flow sheets. Tests with a graphite block at 850{degrees}C demonstrated rapid reactions of Cl{sub 2} and evolution of carbon dioxide (CO{sub 2}) as a product. Use of carbon monoxide (CO) as the reducing agent also gave rapid reactions of Cl{sub 2} and formation of CO{sub 2} at lower temperatures, but the reduction reactions were slower than the chlorinations. Carbon powder in the molten salt melt gave higher rates of reduction and better steady state utilization of Cl{sub 2}. Addition of UO{sub 2} feed while chlorination was in progress greatly improved the operation by avoiding the plugging effects from high UO{sub 2} concentrations and the poor Cl{sub 2} utilizations from low UO{sub 2} concentrations. An UO{sub 3} feed gave undesirable effects while a feed of UO{sub 2}-C spheres was excellent. The UO{sub 2}-C spheres also gave good rates of reaction as a fixed bed without any molten chloride salt. Results with a larger reactor and a bottom condenser for volatilized uranium show collection of condensed uranium chlorides as a loose powder and chlorine utilizations of 95--98% at high feed rates. 14 refs., 7 figs., 14 tabs.

  7. Kinetics of the carbon monoxide oxidation reaction under microwave heating

    SciTech Connect (OSTI)

    Perry, W.L.; Katz, J.D.; Rees, D.; Paffett, M.T. [Los Alamos National Lab., NM (United States); Datye, A. [Univ. of New Mexico, Albuquerque, NM (United States)

    1996-06-01

    915 MHz microwave heating has been used to drive the CO oxidation reaction over Pd/Al{sub 2}O{sub 3} with out significantly affecting the reaction kinetics. As compared to an identical conventionally heated system, the activation energy, pre-exponential factor, and reaction order with respect to CO were unchanged. Temperature was measured using a thermocouple extrapolation technique. Microwave-induced thermal gradients were found to play a significant role in kinetic observations. The authors chose the CO oxidation reaction over a supported metal catalyst because the reaction kinetics are well known, and because of the diverse dielectric properties of the various elements in the system: CO is a polar molecule, O{sub 2} and CO{sub 2} are non-polar, Al{sub 2}O{sub 3} is a dielectric, and Pt and Pd are conductors.

  8. Method of removing carbon monoxide from gases

    DOE Patents [OSTI]

    Gerstein, Bernard C.; Macaulay, David B.

    1976-06-01

    A process and catalyst are disclosed for purifying an atmosphere containing carbon monoxide by passing the atmosphere through a bed of a catalyst of TbO.sub.x, where x = 1.8 to 1.5, which oxidizes the carbon monoxide to carbon dioxide.

  9. Method and apparatus for selective removal of carbon monoxide

    DOE Patents [OSTI]

    Borup, Rodney L.; Skala, Glenn W.; Brundage, Mark A.; LaBarge, William J.

    2000-01-01

    There is provided a method and apparatus for treatment of a hydrogen-rich gas to reduce the carbon monoxide content thereof by reacting the carbon monoxide in the gas with an amount of oxygen sufficient to oxidize at least a portion of the carbon monoxide in the presence of a catalyst in a desired temperature range without substantial reaction of hydrogen. The catalyst is an iridium-based catalyst dispersed on, and supported on, a carrier. In the presence of the catalyst, carbon monoxide in a hydrogen-rich feed gas is selectively oxidized such that a product stream is produced with a very low carbon monoxide content.

  10. REFORMULATION OF COAL-DERIVED TRANSPORTATION FUELS: SELECTIVE OXIDATION OF CARBON MONOXIDE ON METAL FOAM CATALYSTS

    SciTech Connect (OSTI)

    Mr. Paul Chin; Dr. Xiaolei Sun; Professor George W. Roberts; Professor James J. Spivey; Mr. Amornmart Sirijarhuphan; Dr. James G. Goodwin, Jr.; Dr. Richard W. Rice

    2002-12-31

    Several different catalytic reactions must be carried out in order to convert hydrocarbons (or alcohols) into hydrogen for use as a fuel for polyelectrolyte membrane (PEM) fuel cells. Each reaction in the fuel-processing sequence has a different set of characteristics, which influences the type of catalyst support that should be used for that particular reaction. A wide range of supports are being evaluated for the various reactions in the fuel-processing scheme, including porous and non-porous particles, ceramic and metal straight-channel monoliths, and ceramic and metal monolithic foams. These different types of support have distinctly different transport characteristics. The best choice of support for a given reaction will depend on the design constraints for the system, e.g., allowable pressure drop, and on the characteristics of the reaction for which the catalyst is being designed. Three of the most important reaction characteristics are the intrinsic reaction rate, the exothermicity/endothermicity of the reaction, and the nature of the reaction network, e.g., whether more than one reaction takes place and, in the case of multiple reactions, the configuration of the network. Isotopic transient kinetic analysis was used to study the surface intermediates. The preferential oxidation of low concentrations of carbon monoxide in the presence of high concentrations of hydrogen (PROX) is an important final step in most fuel processor designs. Data on the behavior of straight-channel monoliths and foam monolith supports will be presented to illustrate some of the factors involved in choosing a support for this reaction.

  11. Carbon monoxide alleviates ethanol-induced oxidative damage and inflammatory stress through activating p38 MAPK pathway

    SciTech Connect (OSTI)

    Li, Yanyan; Gao, Chao; Shi, Yanru; Tang, Yuhan; Liu, Liang; Xiong, Ting; Du, Min; Xing, Mingyou; Liu, Liegang; Yao, Ping

    2013-11-15

    Stress-inducible protein heme oxygenase-1(HO-1) is well-appreciative to counteract oxidative damage and inflammatory stress involving the pathogenesis of alcoholic liver diseases (ALD). The potential role and signaling pathways of HO-1 metabolite carbon monoxide (CO), however, still remained unclear. To explore the precise mechanisms, ethanol-dosed adult male Balb/c mice (5.0 g/kg.bw.) or ethanol-incubated primary rat hepatocytes (100 mmol/L) were pretreated by tricarbonyldichlororuthenium (II) dimmer (CORM-2, 8 mg/kg for mice or 20 μmol/L for hepatocytes), as well as other pharmacological reagents. Our data showed that CO released from HO-1 induction by quercetin prevented ethanol-derived oxidative injury, which was abolished by CO scavenger hemoglobin. The protection was mimicked by CORM-2 with the attenuation of GSH depletion, SOD inactivation, MDA overproduction, and the leakage of AST, ALT or LDH in serum and culture medium induced by ethanol. Moreover, CORM-2 injection or incubation stimulated p38 phosphorylation and suppressed abnormal Tnfa and IL-6, accompanying the alleviation of redox imbalance induced by ethanol and aggravated by inflammatory factors. The protective role of CORM-2 was abolished by SB203580 (p38 inhibitor) but not by PD98059 (ERK inhibitor) or SP600125 (JNK inhibitor). Thus, HO-1 released CO prevented ethanol-elicited hepatic oxidative damage and inflammatory stress through activating p38 MAPK pathway, suggesting a potential therapeutic role of gaseous signal molecule on ALD induced by naturally occurring phytochemicals. - Highlights: • CO alleviated ethanol-derived liver oxidative and inflammatory stress in mice. • CO eased ethanol and inflammatory factor-induced oxidative damage in hepatocytes. • The p38 MAPK is a key signaling mechanism for the protective function of CO in ALD.

  12. CO (Carbon Monoxide Mixing Ratio System) Handbook (Technical...

    Office of Scientific and Technical Information (OSTI)

    Technical Report: CO (Carbon Monoxide Mixing Ratio System) Handbook Citation Details In-Document Search Title: CO (Carbon Monoxide Mixing Ratio System) Handbook The main function of ...

  13. REFORMULATION OF COAL-DERIVED TRANSPORTATION FUELS: SELECTIVE OXIDATION OF CARBON MONOXIDE ON METAL FOAM CATALYSTS

    SciTech Connect (OSTI)

    Paul Chin; Xiaolei Sun; George W. Roberts; Amornmart Sirijarhuphan; Sourabh Pansare; James G. Goodwin Jr; Richard W. Rice; James J. Spivey

    2005-06-01

    Hydrocarbon fuels must be reformed in a series of steps to provide hydrogen for use in proton exchange membrane fuel cells (PEMFCs). Preferential oxidation (PROX) is one method to reduce the CO concentration to less than 10 ppm in the presence of {approx}40% H{sub 2}, CO{sub 2}, and steam. This will prevent CO poisoning of the PEMFC anode. Structured supports, such as ceramic monoliths, can be used for the PROX reaction. Alternatively, metal foams offer a number of advantages over the traditional ceramic monolith.

  14. REFORMULATION OF COAL-DERIVED TRANSPORTATION FUELS: SELECTIVE OXIDATION OF CARBON MONOXIDE ON METAL FOAM CATALYSTS

    SciTech Connect (OSTI)

    Paul Chin; George W. Roberts; James J. Spivey

    2003-12-31

    Uses for structured catalytic supports, such as ceramic straight-channel monoliths and ceramic foams, have been established for a long time. One of the most prominent examples is the washcoated ceramic monolith as a three-way catalytic converter for gasoline-powered automobiles. A distinct alternative to the ceramic monolith is the metal foam, with potential use in fuel cell-powered automobiles. The metal foams are characterized by their pores per inch (ppi) and density ({rho}). In previous research, using 5 wt% platinum (Pt) and 0.5 wt% iron (Fe) catalysts, washcoated metal foams, 5.08 cm in length and 2.54 cm in diameter, of both varying and similar ppi and {rho} were tested for their activity (X{sub CO}) and selectivity (S{sub CO}) on a CO preferential oxidation (PROX) reaction in the presence of a H{sub 2}-rich gas stream. The variances in these metal foams' activity and selectivity were much larger than expected. Other structured supports with 5 wt% Pt, 0-1 wt% Fe weight loading were also examined. A theory for this phenomenon states that even though these structured supports have a similar nominal catalyst weight loading, only a certain percentage of the Pt/Fe catalyst is exposed on the surface as an active site for CO adsorption. We will use two techniques, pulse chemisorption and temperature programmed desorption (TPD), to characterize our structured supports. Active metal count, metal dispersion, and other calculations will help clarify the causes for the activity and selectivity variations between the supports. Results on ceramic monoliths show that a higher Fe loading yields a lower dispersion, potentially because of Fe inhibition of the Pt surface for CO adsorption. This theory is used to explain the reason for activity and selectivity differences for varying ppi and {rho} metal foams; less active and selective metal foams have a lower Fe loading, which justifies their higher metal dispersion. Data on the CO desorption temperature and average metal

  15. Process for the production of hydrogen and carbonyl sulfide from hydrogen sulfide and carbon monoxide using a multi-metal oxide/sulfide catalyst

    SciTech Connect (OSTI)

    Jevnikar, M. G.; Kuch, Ph. L.

    1985-02-19

    Hydrogen and carbonyl sulfide are produced by a process comprising contacting gaseous hydrogen sulfide with gaseous carbon monoxide in the presence of a catalytic composition containing an oxide and/or sulfide of at least one of molybdenum, tungsten, iron, chromium and vanadium in combination with at least one promoter metal, e.g. a catalyst of the formula Cs Cu /SUB 0.2/ Zn /SUB 0.5/ Mn /SUB 0.5/ Sn /SUB 2.4/ Mo O /SUB x/ S /SUB y/ .

  16. Carbon Monoxide Sensor - Energy Innovation Portal

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Carbon Monoxide Sensor Los Alamos National Laboratory Contact LANL About This Technology Technology Marketing SummaryScientists at Los Alamos National Laboratory (LANL) have developed an electrochemical carbon monoxide (CO) sensor that is more reliable and reproducible than any other CO sensor on the market today. The patented method for producing the sensor ensures reproducibility and reduces the need for calibration of every sensor coming off the production line.DescriptionInaccurate CO

  17. Near-ambient X-ray photoemission spectroscopy and kinetic approach to the mechanism of carbon monoxide oxidation over lanthanum substituted cobaltites

    SciTech Connect (OSTI)

    Hueso, J. L.; Martinez-Martinez, D.; Cabalerro, Alfonso; Gonzalez-Elipe, Agustin Rodriguez; Mun, Bongjin Simon; Salmeron, Miquel

    2009-07-31

    We have studied the oxidation of carbon monoxide over a lanthanum substituted perovskite (La0.5Sr0.5CoO3-d) catalyst prepared by spray pyrolysis. Under the assumption of a first-order kinetics mechanism for CO, it has been found that the activation energy barrier of the reaction changes from 80 to 40 kJ mol-1 at a threshold temperature of ca. 320 oC. In situ XPS near-ambient pressure ( 0.2 torr) shows that the gas phase oxygen concentration over the sample decreases sharply at ca. 300 oC. These two observations suggest that the oxidation of CO undergoes a change of mechanism at temperatures higher than 300 oC.

  18. Carbon monoxide sensor and method of use

    DOE Patents [OSTI]

    Dutta, Prabir K.; Swartz, Scott L.; Holt, Christopher T.; Revur, Ramachandra Rao

    2006-01-10

    A sensor and method of use for detection of low levels of carbon monoxide in gas mixtures. The approach is based on the change in an electrical property (for example: resistance) that occurs when carbon monoxide is selectively absorbed by a film of copper chloride (or other metal halides). The electrical property change occurs rapidly with both increasing and decreasing CO contents, varies with the amount of CO from the gas stream, and is insensitive to the presence of hydrogen. To make a sensor using this approach, the metal halide film will deposited onto an alumina substrate with electrodes. The sensor may be maintained at the optimum temperature with a thick film platinum heater deposited onto the opposite face of the substrate. When the sensor is operating at an appropriate (and constant) temperature, the magnitude of the electrical property measured between the interdigital electrodes will provide a measure of the carbon monoxide content of the gas.

  19. Final Technical Report "Catalytic Hydrogenation of Carbon Monoxide and Olefin Oxidation" Grant number : DE-FG02-86ER13615

    SciTech Connect (OSTI)

    Wayland, B.B.

    2009-08-31

    Title: Catalytic Hydrogenation of Carbon Monoxide and Olefin Oxidation Grant No. DE-FG02-86ER13615 PI: Wayland, B. B. (wayland@sas.upenn.edu) Abstract Development of new mechanistic strategies and catalyst materials for activation of CO, H2, CH4, C2H4, O2, and related substrates relevant to the conversion of carbon monoxide, alkanes, and alkenes to organic oxygenates are central objectives encompassed by this program. Design and synthesis of metal complexes that manifest reactivity patterns associated with potential pathways for the hydrogenation of carbon monoxide through metallo-formyl (M-CHO), dimetal ketone (M-C(O)-M), and dimetal dionyl (M-C(O)-C(O)-M) species is one major focus. Hydrocarbon oxidation using molecular oxygen is a central goal for methane activation and functionalization as well as regioselective oxidation of olefins. Discovery of new reactivity patterns and control of selectivity are pursued through designing new metal complexes and adjusting reaction conditions. Variation of reaction media promotes distinct reaction pathways that control both reaction rates and selectivities. Dimetalloradical diporphyrin complexes preorganize transition states for substrate reactions that involve two metal centers and manifest large rate increases over mono-metalloradical reactions of hydrogen, methane, and other small molecule substrates. Another broad goal and recurring theme of this program is to contribute to the thermodynamic database for a wide scope of organo-metal transformations in a range of reaction media. One of the most complete descriptions of equilibrium thermodynamics for organometallic reactions in water and methanol is emerging from the study of rhodium porphyrin substrate reactions in aqueous and alcoholic media. Water soluble group nine metalloporphyrins manifest remarkably versatile substrate reactivity in aqueous and alcoholic media which includes producing rhodium formyl (Rh-CHO) and hydroxy methyl (Rh-CH2OH) species. Exploratory

  20. Enhanced carbon monoxide utilization in methanation process

    DOE Patents [OSTI]

    Elek, Louis F.; Frost, Albert C.

    1984-01-01

    Carbon monoxide - containing gas streams are passed over a catalyst to deposit a surface layer of active surface carbon thereon essentially without the formation of inactive coke. The active carbon is subsequently reacted with steam or hydrogen to form methane. Surprisingly, hydrogen and water vapor present in the feed gas do not adversely affect CO utilization significantly, and such hydrogen actually results in a significant increase in CO utilization.

  1. Catalyst for the methanation of carbon monoxide in sour gas

    DOE Patents [OSTI]

    Kustes, William A. (Louisville, KY); Hausberger, Arthur L. (Louisville, KY)

    1985-01-01

    The invention involves the synergistic effect of the specific catalytic constituents on a specific series of carriers for the methanation of carbon monoxide in the presence of sulfur at relatively high temperatures and at low steam to gas ratios in the range of 0.2:1 or less. This effect was obtained with catalysts comprising the mixed sulfides and oxides of nickel and chromium supported on carriers comprising magnesium aluminate and magnesium silicate. Conversion of carbon monoxide to methane was in the range of from 40 to 80%. Tests of this combination of metal oxides and sulfides on other carriers and tests of other metal oxides and sulfides on the same carrier produced a much lower level of conversion.

  2. CO (Carbon Monoxide Mixing Ratio System) Handbook

    SciTech Connect (OSTI)

    Biraud, S

    2011-02-23

    The main function of the CO instrument is to provide continuous accurate measurements of carbon monoxide mixing ratio at the ARM SGP Central Facility (CF) 60-meter tower (36.607 °N, 97.489 °W, 314 meters above sea level). The essential feature of the control and data acquisition system is to record signals from a Thermo Electron 48C and periodically calibrate out zero and span drifts in the instrument using the combination of a CO scrubber and two concentrations of span gas (100 and 300 ppb CO in air). The system was deployed on May 25, 2005.

  3. Search of medical literature for indoor carbon monoxide exposure

    SciTech Connect (OSTI)

    Brennan, T.; Ivanovich, M.

    1995-12-01

    This report documents a literature search on carbon monoxide. The search was limited to the medical and toxicological databases at the National Library of Medicine (MEDLARS). The databases searched were Medline, Toxline and TOXNET. Searches were performed using a variety of strategies. Combinations of the following keywords were used: carbon, monoxide, accidental, residential, occult, diagnosis, misdiagnosis, heating, furnace, and indoor. The literature was searched from 1966 to the present. Over 1000 references were identified and summarized using the following abbreviations: The major findings of the search are: (1) Acute and subacute carbon monoxide exposures result in a large number of symptoms affecting the brain, kidneys, respiratory system, retina, and motor functions. (2) Acute and subacute carbon monoxide (CO) poisonings have been misdiagnosed on many occasions. (3) Very few systematic investigations have been made into the frequency and consequences of carbon monoxide poisonings.

  4. Effect of Organic Capping Layers over Monodisperse Platinum Nanoparticles upon Activity for Ethylene Hydrogenation and Carbon Monoxide Oxidation

    SciTech Connect (OSTI)

    Kuhn, John N.; Tsung, Chia-Kuang; Huang, Wenyu; Somorjai, Gabor A.

    2009-03-24

    The influence of oleylamine (OA), trimethyl tetradecyl ammonium bromide (TTAB), and polyvinlypyrrolidone (PVP) capping agents upon the catalytic properties of Pt/silica catalysts was evaluated. Pt nanoparticles that were 1.5 nm in size were synthesized by the same procedure (ethylene glycol reduction under basic conditions) with the various capping agents added afterward for stabilization. Before examining catalytic properties for ethylene hydrogenation and CO oxidation, the Pt NPs were deposited onto mesoporous silica (SBA-15) supports and characterized by transmission electron microscopy (TEM), H{sub 2} chemisorption, and elemental analysis (ICP-MS). PVP- and TTAB-capped Pt yielded mass-normalized reaction rates that decreased with increasing pretreatment temperature, and this trend was attributed to the partial coverage of the Pt surface with decomposition products from the organic capping agent. Once normalized to the Pt surface area, similar intrinsic activities were obtained regardless of the pretreatment temperature, which indicated no influence on the nature of the active sites. Consequently, a chemical probe technique using intrinsic activity for ethylene hydrogenation was demonstrated as an acceptable method for estimating the metallic surface areas of Pt. Amine (OA) capping exhibited a detrimental influence on the catalytic properties as severe deactivation and low activity were observed for ethylene hydrogenation and CO oxidation, respectively. These results were consistent with amine groups being strong poisons for Pt surfaces, and revealed the need to consider the effects of capping agents on the catalytic properties.

  5. Zirconia-based potentiometric sensor using a pair of oxide electrodes for selective detection of carbon monoxide

    SciTech Connect (OSTI)

    Miura, Norio; Raisen, Takahisa; Lu, Geyu; Yamazoe, Noboru

    1997-07-01

    A high-performance solid-state compact gas sensor to detect CO has been needed for monitoring and controlling the combustion condition of gas appliances. By using a pair of oxide electrodes, a stabilized-zirconia-based sensor was developed for selective detection of CO at high temperature. Among the oxide pair examined, the combination of CdO and SnO{sub 2} was best suited for the electrode couple, giving quick and selective response to CO in air at 600 C. The 90% response and the 90% recovery times of the sensor to 200 ppm CO was as short as ca. 8 and 10 s, respectively, at 600 C. The EMF value was linearly related with the logarithm of CO concentration in the range of 20 to 4,000 ppm. Moreover, the cross-sensitivities to other gases, such as H{sub 2}, NO, NO{sub 2}, CO{sub 2}, O{sub 2}, and H{sub 2}O, were small or insignificant.

  6. Acetaldehyde as an intermediate in the electroreduction of carbon monoxide to ethanol on oxide-derived copper

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Bertheussen, Erlend; Verdaguer-Casadevall, Arnau; Ravasio, Davide; Montoya, Joseph H.; Trimarco, Daniel B.; Roy, Claudie; Meier, Sebastian; Wendland, Jürgen; Nørskov, Jens K.; Stephens, Ifan E. L.; et al

    2015-12-21

    Oxide-derived copper (OD-Cu) electrodes exhibit unprecedented CO reduction performance towards liquid fuels, producing ethanol and acetate with >50 % Faradaic efficiency at -0.3 V (vs. RHE). By using static headspace-gas chromatography for liquid phase analysis, we identify acetaldehyde as a minor product and key intermediate in the electroreduction of CO to ethanol on OD-Cu electrodes. Acetaldehyde is produced with a Faradaic efficiency of ≈5 % at -0.33 V (vs. RHE). We show that acetaldehyde forms at low steady-state concentrations, and that free acetaldehyde is difficult to detect in alkaline solutions using NMR spectroscopy, requiring alternative methods for detection and quantification.more » Our results indicate an important step towards understanding the CO reduction mechanism on OD-Cu electrodes.« less

  7. Acetaldehyde as an intermediate in the electroreduction of carbon monoxide to ethanol on oxide-derived copper

    SciTech Connect (OSTI)

    Bertheussen, Erlend; Verdaguer-Casadevall, Arnau; Ravasio, Davide; Montoya, Joseph H.; Trimarco, Daniel B.; Roy, Claudie; Meier, Sebastian; Wendland, Jürgen; Nørskov, Jens K.; Stephens, Ifan E. L.; Chorkendorff, Ib

    2015-12-21

    Oxide-derived copper (OD-Cu) electrodes exhibit unprecedented CO reduction performance towards liquid fuels, producing ethanol and acetate with >50 % Faradaic efficiency at -0.3 V (vs. RHE). By using static headspace-gas chromatography for liquid phase analysis, we identify acetaldehyde as a minor product and key intermediate in the electroreduction of CO to ethanol on OD-Cu electrodes. Acetaldehyde is produced with a Faradaic efficiency of ≈5 % at -0.33 V (vs. RHE). We show that acetaldehyde forms at low steady-state concentrations, and that free acetaldehyde is difficult to detect in alkaline solutions using NMR spectroscopy, requiring alternative methods for detection and quantification. Our results indicate an important step towards understanding the CO reduction mechanism on OD-Cu electrodes.

  8. Reduction of Carbon Monoxide. Past Research Summary

    DOE R&D Accomplishments [OSTI]

    Schrock, R. R.

    1982-01-01

    Research programs for the year on the preparation, characterization, and reactions of binuclear tantalum complexes are described. All evidence to date suggest the following of these dimeric molecules: (1) the dimer does not break into monomers under mild conditions; (2) intermolecular hydride exchange is not negligible, but it is slow; (3) intermolecular non-ionic halide exchange is fast; (4) the ends of the dimers can rotate partially with respect to one another. The binuclear tantalum hydride complexes were found to react with carbon monoxide to give a molecule which is the only example of reduction of CO by a transition metal hydride to give a complex containing a CHO ligand. Isonitrides also reacted in a similar manner with dimeric tantalum hydride. (ATT)

  9. Carbon monoxide sensor and method of use thereof

    DOE Patents [OSTI]

    McDaniel; Anthony H. , Medlin; J. Will , Bastasz; Robert J.

    2007-09-04

    Carbon monoxide sensors suitable for use in hydrogen feed streams and methods of use thereof are disclosed. The sensors are palladium metal/insulator/semiconductor (Pd-MIS) sensors which may possess a gate metal layer having uniform, Type 1, or non-uniform, Type 2, film morphology. Type 1 sensors display an increased sensor response in the presence of carbon monoxide while Type 2 sensors display a decreased response to carbon monoxide. The methods and sensors disclosed herein are particularly suitable for use in proton exchange membrane fuel cells (PEMFCs).

  10. Gold-catalyzed synthesis of carbonates and carbamates from carbon monoxide

    SciTech Connect (OSTI)

    Friend, Cynthia M; Madix, Robert J; Xu, Bingjun

    2015-01-20

    The invention provides a method for producing organic carbonates via the reaction of alcohols and carbon monoxide with oxygen adsorbed on a metallic gold or gold alloy catalyst.

  11. The proposed revision to the NAAQS for carbon monoxide and its...

    Office of Scientific and Technical Information (OSTI)

    STANDARDS; CARBON MONOXIDE; BIOLOGICAL EFFECTS; NEW JERSEY; POLLUTION REGULATIONS; AIR POLLUTION; CARDIOVASCULAR DISEASES; HEALTH HAZARDS; PUBLIC HEALTH; SENSITIVITY; CARBON ...

  12. Terpolymerization of ethylene, sulfur dioxide and carbon monoxide

    DOE Patents [OSTI]

    Johnson, Richard; Steinberg, Meyer

    1981-01-01

    This invention relates to a high molecular weight terpolymer of ethylene, sulfur dioxide and carbon monoxide stable to 280.degree. C. and containing as little as 36 mol % ethylene and about 41-51 mol % sulfur dioxide; and to the method of producing said terpolymer by irradiation of a liquid and gaseous mixture of ethylene, sulfur dioxide and carbon monoxide by means of Co-60 gamma rays or an electron beam, at a temperature of about 10.degree.-50.degree. C., and at a pressure of about 140 to 680 atmospheres, to initiate polymerization.

  13. Terpolymerization of ethylene, sulfur dioxide and carbon monoxide

    DOE Patents [OSTI]

    Johnson, R.; Steinberg, M.

    This invention relates to high molecular weight terpolymer of ethylene, sulfur dioxide and carbon monoxide stable to 280/sup 0/C and containing as little as 36 mo1% ethylene and about 41 to 51 mo1% sulfur dioxide, and to the method of producing said terpolymer by irradiation of a liquid and gaseous mixture of ethylene, sulfur dioxide and carbon monoxide by means of Co-60 gamma rays or an electron beam, at a temperature of about 10 to 50/sup 0/C, and at a pressure of about 140 to 680 atmospheres, to initiate polymerization.

  14. Process for producing methane from gas streams containing carbon monoxide and hydrogen

    DOE Patents [OSTI]

    Frost, Albert C.

    1980-01-01

    Carbon monoxide-containing gas streams are passed over a catalyst capable of catalyzing the disproportionation of carbon monoxide so as to deposit a surface layer of active surface carbon on the catalyst essentially without formation of inactive coke thereon. The surface layer is contacted with steam and is thus converted to methane and CO.sub.2, from which a relatively pure methane product may be obtained. While carbon monoxide-containing gas streams having hydrogen or water present therein can be used only the carbon monoxide available after reaction with said hydrogen or water is decomposed to form said active surface carbon. Although hydrogen or water will be converted, partially or completely, to methane that can be utilized in a combustion zone to generate heat for steam production or other energy recovery purposes, said hydrogen is selectively removed from a CO--H.sub.2 -containing feed stream by partial oxidation thereof prior to disproportionation of the CO content of said stream.

  15. Transient control of carbon monoxide with staged PrOx reactors

    SciTech Connect (OSTI)

    Inbody, M. A.; Borup, R. L.; Tafoya, J.

    2002-01-01

    Fuel Processor systems generate hydrogen for fuel cell systems from hydrocarbon fuels such as gasoline for automotive fuel cell systems and natural gas for stationary fuel cell systems. These fuel processor systems must remove any contaminants to levels that won't poison the fuel cell before the outlet hydrogen-rich gas stream can be used by the fuel cell to generate electricity. Carbon monoxide is a contaminant that must be removed to levels of < 100 ppm or < 10 ppm depending on the CO tolerance of the fuel cell. Typically, the last unit operation in a fuel processor is a preferential oxidation reactor or a selective oxidation reactor, which removes CO by oxidizing it to form C02. These are catalytic reactors where the catalyst and operating conditions are selected so that the oxidation rate of the carbon monoxide is higher than the oxidation rate of hydrogen, even though the hydrogen is present at much higher concentrations (> 30%) than carbon monoxide which is present at trace concentrations (< 1%).

  16. Carbon Monoxide Tolerant Electrocatalyst with Low Platinum Loading and a

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Process for its Preparation - Energy Innovation Portal Startup America Startup America Hydrogen and Fuel Cell Hydrogen and Fuel Cell Find More Like This Return to Search Carbon Monoxide Tolerant Electrocatalyst with Low Platinum Loading and a Process for its Preparation Brookhaven National Laboratory Contact BNL About This Technology Publications: PDF Document Publication Pt Submonolayers on Ru Nanoparticles: A Novel Low Pt Loading, High CO Tolerance Fuel Cell Electrocatalyst (173 KB)

  17. A population-based exposure assessment methodology for carbon monoxide: Development of a carbon monoxide passive sampler and occupational dosimeter

    SciTech Connect (OSTI)

    Apte, M.G.

    1997-09-01

    Two devices, an occupational carbon monoxide (CO) dosimeter (LOCD), and an indoor air quality (IAQ) passive sampler were developed for use in population-based CO exposure assessment studies. CO exposure is a serious public health problem in the U.S., causing both morbidity and mortality (lifetime mortality risk approximately 10{sup -4}). Sparse data from population-based CO exposure assessments indicate that approximately 10% of the U.S. population is exposed to CO above the national ambient air quality standard. No CO exposure measurement technology is presently available for affordable population-based CO exposure assessment studies. The LOCD and IAQ Passive Sampler were tested in the laboratory and field. The palladium-molybdenum based CO sensor was designed into a compact diffusion tube sampler that can be worn. Time-weighted-average (TWA) CO exposure of the device is quantified by a simple spectrophotometric measurement. The LOCD and IAQ Passive Sampler were tested over an exposure range of 40 to 700 ppm-hours and 200 to 4200 ppm-hours, respectively. Both devices were capable of measuring precisely (relative standard deviation <20%), with low bias (<10%). The LOCD was screened for interferences by temperature, humidity, and organic and inorganic gases. Temperature effects were small in the range of 10{degrees}C to 30{degrees}C. Humidity effects were low between 20% and 90% RH. Ethylene (200 ppm) caused a positive interference and nitric oxide (50 ppm) caused a negative response without the presence of CO but not with CO.

  18. New analytical reagents for the determination of sulfur dioxide and carbon monoxide

    SciTech Connect (OSTI)

    Trump, E.L.

    1987-01-01

    Four solid reagent methods were developed for the determination of sulfur dioxide in air, and one method was developed to measure carbon monoxide. When applied to filter paper with acetamide as the humectant and 4-phenylcyclohexanone as a bisulfite absorbent, oxohydroxybis(8-hydroxyquinolinyl-) vanadium (V) changes from yellow to black in the presence of sulfur dioxide. The three other methods, also on a filter paper support, utilized the reduction of bromate to bromine which then changed 3-,3'-, 5-,5'-tetramethylbenzidine from yellow to blue, phenothiazine from white to green, and 4-dimethylamino-4'-,4/double prime/-dimethoxytriphenylmethanol from colorless to red-purple. Quantitative measurements were made by reflectance spectroscopy. The method for carbon monoxide involved the use of tetrakis (acetamide-) Pd(II) ditetrafluoroborate, sodium iodate, and leuco crystal violet all together on a filter paper support. Carbon monoxide reduced the Pd(II)-acetamide complex to metallic palladium. The metallic palladium then reduced iodate to hypoiodous acid, HOI, which, in turn, oxidized leuco crystal violet to crystal violet. The crystal violet color was then measured by reflectance.

  19. Transient PrOx carbon monoxide measurement, control, and optimization

    SciTech Connect (OSTI)

    Inbody, M. A.; Borup, R. L.; Tafoya, J.

    2002-01-01

    Fuel processing systems for low temperature polymer electrolyte membrane (PEM) fuel cell systems require control of the carbon monoxide concentration to less than 100 ppm to 10 ppm in the anode feed. Conventional hydrocarbon fuel processors use a water-gas shift (WGS) reactor to react CO with water to form H2 and reduce the CO concentration. The CO conversion is limited by equilibrium at the outlet temperature of the WGS reactor. The WGS outlet CO concentration can range from over 1% to 2000 ppm depending on the system and its operating parameters. At these concentrations, CO poisons low temperature PEM fuel cells and the concentrations needs to be reduced further.

  20. Methanation of gas streams containing carbon monoxide and hydrogen

    DOE Patents [OSTI]

    Frost, Albert C.

    1983-01-01

    Carbon monoxide-containing gas streams having a relatively high concentration of hydrogen are pretreated so as to remove the hydrogen in a recoverable form for use in the second step of a cyclic, essentially two-step process for the production of methane. The thus-treated streams are then passed over a catalyst to deposit a surface layer of active surface carbon thereon essentially without the formation of inactive coke. This active carbon is reacted with said hydrogen removed from the feed gas stream to form methane. The utilization of the CO in the feed gas stream is appreciably increased, enhancing the overall process for the production of relatively pure, low-cost methane from CO-containing waste gas streams.

  1. ZIRCONIA-BASED MIXED POTENTIAL CARBON MONOXIDE/HYDROCARBON SENSORS WITH LANTHANUM MAGNESIUM OXIDE, AND TERBIUM-DOPED YTTRIUM STABILIZED ZIRCONIA ELECTRODES

    SciTech Connect (OSTI)

    E. L. BROSHA; R. MUKUNDAN; ET AL

    2000-10-01

    We have investigated the performance of dual metal oxide electrode mixed potential sensors in an engine-out, dynamometer environment. Sensors were fabricated by sputtering thin films of LaMnO{sub 3} and Tb-doped YSZ onto YSZ electrolyte. Au gauze held onto the metal oxide thin films with Au ink was used for current collection. The exhaust gas from a 4.8L, V8 engine operated in open loop, steady-state mode around stoichiometry at 1500 RPM and 50 Nm. The sensor showed a stable EMF response (with no hysteresis) to varying concentrations of total exhaust gas HC content. The sensor response was measured at 620 and 670 C and shows temperature behavior characteristic of mixed potential-type sensors. The results of these engine-dynamometer tests are encouraging; however, the limitations associated with Au current collection present the biggest impediment to automotive use.

  2. The effect of carbon monoxide on planetary haze formation

    SciTech Connect (OSTI)

    Hörst, S. M.; Tolbert, M. A

    2014-01-20

    Organic haze plays a key role in many planetary processes ranging from influencing the radiation budget of an atmosphere to serving as a source of prebiotic molecules on the surface. Numerous experiments have investigated the aerosols produced by exposing mixtures of N{sub 2}/CH{sub 4} to a variety of energy sources. However, many N{sub 2}/CH{sub 4} atmospheres in both our solar system and extrasolar planetary systems also contain carbon monoxide (CO). We have conducted a series of atmosphere simulation experiments to investigate the effect of CO on the formation and particle size of planetary haze analogues for a range of CO mixing ratios using two different energy sources, spark discharge and UV. We find that CO strongly affects both number density and particle size of the aerosols produced in our experiments and indicates that CO may play an important, previously unexplored, role in aerosol chemistry in planetary atmospheres.

  3. Cyclic process for producing methane from carbon monoxide with heat removal

    DOE Patents [OSTI]

    Frost, Albert C.; Yang, Chang-lee

    1982-01-01

    Carbon monoxide-containing gas streams are converted to methane by a cyclic, essentially two-step process in which said carbon monoxide is disproportionated to form carbon dioxide and active surface carbon deposited on the surface of a catalyst, and said carbon is reacted with steam to form product methane and by-product carbon dioxide. The exothermic heat of reaction generated in each step is effectively removed during each complete cycle so as to avoid a build up of heat from cycle-to-cycle, with particularly advantageous techniques being employed for fixed bed, tubular and fluidized bed reactor operations.

  4. Production of carbon monoxide-free hydrogen and helium from a high-purity source

    DOE Patents [OSTI]

    Golden, Timothy Christopher; Farris, Thomas Stephen

    2008-11-18

    The invention provides vacuum swing adsorption processes that produce an essentially carbon monoxide-free hydrogen or helium gas stream from, respectively, a high-purity (e.g., pipeline grade) hydrogen or helium gas stream using one or two adsorber beds. By using physical adsorbents with high heats of nitrogen adsorption, intermediate heats of carbon monoxide adsorption, and low heats of hydrogen and helium adsorption, and by using vacuum purging and high feed stream pressures (e.g., pressures of as high as around 1,000 bar), pipeline grade hydrogen or helium can purified to produce essentially carbon monoxide -free hydrogen and helium, or carbon monoxide, nitrogen, and methane-free hydrogen and helium.

  5. Carbon monoxide inhalation increases microparticles causing vascular and CNS dysfunction

    SciTech Connect (OSTI)

    Xu, Jiajun; Yang, Ming; Kosterin, Paul; Salzberg, Brian M.; Milovanova, Tatyana N.; Bhopale, Veena M.; Thom, Stephen R.

    2013-12-01

    We hypothesized that circulating microparticles (MPs) play a role in pro-inflammatory effects associated with carbon monoxide (CO) inhalation. Mice exposed for 1 h to 100 ppm CO or more exhibit increases in circulating MPs derived from a variety of vascular cells as well as neutrophil activation. Tissue injury was quantified as 2000 kDa dextran leakage from vessels and as neutrophil sequestration in the brain and skeletal muscle; and central nervous system nerve dysfunction was documented as broadening of the neurohypophysial action potential (AP). Indices of injury occurred following exposures to 1000 ppm for 1 h or to 1000 ppm for 40 min followed by 3000 ppm for 20 min. MPs were implicated in causing injuries because infusing the surfactant MP lytic agent, polyethylene glycol telomere B (PEGtB) abrogated elevations in MPs, vascular leak, neutrophil sequestration and AP prolongation. These manifestations of tissue injury also did not occur in mice lacking myeloperoxidase. Vascular leakage and AP prolongation were produced in nave mice infused with MPs that had been obtained from CO poisoned mice, but this did not occur with MPs obtained from control mice. We conclude that CO poisoning triggers elevations of MPs that activate neutrophils which subsequently cause tissue injuries. - Highlights: Circulating microparticles (MPs) increase in mice exposed to 100 ppm CO or more. MPs are lysed by infusing the surfactant polyethylene glycol telomere B. CO-induced MPs cause neutrophil activation, vascular leak and CNS dysfunction. Similar tissue injuries do not arise with MPs obtained from air-exposed, control mice.

  6. Heterologous production of an energy-conserving carbon monoxide dehydrogenase complex in the hyperthermophile Pyrococcus furiosus

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Schut, Gerrit J.; Lipscomb, Gina L.; Nguyen, Diep M. N.; Kelly, Robert M.; Adams, Michael W. W.

    2016-01-29

    In this study, carbon monoxide (CO) is an important intermediate in anaerobic carbon fixation pathways in acetogenesis and methanogenesis. In addition, some anaerobes can utilize CO as an energy source. In the hyperthermophilic archaeon Thermococcus onnurineus, which grows optimally at 80°C, CO oxidation and energy conservation is accomplished by a respiratory complex encoded by a 16-gene cluster containing a CO dehydrogenase, a membrane-bound [NiFe]-hydrogenase and a Na+/H+ antiporter module. This complex oxidizes CO, evolves CO2 and H2, and generates a Na+ motive force that is used to conserve energy by a Na+-dependent ATP synthase. Herein we used a bacterial artificialmore » chromosome to insert the 13.2 kb gene cluster encoding the CO-oxidizing respiratory complex of T. onnurineus into the genome of the heterotrophic archaeon, Pyrococcus furiosus, which grows optimally at 100° C. P. furiosus is normally unable to utilize CO, however, the recombinant strain readily oxidized CO and generated H2 at 80° C. Moreover, CO also served as an energy source and allowed the P. furiosus strain to grow with a limiting concentration of sugar or with peptides as the carbon source. Moreover, CO oxidation by P. furiosus was also coupled to the re-utilization, presumably for biosynthesis, of acetate generated by fermentation. The functional transfer of CO utilization between Thermococcus and Pyrococcus species demonstrated herein is representative of the horizontal gene transfer of an environmentally relevant metabolic capability. The transfer of CO utilizing, hydrogen-producing genetic modules also has applications for biohydrogen production and a CO-based industrial platform for various thermophilic organisms.« less

  7. New clean fuel from coal -- Direct dimethyl ether synthesis from hydrogen and carbon monoxide

    SciTech Connect (OSTI)

    Ogawa, T.; Ono, M.; Mizuguchi, M.; Tomura, K.; Shikada, T.; Ohono, Y.; Fujimoto, K.

    1997-12-31

    Dimethyl ether (DME), which has similar physical properties to propane and is easily liquefied at low pressure, has a significant possibility as a clean and non-toxic fuel from coal or coal bed methane. Equilibrium calculation also shows a big advantage of high carbon monoxide conversion of DME synthesis compared to methanol synthesis. By using a 50 kg/day DME bench scale test plant, direct synthesis of DME from hydrogen and carbon monoxide has been studied with newly developed catalysts which are very fine particles. This test plant features a high pressure three-phase slurry reactor and low temperature DME separator. DME is synthesized at temperatures around 533--553 K and at pressures around 3--5 MPa. According to the reaction stoichiometry, the same amount of hydrogen and carbon monoxide react to DME and carbon dioxide. Carbon conversion to DME is one third and the rest of carbon is converted to carbon dioxide. As a result of the experiments, make-up CO conversion is 35--50% on an once-through basis, which is extremely high compared to that of methanol synthesis from hydrogen and carbon monoxide. DME selectivity is around 60 c-mol %. Most of the by-product is CO{sub 2} with a small amount of methanol and water. No heavy by-products have been recognized. Effluent from the reactor is finally cooled to 233--253 K in a DME separator and liquid DME is recovered as a product.

  8. Substantially isotactic, linear, alternating copolymers of carbon monoxide and an olefin

    DOE Patents [OSTI]

    Sen, Ayusman; Jiang, Zhaozhong

    1996-01-01

    The compound, [Pd(Me-DUPHOS)(MeCN).sub.2 ](BF.sub.4).sub.2, [Me-DUPHOS: 1,2-bis(2,5-dimethylphospholano)benzene] is an effective catalyst for the highly enantioselective, alternating copolymerization of olefins, such as aliphatic .alpha.-olefins, with carbon monoxide to form optically active, isotactic polymers which can serve as excellent starting materials for the synthesis of other classes of chiral polymers. For example, the complete reduction of a propylene-carbon monoxide copolymer resulted in the formation of a novel, optically active poly(1,4-alcohol). Also, the previously described catalyst is a catalyst for the novel alternating isomerization cooligomerization of 2-butene with carbon monoxide to form optically active, isotactic poly(1,5-ketone)

  9. Substantially isotactic, linear, alternating copolymers of carbon monoxide and an olefin

    DOE Patents [OSTI]

    Sen, A.; Jiang, Z.

    1996-05-28

    The compound, [Pd(Me-DUPHOS)(MeCN){sub 2}](BF{sub 4}){sub 2}, [Me-DUPHOS: 1,2-bis(2,5-dimethylphospholano)benzene] is an effective catalyst for the highly enantioselective, alternating copolymerization of olefins, such as aliphatic {alpha}-olefins, with carbon monoxide to form optically active, isotactic polymers which can serve as excellent starting materials for the synthesis of other classes of chiral polymers. For example, the complete reduction of a propylene-carbon monoxide copolymer resulted in the formation of a novel, optically active poly(1,4-alcohol). Also, the previously described catalyst is a catalyst for the novel alternating isomerization cooligomerization of 2-butene with carbon monoxide to form optically active, isotactic poly(1,5-ketone).

  10. Generation and Solid Oxide Fuel Cell Carbon Sequestration in Northwest Indiana

    SciTech Connect (OSTI)

    Kevin Peavey; Norm Bessette

    2007-09-30

    The objective of the project is to develop the technology capable of capturing all carbon monoxide and carbon dioxide from natural gas fueled Solid Oxide Fuel Cell (SOFC) system. In addition, the technology to electrochemically oxidize any remaining carbon monoxide to carbon dioxide will be developed. Success of this R&D program would allow for the generation of electrical power and thermal power from a fossil fuel driven SOFC system without the carbon emissions resulting from any other fossil fueled power generationg system.

  11. Molten metal reactor and method of forming hydrogen, carbon monoxide and carbon dioxide using the molten alkaline metal reactor

    DOE Patents [OSTI]

    Bingham, Dennis N.; Klingler, Kerry M.; Turner, Terry D.; Wilding, Bruce M.

    2012-11-13

    A molten metal reactor for converting a carbon material and steam into a gas comprising hydrogen, carbon monoxide, and carbon dioxide is disclosed. The reactor includes an interior crucible having a portion contained within an exterior crucible. The interior crucible includes an inlet and an outlet; the outlet leads to the exterior crucible and may comprise a diffuser. The exterior crucible may contain a molten alkaline metal compound. Contained between the exterior crucible and the interior crucible is at least one baffle.

  12. Genome Annotation Provides Insight into Carbon Monoxide and Hydrogen Metabolism in Rubrivivax gelatinosus

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Wawrousek, Karen; Noble, Scott; Korlach, Jonas; Chen, Jin; Eckert, Carrie; Yu, Jianping; Maness, Pin-Ching

    2014-12-05

    In this article, we report here the sequencing and analysis of the genome of the purple non-sulfur photosynthetic bacterium Rubrivivax gelatinosus CBS. This microbe is a model for studies of its carboxydotrophic life style under anaerobic condition, based on its ability to utilize carbon monoxide (CO) as the sole carbon substrate and water as the electron acceptor, yielding CO2 and H2 as the end products. The CO-oxidation reaction is known to be catalyzed by two enzyme complexes, the CO dehydrogenase and hydrogenase. As expected, analysis of the genome of Rx. gelatinosus CBS reveals the presence of genes encoding both enzymemore » complexes. The CO-oxidation reaction is CO-inducible, which is consistent with the presence of two putative CO-sensing transcription factors in its genome. Genome analysis also reveals the presence of two additional hydrogenases, an uptake hydrogenase that liberates the electrons in H2 in support of cell growth, and a regulatory hydrogenase that senses H2 and relays the signal to a two-component system that ultimately controls synthesis of the uptake hydrogenase. The genome also contains two sets of hydrogenase maturation genes which are known to assemble the catalytic metallocluster of the hydrogenase NiFe active site. Finally and collectively, the genome sequence and analysis information reveals the blueprint of an intricate network of signal transduction pathways and its underlying regulation that enables Rx. gelatinosus CBS to thrive on CO or H2 in support of cell growth.« less

  13. In situ gasification process for producing product gas enriched in carbon monoxide and hydrogen

    DOE Patents [OSTI]

    Capp, John P.; Bissett, Larry A.

    1978-01-01

    The present invention is directed to an in situ coal gasification process wherein the combustion zone within the underground coal bed is fed with air at increasing pressure to increase pressure and temperature in the combustion zone for forcing product gases and water naturally present in the coal bed into the coal bed surrounding the combustion zone. No outflow of combustion products occurs during the build-up of pressure and temperature in the combustion zone. After the coal bed reaches a temperature of about 2000.degree. F and a pressure in the range of about 100-200 psi above pore pressure the airflow is terminated and the outflow of the combustion products from the combustion zone is initiated. The CO.sub.2 containing gaseous products and the water bleed back into the combustion zone to react endothermically with the hot carbon of the combustion zone to produce a burnable gas with a relatively high hydrogen and carbon monoxide content. About 11 to 29 percent of the gas recovered from the combustion zone is carbon monoxide which is considerably better than the 4 to 10 percent carbon monoxide obtained by employing previously known coal gasification techniques.

  14. Effects on carbon monoxide levels in mobile homes using unvented kerosene heaters for residential heating

    SciTech Connect (OSTI)

    Williams, R.; Walsh, D.; White, J.; Jackson, M.; Mumford, J.

    1992-01-01

    Carbon monoxide (CO) emission levels were continuously monitored in 8 mobile trailer homes less than 10 years old. These homes were monitored in an US EPA study on indoor air quality as affected by unvented portable kerosene heaters. Respondents were asked to operate their heaters in a normal fashion. CO, air exchange and temperature values were measured during the study in each home. Results indicate that consumers using unvented kerosene heaters may be unknowingly exposed to high CO levels without taking proper precautions.

  15. Thermal device and method for production of carbon monoxide and hydrogen by thermal dissociation of hydrocarbon gases

    DOE Patents [OSTI]

    Detering, Brent A.; Kong, Peter C.

    2001-01-01

    Carbon monoxide is produced in a fast quench reactor. The production of carbon monoxide includes injecting carbon dioxide and some air into a reactor chamber having a high temperature at its inlet and a rapidly expanding a reactant stream, such as a restrictive convergent-divergent nozzle at its outlet end. Carbon dioxide and other reactants such as methane and other low molecular weight hydrocarbons are injected into the reactor chamber. Other gas may be added at different stages in the process to form a desired end product and prevent back reactions. The resulting heated gaseous stream is then rapidly cooled by expansion of the gaseous stream.

  16. Use of hydrogen-free carbon monoxide with steam in recovery of heavy oil at low temperatures

    SciTech Connect (OSTI)

    Hyne, J. B.; Tyrer, J. D.

    1984-12-11

    A process for recovering oil from a subterranean heavy oil-containing reservoir is provided, wherein steam and carbon monoxide are injected into the reservoir at a temperature less than about 260/sup 0/ C. At these low temperatures, the steam and hydrogen-free carbon monoxide are found to react in the reservoir, by the water gas reaction, to form carbon dioxide and hydrogen. These products both have upgrading effects on the heavy oil, enhancing its quality and producibility. At the low temperatures of the process, gasification and polymerization of the heavy oil are minimized.

  17. Carbon monoxide tolerant electrocatalyst with low platinum loading and a process for its preparation

    DOE Patents [OSTI]

    Adzic, Radoslav; Brankovic, Stanko; Wang, Jia

    2003-12-30

    An electrocatalyst is provided for use in a fuel cell that has low platinum loading and a high tolerance to carbon monoxide poisoning. The fuel cell anode includes an electrocatalyst that has a conductive support material, ruthenium nanoparticles reduced in H.sub.2 and a Group VIII noble metal in an amount of between about 0.1 and 25 wt % of the ruthenium nanoparticles, preferably between about 0.5 and 15 wt %. The preferred Group VIII noble metal is platinum. In one embodiment, the anode can also have a perfluorinated polymer membrane on its surface.

  18. An overview of carbon monoxide generation and release by home appliances

    SciTech Connect (OSTI)

    Batey, J.

    1997-09-01

    Carbon monoxide (CO) is an odorless, colorless and tasteless gas which is highly toxic and can be produced by many combustion sources commonly found within homes. Potential sources include boilers and furnaces, water heaters, space heaters, stoves, ovens, clothes dryers, wood stoves, fireplaces, charcoal grilles, automobiles, cigarettes, oil lamps, and candles. Any fuel that contains carbon can form CO including, natural gas, propane, kerosene, fuel oil, wood, and coal. Exposure to elevated CO levels typically requires its production by a combustion source and its release into the home through a venting system malfunction. The health effects of CO range from headaches and flue-like symptoms to loss of concentration, coma and death depending on the concentration of CO and the exposure time. At levels of only 1%, which is the order of magnitude produced by automobile exhaust, carbon monoxide can cause death in less than 3 minutes. While most combustion equipment operate with low CO levels, many operating factors can contribute to elevated CO levels in the home including: burner adjustment, combustion air supply, house air-tightness, exhaust fan operation, cracked heat exchangers, vent blockages, and flue pipe damage. Test data on CO emissions is presented from a wide range of sources including Brookhaven National Laboratory, Gas Research Institute, American Gas Association, the US Environmental Protection Agency, and the US Consumer Product Safety Commission for many potential CO sources in and near the home.

  19. Process for producing hydrogen and carbonyl sulfide from hydrogen sulfide and carbon monoxide using a heteropolyanionic metal complex catalyst

    SciTech Connect (OSTI)

    Kuch, Ph. L.

    1984-12-18

    Hydrogen and carbonyl sulfide are produced by a process comprising contracting gaseous hydrogen sulfide with gaseous carbon monoxide in the presence of a heteropolymolybdate or tungstate complex. Use of these catalysts reduce the amount of by-product carbon dioxide and methane formation and thus enhance the make of hydrogen and carbonyl sulfide.

  20. Effects of solar radiation on organic matter cycling: Formation of carbon monoxide and carbonyl sulfide (Chapter 11). Book chapter

    SciTech Connect (OSTI)

    Zepp, R.G.

    1994-01-01

    The effects of photoinduced processes on carbon cycling and the biospheric emission of two important trace carbon gases--carbon monoxide and carbonyl sulfide--are examined. Both of these gases are likely to play an important role in the biospheric feedbacks that may reinforce or attenuate future changes in climate. Evidence is presented to support the hypothesis that a significant fraction of the global sources of both of these gases derives from the photochemical fragmentation of decayed plant materials and other biogenic organic matter in terrestrial and marine environments.

  1. Oxygen isotope fractionation in the vacuum ultraviolet photodissociation of carbon monoxide: Wavelength, pressure and temperature dependency.

    SciTech Connect (OSTI)

    Chakraborty, Subrata; Davis, Ryan; Ahmed, Musahid; Jackson, Teresa L.; Thiemens, Mark H.

    2012-01-03

    Several absorption bands exist in the VUV region of Carbon monoxide (CO). Emission spectra indicate that these bands are all predissociative. An experimental investigation of CO photodissociation by vacuum ultraviolet photons (90 to 108 nm; ~13 to 11 eV) from the Advanced Light Source Synchrotron and direct measurement of the associated oxygen isotopic composition of the products are presented here. A wavelength dependency of the oxygen isotopic composition in the photodissociation product was observed. Slope values (δ'{sup 18}O/ δ'{sup 17}O) ranging from 0.76 to 1.32 were observed in oxygen three-isotope space (δ'{sup 18}O vs. δ'{sup 17}O) which correlated with increasing synchrotron photon energy, and indicate a dependency of the upper electronic state specific dissociation dynamics (e.g., perturbation and coupling associated with a particular state). An unprecedented magnitude in isotope separation was observed for photodissociation at the 105 and 107 nm synchrotron bands and are found to be associated with accidental predissociation of the vibrational states ({nu} = 0 and 1) of the upper electronic state E{sup 1}Π. For each synchrotron band, a large (few hundred per mil) extent of isotopic fractionation was observed and the range of fractionation is a combination of column density and exposure time. A significant temperature dependency in oxygen isotopic fractionation was observed, indicating a rotational level dependency in the predissociation process.

  2. Relationship of respiratory symptoms and pulmonary function to tar, nicotine, and carbon monoxide yield of cigarettes

    SciTech Connect (OSTI)

    Krzyzanowski, M.; Sherrill, D.L.; Paoletti, P.; Lebowitz, M.D. )

    1991-02-01

    The data from consecutive surveys of the Tucson Epidemiologic Study (1981-1988) were used to evaluate the relationship in cigarette smokers of respiratory symptoms and pulmonary function to tar, nicotine, and carbon monoxide (CO) yields of the cigarette. There were 690 subjects who reported smoking regularly in at least one survey, over age 15. After adjustment for intensity and duration of smoking and for depth of inhalation, the risk of chronic phlegm, cough, and dyspnea were not related to the tar and nicotine yields. In 414 subjects with pulmonary function tested in at least one of the three surveys the spirometric indices used were significantly related to the daily dose of tar, nicotine, and CO (product of the cigarette yield and daily number of cigarettes smoked). The effects were more pronounced for past than for current doses. However, the differentiation of pulmonary function due to various yields of cigarettes was small in comparison to the difference in pulmonary function between smokers and nonsmokers.

  3. SOFT X-RAY IRRADIATION OF PURE CARBON MONOXIDE INTERSTELLAR ICE ANALOGUES

    SciTech Connect (OSTI)

    Ciaravella, A.; Candia, R.; Collura, A.; Jimenez-Escobar, A.; Munoz Caro, G. M.; Cecchi-Pestellini, C.; Giarrusso, S.; Barbera, M.

    2012-02-10

    There is an increasing evidence for the existence of large organic molecules in the interstellar and circumstellar medium. Very few among such species are readily formed in conventional gas-phase chemistry under typical conditions of interstellar clouds. Attention has therefore focused on interstellar ices as a potential source of these relatively complex species. Laboratory experiments show that irradiation of interstellar ice analogues by fast particles or ultraviolet radiation can induce significant chemical complexity. However, stars are sources of intense X-rays at almost every stage of their formation and evolution. Such radiation may thus provide chemical changes in regions where ultraviolet radiation is severely inhibited. After H{sub 2}O, CO is often the most abundant component of icy grain mantles in dense interstellar clouds and circumstellar disks. In this work we present irradiation of a pure carbon monoxide ice using a soft X-ray spectrum peaked at 0.3 keV. Analysis of irradiated samples shows formation of CO{sub 2}, C{sub 2}O, C{sub 3}O{sub 2}, C{sub 3}, C{sub 4}O, and CO{sub 3}/C{sub 5}. Comparison of X-rays and ultraviolet irradiation experiments, of the same energy dose, shows that X-rays are more efficient than ultraviolet radiation in producing new species. With the exception of CO{sub 2}, X-ray photolysis induces formation of a larger number of products with higher abundances, e.g., C{sub 3}O{sub 2} column density is about one order of magnitude higher in the X-ray experiment. To our knowledge this is the first report on X-ray photolysis of CO ices. The present results show that X-ray irradiation represents an efficient photo-chemical way to convert simple ices to more complex species.

  4. Catalysts for the production of hydrocarbons from carbon monoxide and water

    DOE Patents [OSTI]

    Sapienza, R.S.; Slegeir, W.A.; Goldberg, R.I.

    1985-11-06

    A method of converting low H/sub 2//CO ratio syngas to carbonaceous products comprising reacting the syngas with water or steam at 200 to 350/sup 0/C in the presence of a metal catalyst supported on zinc oxide. Hydrocarbons are produced with a catalyst selected from cobalt, nickel or ruthenium and alcohols are produced with a catalyst selected from palladium, platinum, ruthenium or copper on the zinc oxide support. The ratio of the reactants are such that for alcohols and saturated hydrocarbons: (2n + 1) greater than or equal to x greater than or equal to O and for olefinic hydrocarbons: 2n greater than or equal to x greater than or equal to O where n is the number of carbon atoms in the product and x is the molar amount of water in the reaction mixture.

  5. Catalysts for the production of hydrocarbons from carbon monoxide and water

    DOE Patents [OSTI]

    Sapienza, Richard S.; Slegeir, William A.; Goldberg, Robert I.

    1987-01-01

    A method of converting low H.sub.2 /CO ratio syngas to carbonaceous products comprising reacting the syngas with water or steam at 200.degree. to 350.degree. C. in the presence of a metal catalyst supported on zinc oxide. Hydrocarbons are produced with a catalyst selected from cobalt, nickel or ruthenium and alcohols are produced with a catalyst selected from palladium, platinium, ruthenium or copper on the zinc oxide support. The ratio of the reactants are such that for alcohols and saturated hydrocarbons: (2n+1).gtoreq.x.gtoreq.O and for olefinic hydrocarbons: 2n.gtoreq.x.gtoreq.O where n is the number of carbon atoms in the product and x is the molar amount of water in the reaction mixture.

  6. Integrated Removal of NOx with Carbon Monoxide as Reductant, and Capture of Mercury in a Low Temperature Selective Catalytic and Adsorptive Reactor

    SciTech Connect (OSTI)

    Neville Pinto; Panagiotis Smirniotis; Stephen Thiel

    2010-08-31

    Coal will likely continue to be a dominant component of power generation in the foreseeable future. This project addresses the issue of environmental compliance for two important pollutants: NO{sub x} and mercury. Integration of emission control units is in principle possible through a Low Temperature Selective Catalytic and Adsorptive Reactor (LTSCAR) in which NO{sub x} removal is achieved in a traditional SCR mode but at low temperature, and, uniquely, using carbon monoxide as a reductant. The capture of mercury is integrated into the same process unit. Such an arrangement would reduce mercury removal costs significantly, and provide improved control for the ultimate disposal of mercury. The work completed in this project demonstrates that the use of CO as a reductant in LTSCR is technically feasible using supported manganese oxide catalysts, that the simultaneous warm-gas capture of elemental and oxidized mercury is technically feasible using both nanostructured chelating adsorbents and ceria-titania-based materials, and that integrated removal of mercury and NO{sub x} is technically feasible using ceria-titania-based materials.

  7. Advanced Oxidation & Stabilization of PAN-Based Carbon Precursor...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Vehicle Technologies Office Merit Review 2015: Advanced Oxidation & Stabilization of PAN-Based Carbon Precursor Fibers Advanced Oxidation & Stabilization of PAN-Based Carbon ...

  8. Process for the production of hydrogen and carbonyl sulfide from hydrogen sulfide and carbon monoxide using a metal boride, nitride, carbide and/or silicide catalyst

    SciTech Connect (OSTI)

    McGuiggan, M.F.; Kuch, P.L.

    1984-05-08

    Hydrogen and carbonyl sulfide are produced by a process comprising contacting gaseous hydrogen sulfide with gaseous carbon monoxide in the presence of a metal boride, carbide, nitride and/or silicide catalyst, such as titanium carbide, vanadium boride, manganese nitride or molybdenum silicide.

  9. Regeneration of sulfated metal oxides and carbonates

    DOE Patents [OSTI]

    Hubble, Bill R.; Siegel, Stanley; Cunningham, Paul T.

    1978-03-28

    Alkali metal or alkaline earth metal carbonates such as calcium carbonate and magnesium carbonate found in dolomite or limestone are employed for removal of sulfur dioxide from combustion exhaust gases. The sulfated carbonates are regenerated to oxides through use of a solid-solid reaction, particularly calcium sulfide with calcium sulfate to form calcium oxide and sulfur dioxide gas. The regeneration is performed by contacting the sulfated material with a reductant gas such as hydrogen within an inert diluent to produce calcium sulfide in mixture with the sulfate under process conditions selected to permit the sulfide-sulfate, solid-state reaction to occur.

  10. On the formation of carbonyl sulfide in the reduction of sulfur dioxide by carbon monoxide on lanthanum oxysulfide catalyst: A study by XPS and TPR/MS

    SciTech Connect (OSTI)

    Lau, N.T.; Fang, M. [Hong Kong Univ. of Science and Technology, Clear Water Bay (Hong Kong). Applied Technology Center] [Hong Kong Univ. of Science and Technology, Clear Water Bay (Hong Kong). Applied Technology Center

    1998-10-25

    Both the X-ray photoelectron spectroscopy (XPS) and temperature-programmed reaction, coupled with mass spectrometry (TPR/MS), are used to study the formation of carbonyl sulfide in the reduction of sulfur dioxide on lanthanum oxysulfide catalyst. It was found that the lattice sulfur of the oxysulfide is released and reacts with carbon monoxide to form carbonyl sulfide when the oxysulfide is heated. The oxysulfide is postulated to form sulfur vacancies at a temperature lower than that for the formation of carbonyl sulfide and atomic sulfur is released in the process. The atomic sulfur can either enter the gas phase and leave the oxysulfide catalyst or react with carbon monoxide to form carbonyl sulfide.

  11. Oxidation catalyst

    DOE Patents [OSTI]

    Ceyer, Sylvia T.; Lahr, David L.

    2010-11-09

    The present invention generally relates to catalyst systems and methods for oxidation of carbon monoxide. The invention involves catalyst compositions which may be advantageously altered by, for example, modification of the catalyst surface to enhance catalyst performance. Catalyst systems of the present invention may be capable of performing the oxidation of carbon monoxide at relatively lower temperatures (e.g., 200 K and below) and at relatively higher reaction rates than known catalysts. Additionally, catalyst systems disclosed herein may be substantially lower in cost than current commercial catalysts. Such catalyst systems may be useful in, for example, catalytic converters, fuel cells, sensors, and the like.

  12. EERE Success Story-Plasma Oxidation of Carbon Fiber Precursor |

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Department of Energy Plasma Oxidation of Carbon Fiber Precursor EERE Success Story-Plasma Oxidation of Carbon Fiber Precursor June 23, 2016 - 1:03pm Addthis Plasma oxidation oven. Photo Courtesy: RMX Technologies Plasma oxidation oven. Photo Courtesy: RMX Technologies Plasma oxidation oven. Photo Courtesy: RMX Technologies 1 aMT Plasma Oxidation With the potential to reduce the weight of vehicle components by up to 60%, carbon fiber composites is one of the most promising lightweight

  13. Advanced Oxidation & Stabilization of PAN-Based Carbon Precursor...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    More Documents & Publications Vehicle Technologies Office Merit Review 2015: Advanced Oxidation & Stabilization of PAN-Based Carbon Precursor Fibers Advanced Oxidation & ...

  14. CATALYZED OXIDATION OF URANIUM IN CARBONATE SOLUTIONS

    DOE Patents [OSTI]

    Clifford, W.E.

    1962-05-29

    A process is given wherein carbonate solutions are employed to leach uranium from ores and the like containing lower valent uranium species by utilizing catalytic amounts of copper in the presence of ammonia therein and simultaneously supplying an oxidizing agent thereto. The catalysis accelerates rate of dissolution and increases recovery of uranium from the ore. (AEC)

  15. Advanced Oxidation & Stabilization of PAN-Based Carbon Precursor...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    More Documents & Publications Advanced Oxidation & Stabilization of PAN-Based Carbon Precursor Fibers Vehicle Technologies Office Merit Review 2015: Advanced ...

  16. Effect of Sodium Sulfide on Ni-Containing Carbon Monoxide Dehydrogenases

    SciTech Connect (OSTI)

    Jian Feng; Paul A. Lindahl

    2004-07-28

    OAK-B135 The structure of the active-site C-cluster in CO dehydrogenase from Carboxythermus hydrogenoformans includes a {mu}{sup 2}-sulfide ion bridged to the Ni and unique Fe, while the same cluster in enzymes from Rhodospirillum rubrum (CODH{sub Rr}) and Moorella thermoacetica (CODH{sub Mt}) lack this ion. This difference was investigated by exploring the effects of sodium sulfide on activity and spectral properties. Sulfide partially inhibited the CO oxidation activity of CODH{sub Rr} and generated a lag prior to steady-state. CODH{sub Mt} was inhibited similarly but without a lag. Adding sulfide to CODH{sub Mt} in the C{sub red1} state caused the g{sub av} = 1.82 EPR signal to decline and new features to appear, including one with g = 1.95, 1.85 and (1.70 or 1.62). Removing sulfide caused the g{sub av} = 1.82 signal to reappear and activity to recover. Sulfide did not affect the g{sub av} = 1.86 signal from the C{sub red2} state. A model was developed in which sulfide binds reversibly to C{sub red1}, inhibiting catalysis. Reducing this adduct causes sulfide to dissociate, C{sub red2} to develop, and activity to recover. Using this model, apparent K{sub I} values are 40 {+-} 10 nM for CODH{sub Rr} and 60 {+-} 30 {micro}M for CODH{sub Mt}. Effects of sulfide are analogous to those of other anions, including the substrate hydroxyl group, suggesting that these ions also bridge the Ni and unique Fe. This proposed arrangement raises the possibility that CO binding labilizes the bridging hydroxyl and increases its nucleophilic tendency towards attacking Ni-bound carbonyl.

  17. THE FAR-ULTRAVIOLET 'CONTINUUM' IN PROTOPLANETARY DISK SYSTEMS. II. CARBON MONOXIDE FOURTH POSITIVE EMISSION AND ABSORPTION

    SciTech Connect (OSTI)

    France, Kevin; Schindhelm, Eric; Burgh, Eric B.; Brown, Alexander; Green, James C.; Herczeg, Gregory J.; Brown, Joanna M.; Harper, Graham M.; Linsky, Jeffrey L.; Yang Hao; Abgrall, Herve; Ardila, David R.; Bergin, Edwin; Bethell, Thomas; Calvet, Nuria; Ingleby, Laura; Espaillat, Catherine; Gregory, Scott G.; Hillenbrand, Lynne A.; Hussain, Gaitee

    2011-06-10

    We exploit the high sensitivity and moderate spectral resolution of the Hubble Space Telescope Cosmic Origins Spectrograph to detect far-ultraviolet (UV) spectral features of carbon monoxide (CO) present in the inner regions of protoplanetary disks for the first time. We present spectra of the classical T Tauri stars HN Tau, RECX-11, and V4046 Sgr, representative of a range of CO radiative processes. HN Tau shows CO bands in absorption against the accretion continuum. The CO absorption most likely arises in warm inner disk gas. We measure a CO column density and rotational excitation temperature of N(CO) = (2 {+-} 1) x 10{sup 17} cm{sup -2} and T{sub rot}(CO) 500 {+-} 200 K for the absorbing gas. We also detect CO A-X band emission in RECX-11 and V4046 Sgr, excited by UV line photons, predominantly H I Ly{alpha}. All three objects show emission from CO bands at {lambda} > 1560 A, which may be excited by a combination of UV photons and collisions with non-thermal electrons. In previous observations these emission processes were not accounted for due to blending with emission from the accretion shock, collisionally excited H{sub 2}, and photo-excited H{sub 2}, all of which appeared as a 'continuum' whose components could not be separated. The CO emission spectrum is strongly dependent upon the shape of the incident stellar Ly{alpha} emission profile. We find CO parameters in the range: N(CO) {approx} 10{sup 18}-10{sup 19} cm{sup -2}, T{sub rot}(CO) {approx}> 300 K for the Ly{alpha}-pumped emission. We combine these results with recent work on photo-excited and collisionally excited H{sub 2} emission, concluding that the observations of UV-emitting CO and H{sub 2} are consistent with a common spatial origin. We suggest that the CO/H{sub 2} ratio ({identical_to} N(CO)/N(H{sub 2})) in the inner disk is {approx}1, a transition between the much lower interstellar value and the higher value observed in solar system comets today, a result that will require future

  18. Metal atom oxidation laser

    DOE Patents [OSTI]

    Jensen, R.J.; Rice, W.W.; Beattie, W.H.

    1975-10-28

    A chemical laser which operates by formation of metal or carbon atoms and reaction of such atoms with a gaseous oxidizer in an optical resonant cavity is described. The lasing species are diatomic or polyatomic in nature and are readily produced by exchange or other abstraction reactions between the metal or carbon atoms and the oxidizer. The lasing molecules may be metal or carbon monohalides or monoxides. (auth)

  19. Metal atom oxidation laser

    DOE Patents [OSTI]

    Jensen, R.J.; Rice, W.W.; Beattie, W.H.

    1975-10-28

    A chemical laser which operates by formation of metal or carbon atoms and reaction of such atoms with a gaseous oxidizer in an optical resonant cavity is described. The lasing species are diatomic or polyatomic in nature and are readily produced by exchange or other abstraction reactions between the metal or carbon atoms and the oxidizer. The lasing molecules may be metal or carbon monohalides or monoxides.

  20. Gas-phase energies of actinide oxides -- an assessment of neutral and cationic monoxides and dioxides from thorium to curium

    SciTech Connect (OSTI)

    Marcalo, Joaquim; Gibson, John K.

    2009-08-10

    An assessment of the gas-phase energetics of neutral and singly and doubly charged cationic actinide monoxides and dioxides of thorium, protactinium, uranium, neptunium, plutonium, americium, and curium is presented. A consistent set of metal-oxygen bond dissociation enthalpies, ionization energies, and enthalpies of formation, including new or revised values, is proposed, mainly based on recent experimental data and on correlations with the electronic energetics of the atoms or cations and with condensed-phase thermochemistry.

  1. Recovery of iron, carbon and zinc from steel plant waste oxides using the AISI-DOE postcombustion smelting technology

    SciTech Connect (OSTI)

    Sarma, B.; Downing, K.B.; Aukrust, E.

    1996-09-01

    This report describes a process to recover steel plant waste oxides to be used in the production of hot metal. The process flowsheet used at the pilot plant. Coal/coke breeze and iron ore pellets/waste oxides are charged into the smelting reactor. The waste oxides are either agglomerated into briquettes (1 inch) using a binder or micro-agglomerated into pellets (1/4 inch) without the use of a binder. The iron oxides dissolve in the slag and are reduced by carbon to produce molten iron. The gangue oxides present in the raw materials report to the slag. Coal charged to the smelter is both the fuel as well as the reductant. Carbon present in the waste oxides is also used as the fuel/reductant resulting in a decrease in the coal requirement. Oxygen is top blown through a central, water-cooled, dual circuit lance. Nitrogen is injected through tuyeres at the bottom of the reactor for stirring purposes. The hot metal and slag produced in the smelting reactor are tapped at regular intervals through a single taphole using a mudgun and drill system. The energy requirements of the process are provided by (i) the combustion of carbon to carbon monoxide, referred to as primary combustion and (ii) the combustion of CO and H{sub 2} to CO{sub 2} and H{sub 2}O, known as postcombustion.

  2. Rapid oxidation/stabilization technique for carbon foams, carbon fibers and C/C composites

    DOE Patents [OSTI]

    Tan, Seng; Tan, Cher-Dip

    2004-05-11

    An enhanced method for the post processing, i.e. oxidation or stabilization, of carbon materials including, but not limited to, carbon foams, carbon fibers, dense carbon-carbon composites, carbon/ceramic and carbon/metal composites, which method requires relatively very short and more effective such processing steps. The introduction of an "oxygen spill over catalyst" into the carbon precursor by blending with the carbon starting material or exposure of the carbon precursor to such a material supplies required oxygen at the atomic level and permits oxidation/stabilization of carbon materials in a fraction of the time and with a fraction of the energy normally required to accomplish such carbon processing steps. Carbon based foams, solids, composites and fiber products made utilizing this method are also described.

  3. Magnesium oxide inserts for the LECO Carbon Analyzer

    SciTech Connect (OSTI)

    Bagaasen, L.M.; Jensen, C.M.

    1991-01-16

    LECO carbon analysis of plutonium metal and plutonium oxide at the Rocky Flats Plant generates several hundred kilograms of high silica residues each year. The plutonium in these residues is difficult and expensive to recover using production dissolution processes. A magnesium oxide (MgO) insert has been developed that significantly lowers the plutonium recovery costs without adversely affecting accuracy of the carbon analysis.

  4. Influence of solid fuel on the carbon-monoxide and nitrogen-oxide emissions on sintering

    SciTech Connect (OSTI)

    M.F. Vitushchenko; N.L. Tatarkin; A.I. Kuznetsov; A.E. Vilkov

    2007-07-01

    Laboratory and industrial research now underway at the sintering plant of AO Mittal Steel Temirtau is focusing on the preparation of fuel of optimal granulometric composition, the replacement of coke fines, and the adaptation of fuel-input technology so as to reduce fuel consumption and toxic emissions without loss of sinter quality.

  5. Method of removing nitrogen monoxide from a nitrogen monoxide-containing gas using a water-soluble iron ion-dithiocarbamate, xanthate or thioxanthate

    DOE Patents [OSTI]

    Liu, David K.; Chang, Shih-Ger

    1989-01-01

    A method of removing nitrogen monoxide from a nitrogen monoxide-containing gas, which method comprises: (a) contacting a nitrogen oxide-containing gas with an aqueous solution of water soluble organic compound-iron ion chelate of the formula: ##STR1## wherein the water-soluble organic compound is selected from compounds of the formula: ##STR2## wherein: R is selected from hydrogen or an organic moiety having at least one polar functional group; Z is selected from oxygen, sulfur, or --N--A wherein N is nitrogen and A is hydrogen or lower alkyl having from one to four carbon atoms; and M is selected from hydrogen, sodium or potassium; and n is 1 or 2, in a contacting zone for a time and at a temperature effective to reduce the nitrogen monoxide. These mixtures are useful to provide an unexpensive method of removing NO from gases, thus reducing atmospheric pollution from flue gases.

  6. Catalysts for low temperature oxidation

    DOE Patents [OSTI]

    Toops, Todd J.; Parks, III, James E.; Bauer, John C.

    2016-03-01

    The invention provides a composite catalyst containing a first component and a second component. The first component contains nanosized gold particles. The second component contains nanosized platinum group metals. The composite catalyst is useful for catalyzing the oxidation of carbon monoxide, hydrocarbons, oxides of nitrogen, and other pollutants at low temperatures.

  7. Thermochemical cyclic system for splitting water and/or carbon dioxide by means of cerium compounds and reactions useful therein

    DOE Patents [OSTI]

    Bamberger, C.E.; Robinson, P.R.

    A thermochemical cyclic process for producing hydrogen from water comprises reacting ceric oxide with monobasic or dibasic alkali metal phosphate to yield a solid reaction product, oxygen and water. The solid reaction product, alkali metal carbonate or bicarbonate, and water, are reacted to yield hydrogen, ceric oxide, carbon dioxide and trialkali metal phosphate. Ceric oxide is recycled. Trialkali metal phosphate, carbon dioxide and water are reacted to yield monobasic or dibasic alkali metal phosphate and alkali metal bicarbonate, which are recycled. The cyclic process can be modified for producing carbon monoxide from carbon dioxide by reacting the alkali metal cerous phosphate and alkali metal carbonate or bicarbonate in the absence of water to produce carbon monoxide, ceric oxide, carbon dioxide and trialkali metal phosphate. Carbon monoxide can be converted to hydrogen by the water gas shift reaction.

  8. Thermochemical cyclic system for splitting water and/or carbon dioxide by means of cerium compounds and reactions useful therein

    DOE Patents [OSTI]

    Bamberger, Carlos E.; Robinson, Paul R.

    1980-01-01

    A thermochemical cyclic process for producing hydrogen from water comprises reacting ceric oxide with monobasic or dibasic alkali metal phosphate to yield a solid reaction product, oxygen and water. The solid reaction product, alkali metal carbonate or bicarbonate, and water, are reacted to yield hydrogen, ceric oxide, carbon dioxide and trialkali metal phosphate. Ceric oxide is recycled. Trialkali metal phosphate, carbon dioxide and water are reacted to yield monobasic or dibasic alkali metal phosphate and alkali metal bicarbonate, which are recycled. The cylic process can be modified for producing carbon monoxide from carbon dioxide by reacting the alkali metal cerous phosphate and alkali metal carbonate or bicarbonate in the absence of water to produce carbon monoxide, ceric oxide, carbon dioxide and trialkali metal phosphate. Carbon monoxide can be converted to hydrogen by the water gas shift reaction.

  9. Preparation of olefins from synthesis gas using ruthenium supported on ceric oxide

    DOE Patents [OSTI]

    Pierantozzi, R.

    1985-04-09

    A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

  10. Ruthenium carbonyl catalyst supported on ceric oxide for preparation of olefins from synthesis gas

    DOE Patents [OSTI]

    Pierantozzi, R.

    1985-04-02

    A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

  11. Preparation of olefins from synthesis gas using ruthenium supported on ceric oxide

    DOE Patents [OSTI]

    Pierantozzi, Ronald

    1985-01-01

    A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

  12. Ruthenium carbonyl catalyst supported on ceric oxide for preparation of olefins from synthesis gas

    DOE Patents [OSTI]

    Pierantozzi, Ronald

    1985-01-01

    A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

  13. Catalytic oxidation of hydrocarbons and alcohols by carbon dioxide on oxide catalysts

    SciTech Connect (OSTI)

    Krylov, O.V. . N.N. Semenov Inst. of Chemical Physics); Mamedov, A.Kh.; Mirzabekova, S.R. . Yu.G. Mamedaliev Inst. of Petrochemical Processes)

    1995-02-01

    The great interest displayed lately in heterogeneous catalytic reactions of carbon dioxide is caused by two reasons: (1) the necessity to fight the greenhouse effect and (2) the exhaust of carbon raw material sources. Reactions of oxidative transformation of organic compounds of different classes (alkanes, alkenes, and alcohols) with a nontraditional oxidant, carbon dioxide, were studied on oxide catalysts Fe-O, Cr-O, Mn-O and on multicomponent systems based on manganese oxide. The supported manganese oxide catalysts are active, selective, and stable in conversion of the CH[sub 4] + CO[sub 2] mixture into synthesis gas and in oxidative dehydrogenation of C[sub 2] [minus] C[sub 7] hydrocarbons and the lower alcohols. Unlike metal catalysts manganese oxide based catalysts do not form a carbon layer during the reaction.

  14. Growth of tungsten oxide on carbon nanowalls templates

    SciTech Connect (OSTI)

    Wang, Hua; Su, Yan; Chen, Shuo; Quan, Xie

    2013-03-15

    Highlights: ? Tungsten oxide deposited on carbon nanowalls by hot filament chemical vapor deposition technique. ? This composite has two-dimensional uniform morphology with a crystalline structure of monoclinic tungsten trioxide. ? Surface photoelectric voltage measurements show that this product has photoresponse properties. - Abstract: In the present work we present a simple approach for coupling tungsten oxide with carbon nanowalls. The two-dimensional carbon nanowalls with open boundaries were grown using plasma enhanced hot filament chemical vapor deposition, and the subsequent tungsten oxide growth was performed in the same equipment by direct heating of a tungsten filament. The tungsten oxide coating is found to have uniform morphology with a crystalline structure of monoclinic tungsten trioxide. Surface photoelectric voltage measurements show that this product has photoresponse properties. The method of synthesis described here provides an operable route to the production of two-dimensional tungsten oxide nanocomposites.

  15. Thief carbon catalyst for oxidation of mercury in effluent stream

    DOE Patents [OSTI]

    Granite, Evan J.; Pennline, Henry W.

    2011-12-06

    A catalyst for the oxidation of heavy metal contaminants, especially mercury (Hg), in an effluent stream is presented. The catalyst facilitates removal of mercury through the oxidation of elemental Hg into mercury (II) moieties. The active component of the catalyst is partially combusted coal, or "Thief" carbon, which can be pre-treated with a halogen. An untreated Thief carbon catalyst can be self-promoting in the presence of an effluent gas streams entrained with a halogen.

  16. Formation of ketene (H{sub 2}CCO) in interstellar analogous methane (CH{sub 4})-carbon monoxide (CO) ices: A combined FTIR and reflectron time-of-flight mass spectroscopic study

    SciTech Connect (OSTI)

    Maity, Surajit; Kaiser, Ralf I.; Jones, Brant M.

    2014-07-01

    The formation of ketene (H{sub 2}CCO) in methane-carbon monoxide (CH{sub 4}-CO) ices was investigated upon its exposure to ionizing radiation in the form of energetic electrons at 5.5 K. The radiation-induced nonthermal equilibrium processing of these ices was monitored online and in situ via infrared spectroscopy complimented with post-irradiation temperature programmed desorption studies exploiting highly sensitive reflectron time-of-flight mass spectrometry (ReTOF) coupled with single photon fragment-free photo ionization (PI) at 10.49 eV. The detection of ketene in irradiated (isotopically labeled) methane-carbon monoxide ices was confirmed via the ?{sub 2} infrared absorption band and substantiated during the warm-up phase based on sublimation profiles obtained from the ReTOF-PI spectra of the corresponding isotopic masses. The experiments conducted with the mixed isotopic ices of {sup 12}CD{sub 4}-{sup 13}CO provide clear evidence of the formation of at least two ketene isotopomers (D{sub 2} {sup 12}C{sup 13}CO and D{sub 2} {sup 13}C{sup 13}CO), allowing for the derivation of two competing formation pathways. We have also proposed underlying reaction mechanisms to the formation of ketene based on kinetic fitting of the temporal evolution of the ketene isotopomers.

  17. Visible-Light Photoredox Catalysis: Selective Reduction of Carbon Dioxide to Carbon Monoxide by a Nickel N-Heterocyclic Carbene-Isoquinoline Complex

    SciTech Connect (OSTI)

    Thoi, VanSara; Kornienko, Nick; Margarit, C; Yang, Peidong; Chang, Christopher

    2013-06-07

    The solar-driven reduction of carbon dioxide to value-added chemical fuels is a longstanding challenge in the fields of catalysis, energy science, and green chemistry. In order to develop effective CO2 fixation, several key considerations must be balanced, including (1) catalyst selectivity for promoting CO2 reduction over competing hydrogen generation from proton reduction, (2) visible-light harvesting that matches the solar spectrum, and (3) the use of cheap and earth-abundant catalytic components. In this report, we present the synthesis and characterization of a new family of earth-abundant nickel complexes supported by N-heterocyclic carbene amine ligands that exhibit high selectivity and activity for the electrocatalytic and photocatalytic conversion of CO2 to CO. Systematic changes in the carbene and amine donors of the ligand have been surveyed, and [Ni(Prbimiq1)]2+ (1c, where Prbimiq1 = bis(3-(imidazolyl)isoquinolinyl)propane) emerges as a catalyst for electrochemical reduction of CO2 with the lowest cathodic onset potential (Ecat = 1.2 V vs SCE). Using this earth-abundant catalyst with Ir(ppy)3 (where ppy = 2-phenylpyridine) and an electron donor, we have developed a visible-light photoredox system for the catalytic conversion of CO2 to CO that proceeds with high selectivity and activity and achieves turnover numbers and turnover frequencies reaching 98,000 and 3.9 s1, respectively. Further studies reveal that the overall efficiency of this solar-to-fuel cycle may be limited by the formation of the active Ni catalyst and/or the chemical reduction of CO2 to CO at the reduced nickel center and provide a starting point for improved photoredox systems for sustainable carbon-neutral energy conversion.

  18. Development of carbon-metal oxide supercapacitors from sol-gel derived carbon-ruthenium xerogels

    SciTech Connect (OSTI)

    Lin, C.; Ritter, J.A.; Popov, B.N.

    1999-09-01

    There has been increasing interest in electrochemical capacitors as energy storage systems because of their high power density and long cycle life, compared to battery devices. According to the mechanism of energy storage, there are two types of electrochemical capacitors. One type is based on double layer (dl) formation due to charge separation, and the other type is based on a faradaic process due to redox reactions. Sol-gel derived high surface area carbon-ruthenium xerogels were prepared from carbonized resorcinol-formaldehyde resins containing an electrochemically active form of ruthenium oxide. The electrochemical capacitance of these materials increased with an increase in the ruthenium content indicating the presence of pseudocapacitance associated with the ruthenium oxide undergoing reversible faradaic redox reactions. A specific capacitance of 256 F/g (single electrode) was obtained from a carbon xerogel containing 14 wt% Ru, which corresponded to more than 50% utilization of the ruthenium. The double layer accounted for 40% of this capacitance. This material was also electrochemically stable, showing no change in a cyclic voltammogram for over 2,000 cycles.

  19. Carbon dioxide capture process with regenerable sorbents

    DOE Patents [OSTI]

    Pennline, Henry W.; Hoffman, James S.

    2002-05-14

    A process to remove carbon dioxide from a gas stream using a cross-flow, or a moving-bed reactor. In the reactor the gas contacts an active material that is an alkali-metal compound, such as an alkali-metal carbonate, alkali-metal oxide, or alkali-metal hydroxide; or in the alternative, an alkaline-earth metal compound, such as an alkaline-earth metal carbonate, alkaline-earth metal oxide, or alkaline-earth metal hydroxide. The active material can be used by itself or supported on a substrate of carbon, alumina, silica, titania or aluminosilicate. When the active material is an alkali-metal compound, the carbon-dioxide reacts with the metal compound to generate bicarbonate. When the active material is an alkaline-earth metal, the carbon dioxide reacts with the metal compound to generate carbonate. Spent sorbent containing the bicarbonate or carbonate is moved to a second reactor where it is heated or treated with a reducing agent such as, natural gas, methane, carbon monoxide hydrogen, or a synthesis gas comprising of a combination of carbon monoxide and hydrogen. The heat or reducing agent releases carbon dioxide gas and regenerates the active material for use as the sorbent material in the first reactor. New sorbent may be added to the regenerated sorbent prior to subsequent passes in the carbon dioxide removal reactor.

  20. Quantitative X-ray microanalysis of submicron carbide formation in chromium (III) oxide rich scale

    SciTech Connect (OSTI)

    Collins, W.K.; Ziomek-Moroz, M.; Holcomb, G.R.; Danielson, P.; Hunt, A.H

    2007-08-01

    This paper discusses the chemical microanalysis techniques adapted to identify the precipitates that form on the surface of, or within, the oxide scale of a Fe-22Cr ferritic steel during exposure to a carbon-monoxide rich environment at 750C for 800 hours. Examination of oxidized test coupons revealed the presence of a fiber like structure at the surface, shown in figure 1. Other studies have reported that these structures are carbon precipitates.

  1. Metal oxide coating of carbon supports for supercapacitor applications.

    SciTech Connect (OSTI)

    Boyle, Timothy J.; Tribby, Louis, J; Lakeman, Charles D. E.; Han, Sang M.; Lambert, Timothy N.; Fleig, Patrick F.

    2008-07-01

    The global market for wireless sensor networks in 2010 will be valued close to $10 B, or 200 M units. TPL, Inc. is a small Albuquerque based business that has positioned itself to be a leader in providing uninterruptible power supplies in this growing market with projected revenues expected to exceed $26 M in 5 years. This project focused on improving TPL, Inc.'s patent-pending EnerPak{trademark} device which converts small amounts of energy from the environment (e.g., vibrations, light or temperature differences) into electrical energy that can be used to charge small energy storage devices. A critical component of the EnerPak{trademark} is the supercapacitor that handles high power delivery for wireless communications; however, optimization and miniaturization of this critical component is required. This proposal aimed to produce prototype microsupercapacitors through the integration of novel materials and fabrication processes developed at New Mexico Technology Research Collaborative (NMTRC) member institutions. In particular, we focused on developing novel ruthenium oxide nanomaterials and placed them into carbon supports to significantly increase the energy density of the supercapacitor. These improvements were expected to reduce maintenance costs and expand the utility of the TPL, Inc.'s device, enabling New Mexico to become the leader in the growing global wireless power supply market. By dominating this niche, new customers were expected to be attracted to TPL, Inc. yielding new technical opportunities and increased job opportunities for New Mexico.

  2. Sulfur tolerant molten carbonate fuel cell anode and process

    DOE Patents [OSTI]

    Remick, Robert J.

    1990-01-01

    Molten carbonate fuel cell anodes incorporating a sulfur tolerant carbon monoxide to hydrogen water-gas-shift catalyst provide in situ conversion of carbon monoxide to hydrogen for improved fuel cell operation using fuel gas mixtures of over about 10 volume percent carbon monoxide and up to about 10 ppm hydrogen sulfide.

  3. Carbon nanotube-induced preparation of vanadium oxide nanorods: Application as a catalyst for the partial oxidation of n-butane

    SciTech Connect (OSTI)

    Chen Xiaowei; Zhu Zhenping; Haevecker, Michael; Su Dangsheng . E-mail: dangsheng@fhi-berlin.mpg.de; Schloegl, Robert

    2007-02-15

    A vanadium oxide-carbon nanotube composite was prepared by solution-based hydrolysis of NH{sub 4}VO{sub 3} in the presence of carbon nanotubes. The carbon nanotubes induce the nucleation of the 1D vanadium oxide nanostructures, with the nuclei growing into long freestanding nanorods. The vanadium oxide nanorods with the lengths up to 20 {mu}m and the widths of 5-15 nm exhibit a well-ordered crystalline structure. Catalytic tests show that the composite with nanostructured vanadium oxide is active for the partial oxidation of n-butane to maleic anhydride at 300 deg. C.

  4. Reduction of iron-oxide-carbon composites: part I. Estimation of the rate constants

    SciTech Connect (OSTI)

    Halder, S.; Fruehan, R.J.

    2008-12-15

    A new ironmaking concept using iron-oxide-carbon composite pellets has been proposed, which involves the combination of a rotary hearth furnace (RHF) and an iron bath smelter. This part of the research focuses on studying the two primary chemical kinetic steps. Efforts have been made to experimentally measure the kinetics of the carbon gasification by CO{sub 2} and wustite reduction by CO by isolating them from the influence of heat- and mass-transport steps. A combined reaction model was used to interpret the experimental data and determine the rate constants. Results showed that the reduction is likely to be influenced by the chemical kinetics of both carbon oxidation and wustite reduction at the temperatures of interest. Devolatilized wood-charcoal was observed to be a far more reactive form of carbon in comparison to coal-char. Sintering of the iron-oxide at the high temperatures of interest was found to exert a considerable influence on the reactivity of wustite by virtue of altering the internal pore surface area available for the reaction. Sintering was found to be predominant for highly porous oxides and less of an influence on the denser ores. It was found using an indirect measurement technique that the rate constants for wustite reduction were higher for the porous iron-oxide than dense hematite ore at higher temperatures (> 1423 K). Such an indirect mode of measurement was used to minimize the influence of sintering of the porous oxide at these temperatures.

  5. Method of removing nitrogen monoxide from a nitrogen monoxide-containing gas using a water-soluble iron ion-dithiocarbamate, xanthate or thioxanthate

    DOE Patents [OSTI]

    Liu, D. Kwok-Keung; Chang, Shih-Ger

    1987-08-25

    The present invention relates to a method of removing of nitrogen monoxide from a nitrogen monoxide-containing gas which method comprises contacting a nitrogen oxide-containing gas with an aqueous solution of water soluble organic compound-iron ion chelate complex. The NO absorption efficiency of ferrous urea-dithiocarbamate and ferrous diethanolamine-xanthate as a function of time, oxygen content and solution ph is presented. 3 figs., 1 tab.

  6. Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol

    SciTech Connect (OSTI)

    Massachusetts Institute of Technology; Kroll, Jesse H.; Donahue, Neil M.; Jimenez, Jose L.; Kessler, Sean H.; Canagaratna, Manjula R.; Wilson, Kevin R.; Altieri, Katye E.; Mazzoleni, Lynn R.; Wozniak, Andrew S.; Bluhm, Hendrik; Mysak, Erin R.; Smith, Jared D.; Kolb, Charles E.; Worsnop, Douglas R.

    2010-11-05

    A detailed understanding of the sources, transformations, and fates of organic species in the environment is crucial because of the central roles that organics play in human health, biogeochemical cycles, and Earth's climate. However, such an understanding is hindered by the immense chemical complexity of environmental mixtures of organics; for example, atmospheric organic aerosol consists of at least thousands of individual compounds, all of which likely evolve chemically over their atmospheric lifetimes. Here we demonstrate the utility of describing organic aerosol (and other complex organic mixtures) in terms of average carbon oxidation state (OSC), a quantity that always increases with oxidation, and is readily measured using state-of-the-art analytical techniques. Field and laboratory measurements of OSC , using several such techniques, constrain the chemical properties of the organics and demonstrate that the formation and evolution of organic aerosol involves simultaneous changes to both carbon oxidation state and carbon number (nC).

  7. Photo-oxidation of polymer-like amorphous hydrogenated carbon under visible light illumination

    SciTech Connect (OSTI)

    Baxamusa, Salmaan; Laurence, Ted; Worthington, Matthew; Ehrmann, Paul

    2015-11-10

    Amorphous hydrogenated carbon (a-C:H), a polymer-like network typically synthesized by plasma chemical vapor deposition, has long been understood to exhibit optical absorption of visible light (λ > 400 nm). In this report we explain that this absorption is accompanied by rapid photo-oxidation (within minutes) that behaves in most respects like classic polymer photo-oxidation with the exception that it occurs under visible light illumination rather than ultraviolet illumination.

  8. Photo-oxidation of polymer-like amorphous hydrogenated carbon under visible light illumination

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Baxamusa, Salmaan; Laurence, Ted; Worthington, Matthew; Ehrmann, Paul

    2015-11-10

    Amorphous hydrogenated carbon (a-C:H), a polymer-like network typically synthesized by plasma chemical vapor deposition, has long been understood to exhibit optical absorption of visible light (? > 400 nm). In this report we explain that this absorption is accompanied by rapid photo-oxidation (within minutes) that behaves in most respects like classic polymer photo-oxidation with the exception that it occurs under visible light illumination rather than ultraviolet illumination.

  9. Electrocatalytic Activity of Transition Metal Oxide-Carbon Composites for Oxygen Reduction in Alkaline Batteries and Fuel Cells

    SciTech Connect (OSTI)

    Malkhandi, S; Trinh, P; Manohar, AK; Jayachandrababu, KC; Kindler, A; Prakash, GKS; Narayanan, SR

    2013-06-07

    Conductive transition metal oxides (perovskites, spinels and pyrochlores) are attractive as catalysts for the air electrode in alkaline rechargeable metal-air batteries and fuel cells. We have found that conductive carbon materials when added to transition metal oxides such as calcium-doped lanthanum cobalt oxide, nickel cobalt oxide and calcium-doped lanthanum manganese cobalt oxide increase the electrocatalytic activity of the oxide for oxygen reduction by a factor of five to ten. We have studied rotating ring-disk electrodes coated with (a) various mass ratios of carbon and transition metal oxide, (b) different types of carbon additives and (c) different types of transition metal oxides. Our experiments and analysis establish that in such composite catalysts, carbon is the primary electro- catalyst for the two-electron electro-reduction of oxygen to hydroperoxide while the transition metal oxide decomposes the hydroperoxide to generate additional oxygen that enhances the observed current resulting in an apparent four-electron process. These findings are significant in that they change the way we interpret previous reports in the scientific literature on the electrocatalytic activity of various transition metal oxide- carbon composites for oxygen reduction, especially where carbon is assumed to be an additive that just enhances the electronic conductivity of the oxide catalyst. (C) 2013 The Electrochemical Society. All rights reserved.

  10. Selective Catalytic Oxidation of Hydrogen Sulfide on Activated Carbons Impregnated with Sodium Hydroxide

    SciTech Connect (OSTI)

    Schwartz, Viviane [ORNL; Baskova, Svetlana [ORNL; Armstrong, Timothy R. [ORNL

    2009-01-01

    Two activated carbons of different origin were impregnated with the solution of sodium hydroxide (NaOH) of various concentrations up to 10 wt %, and the effect of impregnation on the catalytic performance of the carbons was evaluated. The catalytic activity was analyzed in terms of the capacity of carbons for hydrogen sulfide (H2S) conversion and removal from hydrogen-rich fuel streams and the emission times of H2S and the products of its oxidation [e.g., sulfur dioxide (SO2) and carbonyl sulfide (COS)]. The results of impregnation showed a significant improvement in the catalytic activity of both carbons proportional to the amount of NaOH introduced. NaOH introduces hydroxyl groups (OH-) on the surface of the activated carbon that increase its surface reactivity and its interaction with sulfur-containing compounds.

  11. Molten carbonate fuel cell cathode with mixed oxide coating

    DOE Patents [OSTI]

    Hilmi, Abdelkader; Yuh, Chao-Yi

    2013-05-07

    A molten carbonate fuel cell cathode having a cathode body and a coating of a mixed oxygen ion conductor materials. The mixed oxygen ion conductor materials are formed from ceria or doped ceria, such as gadolinium doped ceria or yttrium doped ceria. The coating is deposited on the cathode body using a sol-gel process, which utilizes as precursors organometallic compounds, organic and inorganic salts, hydroxides or alkoxides and which uses as the solvent water, organic solvent or a mixture of same.

  12. Oxidation of carbon fiber surfaces for use as reinforcement in high-temperature cementitious material systems

    DOE Patents [OSTI]

    Sugama, Toshifumi.

    1990-05-22

    The interfacial bond characteristics between carbon fiber and a cement matrix, in high temperature fiber-reinforced cementitious composite systems, can be improved by the oxidative treatment of the fiber surfaces. Compositions and the process for producing the compositions are disclosed. 2 figs.

  13. Oxidation of carbon fiber surfaces for use as reinforcement in high-temperature cementitious material systems

    DOE Patents [OSTI]

    Sugama, Toshifumi

    1990-01-01

    The interfacial bond characteristics between carbon fiber and a cement matrix, in high temperature fiber-reinforced cementitious composite systems, can be improved by the oxidative treatment of the fiber surfaces. Compositions and the process for producing the compositions are disclosed.

  14. Multi-stage, isothermal CO preferential oxidation reactor

    SciTech Connect (OSTI)

    Skala, Glenn William; Brundage, Mark A.; Borup, Rodney Lynn; Pettit, William Henry; Stukey, Kevin; Hart-Predmore, David James; Fairchok, Joel

    2000-01-01

    A multi-stage, isothermal, carbon monoxide preferential oxidation (PrOx) reactor comprising a plurality of serially arranged, catalyzed heat exchangers, each separated from the next by a mixing chamber for homogenizing the gases exiting one heat exchanger and entering the next. In a preferred embodiment, at least some of the air used in the PrOx reaction is injected directly into the mixing chamber between the catalyzed heat exchangers.

  15. Simultaneous removal of nitrogen oxides and sulfur oxides from combustion gases

    DOE Patents [OSTI]

    Clay, David T.; Lynn, Scott

    1976-10-19

    A process for the simultaneous removal of sulfur oxides and nitrogen oxides from power plant stack gases comprising contacting the stack gases with a supported iron oxide catalyst/absorbent in the presence of sufficient reducing agent selected from the group consisting of carbon monoxide, hydrogen, and mixtures thereof, to provide a net reducing atmosphere in the SO.sub.x /NO.sub.x removal zone. The sulfur oxides are removed by absorption substantially as iron sulfide, and nitrogen oxides are removed by catalytic reduction to nitrogen and ammonia. The spent iron oxide catalyst/absorbent is regenerated by oxidation and is recycled to the contacting zone. Sulfur dioxide is also produced during regeneration and can be utilized in the production of sulfuric acid and/or sulfur.

  16. Genetics of Bacteria That Oxidize On-Carbon Compounds

    SciTech Connect (OSTI)

    Hanson, Richard S.

    2001-01-01

    Facultative methanol oxidizing bacteria contain large amounts of methanol dehydrogenase which is expressed only in the presence of methanol. This technical report describes two-two component regulatory systems encoding histidine kinases and response regulators and another response regulator all of which are required for the expression of mxaF, the open reading frame encoding methanol dehydrogenase. The response regulators bind to sequences upstream of the mxaF when phosphoryled in a reaction catalyzed by the histidine kinases. The binding of the response regulators is required for the transcription of mxaF.

  17. Preparation and electrochemical properties of multiwalled carbon nanotubes-nickel oxide porous composite for supercapacitors

    SciTech Connect (OSTI)

    Zheng Yanzhen; Zhang Milin . E-mail: dhyzyz@yahoo.com.cn; Gao Peng

    2007-09-04

    Porous nickel oxide/multiwalled carbon nanotubes (NiO/MWNTs) composite material was synthesized using sodium dodecyl phenyl sulfate as a soft template and urea as hydrolysis-controlling agent. Scanning electron microscopy (SEM) results show that the as-prepared nickel oxide nanoflakes aggregate to form a submicron ball shape with a porous structure, and the MWNTs with entangled and cross-linked morphology are well dispersed in the porous nickel oxide. The composite shows an excellent cycle performance at a high current of 2 A g{sup -1} and keeps a capacitance retention of about 89% over 200 charge/discharge cycles. A specific capacitance approximate to 206 F g{sup -1} has been achieved with NiO/MWNTs (10 wt.%) in 2 M KOH electrolyte. The electrical conductivity and the active sites for redox reaction of nickel oxide are significantly improved due to the connection of nickel nanoflakes by the long entangled MWNTs.

  18. Electro-catalytic oxidation device for removing carbon from a fuel reformate

    DOE Patents [OSTI]

    Liu, Di-Jia

    2010-02-23

    An electro-catalytic oxidation device (ECOD) for the removal of contaminates, preferably carbonaceous materials, from an influent comprising an ECOD anode, an ECOD cathode, and an ECOD electrolyte. The ECOD anode is at a temperature whereby the contaminate collects on the surface of the ECOD anode as a buildup. The ECOD anode is electrically connected to the ECOD cathode, which consumes the buildup producing electricity and carbon dioxide. The ECOD anode is porous and chemically active to the electro-catalytic oxidation of the contaminate. The ECOD cathode is exposed to oxygen, and made of a material which promotes the electro-chemical reduction of oxygen to oxidized ions. The ECOD electrolyte is non-permeable to gas, electrically insulating and a conductor to oxidized. The ECOD anode is connected to the fuel reformer and the fuel cell. The ECOD electrolyte is between and in ionic contact with the ECOD anode and the ECOD cathode.

  19. MINIMIZING NET CARBON DIOXIDE EMISSIONS BY OXIDATIVE CO-PYROLYSIS OF COAL/BIOMASS BLENDS

    SciTech Connect (OSTI)

    Robert Hurt; Todd Lang

    2001-06-25

    Solid fuels vary significantly with respect to the amount of CO{sub 2} directly produced per unit heating value. Elemental carbon is notably worse than other solid fuels in this regard, and since carbon (char) is an intermediate product of the combustion of almost all solid fuels, there is an opportunity to reduce specific CO{sub 2} emissions by reconfiguring processes to avoid char combustion wholly or in part. The primary goal of this one-year Innovative Concepts project is to make a fundamental thermodynamic assessment of three modes of solid fuel use: (1) combustion, (2) carbonization, and (3) oxidative pyrolysis, for a wide range of coal and alternative solid fuels. This period a large set of thermodynamic calculations were carried out to assess the potential of the three processes. The results show that the net carbon dioxide emissions and the relative ranking of the different processes depends greatly on the particular baseline fossil fuel being displaced by the new technology. As an example, in a baseline natural gas environment, it is thermodynamically more advantageous to carbonize biomass than to combust it, and even more advantageous to oxidatively pyrolyze the biomass.

  20. Selective decoration of nickel and nickel oxide nanocrystals on multiwalled carbon nanotubes

    SciTech Connect (OSTI)

    Martis, P.; Venugopal, B.R.; Delhalle, J.; Mekhalif, Z.

    2011-05-15

    A simple route to selective decoration of nickel and nickel oxide nanocrystals on multiwalled carbon nanotubes (MWCNTs) using nickel acetylacetonate (NAA) was successfully achieved for the first time. The homogeneously decorated nanocrystals on MWCNTs were investigated for their structure and morphology by various techniques, such as powder X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, field emission scanning electron microscopy and thermogravimetric analysis. It was found that the size distributions of the nanocrystals on MWCNTs ranged from 8 to 15 nm and they were well resolved. The precursor, NAA, was effectively employed to impregnate the MWCNTs, which on calcination at suitable temperatures and in the presence of hydrogen and nitrogen atmosphere gave rise to nickel and nickel oxide nanocrystals, respectively. -- Graphical abstract: Nickel and nickel oxide nanocrystals were selectively and homogeneously decorated on multiwalled carbon nanotubes using nickel acetylacetonate, as a precursor in a simple and efficient route. Display Omitted Highlights: {yields} A simple route for decoration of nickel and nickel oxide nanocrystals on MWCNTs. {yields} Nickel acetylacetonate used as nickel source for the first time to impregnate on MWCNTs. {yields} Selective decoration was achieved by calcination in hydrogen and nitrogen atmospheres. {yields} The as-decorated nickel and nickel oxide nanocrystals are in the range of 8-15 nm.

  1. Catalytic Templating Approaches for Three-Dimensional Hollow Carbon/Graphene Oxide Nano-Architectures

    SciTech Connect (OSTI)

    Moon, Gun-Hee; Shin, Yongsoon; Choi, Daiwon; Arey, Bruce W.; Exarhos, Gregory J.; Wang, Chong M.; Choi, Wonyong; Liu, Jun

    2013-01-01

    We report a catalytic templating method to synthesize well-controlled, three-dimensional (3D) nano-architectures with graphene oxide sheets. The 3D composites are prepared via self-assembly of carbon, GO, and spherical alumina-coated silica (ACS) templates during a catalytic reaction porcess. By changing the GO content, we can systematically tune the architecture from layered composites to 3D hollow structures to microporous materials. The composites show a synergistic effect with significantly superior properties than either pure carbon or r-GO prepared with a significant enhancement to its capacitance at high current density.

  2. Electrical transport characteristics of DNA wrapped carbon nanotubes contacted to palladium and palladium oxide electrodes.

    SciTech Connect (OSTI)

    Dentinger, Paul M.; Leonard, Francois; Jones, Frank Eugene; Talin, Albert Alec

    2005-03-01

    DNA-wrapped carbon nanotubes (DNA-CNT) have generated attention due the ability to disperse cleanly into solution, and by the possibility of sorting nanotubes according to size and conductivity. In order to learn more about the effects of DNA on the electrical transport characteristics of single wall carbon nanotubes, we fabricate and test a series of devices consisting of DNA-wrapped CNTs placed across gold, palladium, and palladium oxide electrodes. In addition, we look at how DNA functionalized CNTs react to presence of hydrogen, which has previously been shown to affect the conductivity of CNTs when in contact with palladium.

  3. ReaxFF Study of the Oxidation of Softwood Lignin in View of Carbon Fiber Production

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Beste, Ariana

    2014-10-06

    We investigate the oxidative, thermal conversion of softwood lignin by performing molecular dynamics simulations based on a reactive force field (ReaxFF). The lignin samples are constructed from coniferyl alcohol units, which are connected through linkages that are randomly selected from a natural distribution of linkages in softwood. The goal of this work is to simulate the oxidative stabilization step during carbon fiber production from lignin precursor. We find that at simulation conditions where stabilization reactions occur, the lignin fragments have already undergone extensive degradation. The 5-5 linkage shows the highest reactivity towards cyclization and dehydrogenation.

  4. ReaxFF Study of the Oxidation of Softwood Lignin in View of Carbon Fiber Production

    SciTech Connect (OSTI)

    Beste, Ariana

    2014-01-01

    We investigate the oxidative, thermal conversion of softwood lignin by performing molecular dynamics simulations based on a reactive force field (ReaxFF). The lignin samples are constructed from coniferyl alcohol units, which are connected through linkages that are randomly selected from a natural distribution of linkages in softwood. The goal of this work is to simulate the oxidative stabilization step during carbon fiber production from lignin precursor. We find that at simulation conditions where stabilization reactions occur, the lignin fragments have already undergone extensive degradation. The 5-5 linkage shows the highest reactivity towards cyclization and dehydrogenation.

  5. Method and apparatus for detecting the presence and thickness of carbon and oxide layers on EUV reflective surfaces

    DOE Patents [OSTI]

    Malinowski, Michael E.

    2005-01-25

    The characteristics of radiation that is reflected from carbon deposits and oxidation formations on highly reflective surfaces such as Mo/Si mirrors can be quantified and employed to detect and measure the presence of such impurities on optics. Specifically, it has been shown that carbon deposits on a Mo/Si multilayer mirror decreases the intensity of reflected HeNe laser (632.8 nm) light. In contrast, oxide layers formed on the mirror should cause an increase in HeNe power reflection. Both static measurements and real-time monitoring of carbon and oxide surface impurities on optical elements in lithography tools should be achievable.

  6. Photochemical Oxidation of Dissolved Elemental Mercury by Carbonate Radicals in Water

    SciTech Connect (OSTI)

    He, Feng; Zhao, Wenrong; Liang, Liyuan; Gu, Baohua

    2014-01-01

    Photochemical oxidation of dissolved elemental mercury [Hg(0)] affects mercury chemical speciation and its transfer at the water-air interface in the aquatic environment. The mechanisms and factors that control Hg(0) photooxidation, however, are not completely understood, especially in natural freshwaters containing dissolved organic matter (DOM) and carbonate. Here, we evaluate Hg(0) photooxidation rates affected by various reactive ionic species [e.g., DOM, HCO3-, NO3-] and free radicals in a creek water and a phosphate buffer solution (pH=8) under simulated solar irradiation. We report a high Hg(0) photooxidation rate (k = 1.44 h-1) in the presence of both HCO3- and NO3-, whereas HCO3-, NO3-, or DOM alone increased the oxidation rate slightly (k = 0.1 0.17 h-1). Using scavengers and enhancers for singlet oxygen (1O2) and hydroxyl (HO ) radicals, as well as electron paramagnetic resonance spectroscopy, we identify that carbonate radicals (CO3 -) primarily drive the Hg(0) photooxidation, whereas addition of DOM resulted in a 2-fold decrease in Hg(0) oxidation. This study identifies an unrecognized pathway of Hg(0) photooxidation by CO3 - radicals and the inhibitory effect of DOM, which could be important in assessing Hg transformation and fate in water containing carbonate such as hard water and seawater.

  7. Photochemical Oxidation of Dissolved Elemental Mercury by Carbonate Radicals in Water

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    He, Feng; Zhao, Weirong; Liang, Liyuan; Gu, Baohua

    2014-11-11

    Photochemical oxidation of dissolved elemental mercury [Hg(0)] affects mercury chemical speciation and its transfer at the water-air interface in the aquatic environment. The mechanisms and factors that control Hg(0) photooxidation, however, are not completely understood, especially in natural freshwaters containing dissolved organic matter (DOM) and carbonate. Here, we evaluate Hg(0) photooxidation rates affected by various reactive ionic species [e.g., DOM, CO32-, NO3-] and free radicals in a creek water and a phosphate buffer solution (pH=8) under simulated solar irradiation. We report a high Hg(0) photooxidation rate (k = 1.44 h-1) in the presence of both HCO32- and NO3-, whereas HCO32-,more » NO3-, or DOM alone increased the oxidation rate slightly (k = 0.1 0.17 h-1). Using scavengers and enhancers for singlet oxygen (1O2) and hydroxyl (HO∙ ) radicals, as well as electron paramagnetic resonance spectroscopy, we identify that carbonate radicals (CO3 ∙-) primarily drive the Hg(0) photooxidation, whereas addition of DOM resulted in a 2-fold decrease in Hg(0) oxidation. This study identifies an unrecognized pathway of Hg(0) photooxidation by CO3 ∙- radicals and the inhibitory effect of DOM, which could be important in assessing Hg transformation and fate in water containing carbonate such as hard water and seawater.« less

  8. A Semi-Empirical Two Step Carbon Corrosion Reaction Model in PEM Fuel Cells

    SciTech Connect (OSTI)

    Young, Alan; Colbow, Vesna; Harvey, David; Rogers, Erin; Wessel, Silvia

    2013-01-01

    The cathode CL of a polymer electrolyte membrane fuel cell (PEMFC) was exposed to high potentials, 1.0 to 1.4 V versus a reversible hydrogen electrode (RHE), that are typically encountered during start up/shut down operation. While both platinum dissolution and carbon corrosion occurred, the carbon corrosion effects were isolated and modeled. The presented model separates the carbon corrosion process into two reaction steps; (1) oxidation of the carbon surface to carbon-oxygen groups, and (2) further corrosion of the oxidized surface to carbon dioxide/monoxide. To oxidize and corrode the cathode catalyst carbon support, the CL was subjected to an accelerated stress test cycled the potential from 0.6 VRHE to an upper potential limit (UPL) ranging from 0.9 to 1.4 VRHE at varying dwell times. The reaction rate constants and specific capacitances of carbon and platinum were fitted by evaluating the double layer capacitance (Cdl) trends. Carbon surface oxidation increased the Cdl due to increased specific capacitance for carbon surfaces with carbon-oxygen groups, while the second corrosion reaction decreased the Cdl due to loss of the overall carbon surface area. The first oxidation step differed between carbon types, while both reaction rate constants were found to have a dependency on UPL, temperature, and gas relative humidity.

  9. Oxidation of activated carbon fibers: Effect on pore size, surface chemistry, and adsorption properties

    SciTech Connect (OSTI)

    Mangun, C.L.; Benak, K.R.; Daley, M.A.; Economy, J.

    1999-12-01

    Activated carbon fibers (ACFs) were oxidized using both aqueous and nonaqueous treatments. As much as 29 wt% oxygen can be incorporated onto the pore surface in the form of phenolic hydroxyl, quinine, and carboxylic acid groups. The effect of oxidation on the pore size, pore volume, and the pore surface chemistry was thoroughly examined. The average micropore size is typically affected very little by aqueous oxidation while the micropore volume and surface area decreases with such a treatment. In contrast, the micropore size and micropore volume both increase with oxidation in air. Oxidation of the fibers produces surface chemistries in the pore that provide for enhanced adsorption of basic (ammonia) and polar (acetone) molecules at ambient and nonambient temperatures. The adsorption capacity of the oxidized fibers for acetone is modestly better than the untreated ACFs while the adsorption capacity for ammonia can increase up to 30 times compared to untreated ACFs. The pore surface chemical makeup was analyzed using elemental analysis, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and X-ray photoelectron spectroscopy (XPS).

  10. Carbon dioxide adsorbents containing magnesium oxide suitable for use at high temperatures

    DOE Patents [OSTI]

    Mayorga, Steven Gerard; Weigel, Scott Jeffrey; Gaffney, Thomas Richard; Brzozowski, Jeffrey Richard

    2001-01-01

    Adsorption of carbon dioxide from gas streams at temperatures in the range of 300 to 500.degree. C. is carried out with a solid adsorbent containing magnesium oxide, preferably promoted with an alkali metal carbonate or bicarbonate so that the atomic ratio of alkali metal to magnesium is in the range of 0.006 to 2.60. Preferred adsorbents are made from the precipitate formed on addition of alkali metal and carbonate ions to an aqueous solution of a magnesium salt. Atomic ratios of alkali metal to magnesium can be adjusted by washing the precipitate with water. Low surface area adsorbents can be made by dehydration and CO.sub.2 removal of magnesium hydroxycarbonate, with or without alkali metal promotion. The process is especially valuable in pressure swing adsorption operations.

  11. Influence of surface oxidation on ion dynamics and capacitance in porous and nonporous carbon electrodes

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Dyatkin, Boris; Zhang, Yu; Mamontov, Eugene; Kolesnikov, Alexander I.; Cheng, Yongqiang; Meyer, III, Harry M.; Cummings, Peter T.; Gogotsi, Yury G.

    2016-04-07

    Here, we investigate the influence of surface chemistry and ion confinement on capacitance and electrosorption dynamics of room-temperature ionic liquids (RTILs) in supercapacitors. Using air oxidation and vacuum annealing, we produced defunctionalized and oxygen-rich surfaces of carbide-derived carbons (CDCs) and graphene nanoplatelets (GNPs). While oxidized surfaces of porous CDCs improve capacitance and rate handling abilities of ions, defunctionalized nonporous GNPs improve charge storage densities on planar electrodes. Quasi-elastic neutron scattering (QENS) and inelastic neutron scattering (INS) probed the structure, dynamics, and orientation of RTIL ions confined in divergently functionalized pores. Oxidized, ionophilic surfaces draw ions closer to pore surfaces andmore » enhance potential-driven ion transport during electrosorption. Molecular dynamics (MD) simulations corroborated experimental data and demonstrated the significance of surface functional groups on ion orientations, accumulation densities, and capacitance.« less

  12. Mechanisms of carbon nanotube-induced toxicity: Focus on oxidative stress

    SciTech Connect (OSTI)

    Shvedova, Anna A.; Pietroiusti, Antonio; Fadeel, Bengt; Kagan, Valerian E.

    2012-06-01

    Nanotechnologies are emerging as highly promising technologies in many sectors in the society. However, the increasing use of engineered nanomaterials also raises concerns about inadvertent exposure to these materials and the potential for adverse effects on human health and the environment. Despite several years of intensive investigations, a common paradigm for the understanding of nanoparticle-induced toxicity remains to be firmly established. Here, the so-called oxidative stress paradigm is scrutinized. Does oxidative stress represent a secondary event resulting inevitably from disruption of biochemical processes and the demise of the cell, or a specific, non-random event that plays a role in the induction of cellular damage e.g. apoptosis? The answer to this question will have important ramifications for the development of strategies for mitigation of adverse effects of nanoparticles. Recent examples of global lipidomics studies of nanoparticle-induced tissue damage are discussed along with proteomics and transcriptomics approaches to achieve a comprehensive understanding of the complex and interrelated molecular changes in cells and tissues exposed to nanoparticles. We also discuss instances of non-oxidative stress-mediated cellular damage resulting from direct physical interference of nanomaterials with cellular structures. -- Highlights: ► CNT induced non-random oxidative stress associated with apoptosis. ► Non-oxidative mechanisms for cellular toxicity of carbon nanotubes. ► Biodegradation of CNT by cells of innate immune system. ► “Omics”-based biomarkers of CNT exposures.

  13. Investigation of coal char-slag transition during oxidation: effect of temperature and residual carbon

    SciTech Connect (OSTI)

    Suhui Li; Kevin J. Whitty

    2009-04-15

    The transition of coal char to molten slag at high conversion was studied for a bituminous coal using a laminar entrained-flow reactor under oxidizing conditions. Post-oxidized char particles were analyzed by various techniques including loss-on-ignition, gas adsorption analysis, and scanning electron microscopy to determine carbon content, internal surface area and pore size distribution, and char morphology, respectively. These analyses provide information concerning the effect of temperature and residual carbon on the transition from porous char to molten slag. Results showed that, at temperatures above the ash flow temperature, the transition from porous char to molten slag occurred at about 90% conversion for the coal used in this study. No transition occurred at temperatures below the ash flow temperature. This finding explains previous observations that there is a coal-dependent critical carbon conversion at which the ash stickiness increases dramatically. This result also indicates that surface area can be used as a criterion for determining the critical conversion of the transition. In addition, it was found that the randomly overlapping pore model cannot be directly applied to predict the surface area evolution of char particles during the transition without considering the reopening of closed micropores during the initial reaction and the ash fusion effect. 33 refs., 9 figs., 2 tabs.

  14. Reduction of iron-oxide-carbon composites: part III. Shrinkage of composite pellets during reduction

    SciTech Connect (OSTI)

    Halder, S.; Fruehan, R.J.

    2008-12-15

    This article involves the evaluation of the volume change of iron-oxide-carbon composite pellets and its implications on reduction kinetics under conditions prevalent in a rotary hearth furnace (RHF) that were simulated in the laboratory. The pellets, in general, were found to shrink considerably during the reduction due to the loss of carbon and oxygen from the system, sintering of the iron-oxide, and formation of a molten slag phase at localized regions inside the pellets due to the presence of binder and coal/wood-charcoal ash at the reduction temperatures. One of the shortcomings of the RHF ironmaking process has been the inability to use multiple layers of composite pellets because of the impediment in heat transport to the lower layers of a multilayer bed. However, pellet shrinkage was found to have a strong effect on the reduction kinetics by virtue of enhancing the external heat transport to the lower layers. The volume change of the different kinds of composite pellets was studied as a function of reduction temperature and time. The estimation of the change in the amount of external heat transport with varying pellet sizes for a particular layer of a multilayer bed was obtained by conducting heat-transfer tests using inert low-carbon steel spheres. It was found that if the pellets of the top layer of the bed shrink by 30 pct, the external heat transfer to the second layer increases by nearly 6 times.

  15. Photochemical oxidation of dissolved elemental mercury by carbonate radicals in water

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    He, Feng; Gu, Baohua; Zhao, Weirong; Liang, Liyuan

    2014-11-11

    In this study, photochemical oxidation of dissolved elemental mercury, Hg(0), affects mercury chemical speciation and its transfer at the water-air interface in the aquatic environment. The mechanisms and factors that control Hg(0) photooxidation, however, are not completely understood, especially concerning the role of dissolved organic matter (DOM) and carbonate (CO32-) in natural freshwaters. Here, we evaluate Hg(0) photooxidation rates affected by reactive ionic species (e.g., DOM, CO32-, and NO3–) and free radicals in creek water and a phosphate buffer solution (pH 8) under simulated solar irradiation. The Hg(0) photooxidation rate (k = 1.44 h-1) is much higher in the presencemore » of both CO32- and NO3- than in the presence of CO32-, NO3-, or DOM alone (k = 0.1–0.17 h-1). Using scavengers and enhancers for singlet oxygen (1O2) and hydroxyl (HO•) radicals, as well as electron paramagnetic resonance spectroscopy, we found that carbonate radicals (CO3•-) primarily drive Hg(0) photooxidation. The addition of DOM to the solution of CO32- and NO3- decreased the oxidation rate by half. This study identifies an unrecognized pathway of Hg(0) photooxidation by CO3•- radicals and the inhibitory effect of DOM, which could be important in assessing Hg transformation and the fate of Hg in water containing carbonate such as hard water and seawater.« less

  16. Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Zhuang, Zhongbin; Giles, Stephen A.; Zheng, Jie; Jenness, Glen R.; Caratzoulas, Stavros; Vlachos, Dionisios G.; Yan, Yushan

    2016-01-14

    The development of a low-cost, high-performance platinum-group-metal-free hydroxide exchange membrane fuel cell is hindered by the lack of a hydrogen oxidation reaction catalyst at the anode. Here we report that a composite catalyst, nickel nanoparticles supported on nitrogen-doped carbon nanotubes, has hydrogen oxidation activity similar to platinum-group metals in alkaline electrolyte. Although nitrogen-doped carbon nanotubes are a very poor hydrogen oxidation catalyst, as a support, it increases the catalytic performance of nickel nanoparticles by a factor of 33 (mass activity) or 21 (exchange current density) relative to unsupported nickel nanoparticles. Density functional theory calculations indicate that the nitrogen-doped support stabilizesmore » the nanoparticle against reconstruction, while nitrogen located at the edge of the nanoparticle tunes local adsorption sites by affecting the d-orbitals of nickel. Here, owing to its high activity and low cost, our catalyst shows significant potential for use in low-cost, high-performance fuel cells.« less

  17. Modeling the Impact of Carbon Dioxide Leakage into an Unconfined, Oxidizing Carbonate Aquifer

    SciTech Connect (OSTI)

    Bacon, Diana H.; Qafoku, Nikolla; Dai, Zhenxue; Keating, Elizabeth; Brown, Christopher F.

    2016-01-01

    Multiphase, reactive transport modeling was used to identify the mechanisms controlling trace metal release under elevated CO2 conditions from a well-characterized carbonate aquifer. Modeling was conducted for two experimental scenarios: batch experiments to simulate sudden, fast, and short-lived release of CO2 as would occur in the case of well failure during injection, and column experiments to simulate more gradual leaks such as those occurring along undetected faults, fractures, or well linings. Observed and predicted trace metal concentrations are compared to groundwater concentrations from this aquifer to determine the potential for leaking CO2 to adversely impact drinking water quality. Finally, a three-dimensional multiphase flow and reactive-transport simulation of CO2 leakage from an abandoned wellbore into a generalized model of the shallow, unconfined portion of the aquifer is used to determine potential impacts on groundwater quality. As a measure of adverse impacts on groundwater quality, both the EPAs MCL limits and the maximum trace metal concentration observed in the aquifer were used as threshold values.

  18. Iron optimization for Fenton-driven oxidation of MTBE-spent granular activated carbon

    SciTech Connect (OSTI)

    Scott G. Huling; Patrick K. Jones; Tony R. Lee

    2007-06-01

    Fenton-driven chemical oxidation of methyl tert-butyl ether (MTBE)-spent granular activated carbon (GAC) was accomplished through the addition of iron (Fe) and hydrogen peroxide (H{sub 2}O{sub 2}) (15.9 g/L; pH 3). The GAC used was URV, a bituminous-coal based carbon. The Fe concentration in GAC was incrementally varied (1020-25 660 mg/kg) by the addition of increasing concentrations of Fe solution (FeSO4{center_dot}7H{sub 2}O). MTBE degradation in Fe-amended GAC increased by an order of magnitude over Fe-unamended GAC and H{sub 2}O{sub 2} reaction was predominantly (99%) attributed to GAC-bound Fe within the porous structure of the GAC. Imaging and microanalysis of GAC particles indicated limited penetration of Fe into GAC. The optimal Fe concentration was 6710 mg/kg (1020 mg/kg background; 5690 mg/kg amended Fe) and resulted in the greatest MTBE removal and maximum Fe loading oxidation efficiency (MTBE oxidized (g)/Fe loaded to GAC(mg/Kg)). At lower Fe concentrations, the H{sub 2}O{sub 2} reaction was Fe limited. At higher Fe concentrations, the H{sub 2}O{sub 2} reaction was not entirely Fe limited, and reductions in GAC surface area, GAC pore volume, MTBE adsorption, and Fe loading oxidation efficiency were measured. Results are consistent with nonuniform distribution of Fe, pore blockage in H{sub 2}O{sub 2} transport, unavailable Fe, and limitations in H{sub 2}O{sub 2} diffusive transport, and emphasize the importance of optimal Fe loading. 22 refs., 6 figs., 2 tabs.

  19. Ethanol oxidation on metal oxide-supported platinum catalysts

    SciTech Connect (OSTI)

    L. M. Petkovic 090468; Sergey N. Rashkeev; D. M. Ginosar

    2009-09-01

    Ethanol is a renewable fuel that can be used as an additive to gasoline (or its substitute) with the advantage of octane enhancement and reduced carbon monoxide exhaust emissions. However, on Ethanol is a renewable fuel that can be used as an additive to gasoline (or its substitute) with the advantage of octane enhancement and reduced carbon monoxide exhaust emissions. However, on the standard three-way catalysts, the conversion of unburned ethanol is low because both ethanol and some of its partially oxidized derivatives are highly resistant to oxidation. A combination of first-principles density-functional theory (DFT) based calculations and in-situ diffuse reflectance infrared spectroscopy (DRIFTS) analysis was applied to uncover some of the fundamental phenomena associated with ethanol oxidation on Pt containing catalysts. In particular, the objective was to analyze the role of the oxide (i.e., ?-Al2O3 or SiO2) substrate on the ethanol oxidation activity. The results showed that Pt nanoparticles trap and accumulate oxygen at their surface and perimeter sites and play the role of stoves that burn ethanol molecules and their partially oxidized derivatives to the final products. The ?-Al2O3 surfaces provided higher mobility of the fragments of ethanol molecules than the SiO2 surface and hence increased the supply rate of these objects to the Pt particles. This will in turn produce a higher conversion rate of unburned ethanol.and some of its partially oxidized derivatives are highly resistant to oxidation. A combination of first-principles density-functional theory (DFT) based calculations and in-situ diffuse reflectance infrared spectroscopy (DRIFTS) analysis was applied to uncover some of the fundamental phenomena associated with ethanol oxidation on Pt containing catalysts. In particular, the objective was to analyze the role of the oxide (i.e., ?-Al2O3 or SiO2) substrate on the ethanol oxidation activity. The results showed that Pt nanoparticles trap and

  20. Influences of Organic Carbon Supply Rate on Uranium Bioreduction in Initially Oxidizing, Contaminated Sediment

    SciTech Connect (OSTI)

    Tokunaga, Tetsu K.; Wan, Jiamin; Kim, Yongman; Daly, Rebecca A.; Brodie, Eoin L.; Hazen, Terry C.; Herman, Don; Firestone, Mary K.

    2008-06-10

    Remediation of uranium (U) contaminated sediments through in-situ stimulation of bioreduction to insoluble UO{sub 2} is a potential treatment strategy under active investigation. Previously, we found that newly reduced U(IV) can be reoxidized under reducing conditions sustained by a continuous supply of organic carbon (OC) because of residual reactive Fe(III) and enhanced U(VI) solubility through complexation with carbonate generated through OC oxidation. That finding motivated this investigation directed at identifying a range of OC supply rates that is optimal for establishing U bioreduction and immobilization in initially oxidizing sediments. The effects of OC supply rate, from 0 to 580 mmol OC (kg sediment){sup -1} year{sup -1}, and OC form (lactate and acetate) on U bioreduction were tested in flow-through columns containing U-contaminated sediments. An intermediate supply rate on the order of 150 mmol OC (kg sediment){sup -1} year{sup -1} was determined to be most effective at immobilizing U. At lower OC supply rates, U bioreduction was not achieved, and U(VI) solubility was enhanced by complexation with carbonate (from OC oxidation). At the highest OC supply rate, resulting highly carbonate-enriched solutions also supported elevated levels of U(VI), even though strongly reducing conditions were established. Lactate and acetate were found to have very similar geochemical impacts on effluent U concentrations (and other measured chemical species), when compared at equivalent OC supply rates. While the catalysts of U(VI) reduction to U(IV) are presumably bacteria, the composition of the bacterial community, the Fe reducing community, and the sulfate reducing community had no direct relationship with effluent U concentrations. The OC supply rate has competing effects of driving reduction of U(VI) to low solubility U(IV) solids, as well as causing formation of highly soluble U(VI)-carbonato complexes. These offsetting influences will require careful control of OC

  1. Co-Al mixed metal oxides/carbon nanotubes nanocomposite prepared via a precursor route and enhanced catalytic property

    SciTech Connect (OSTI)

    Fan Guoli; Wang Hui; Xiang Xu; Li Feng

    2013-01-15

    The present work reported the synthesis of Co-Al mixed metal oxides/carbon nanotubes (CoAl-MMO/CNT) nanocomposite from Co-Al layered double hydroxide/CNTs composite precursor (CoAl-LDH/CNT). The materials were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), low temperature nitrogen adsorption-desorption experiments, thermogravimetric and differential thermal analyses (TG-DTA), Raman spectra and X-ray photoelectron spectroscopy (XPS). The results revealed that in CoAl-MMO/CNT nanocomposite, the nanoparticles of cobalt oxide (CoO) and Co-containing spinel-type complex metal oxides could be well-dispersed on the surface of CNTs, thus forming the heterostructure of CoAl-MMO and CNTs. Furthermore, as-synthesized CoAl-MMO/CNT nanocomposite was utilized as additives for catalytic thermal decomposition of ammonium perchlorate (AP). Compared to those for pure AP and CoAl-MMO, the peak temperature of AP decomposition for CoAl-MMO/CNT was significantly decreased, which is attributed to the novel heterostructure and synergistic effect of multi-component metal oxides of nanocomposite. - Graphical abstract: Hybrid Co-Al mixed metal oxides/carbon nanotubes nanocomposite showed the enhanced catalytic activity in the thermal decomposition of ammonium perchlorate, as compared to carbon nanotubes and pure Co-Al mixed metal oxides. Highlights: Black-Right-Pointing-Pointer Co-Al mixed metal oxides/carbon nanotubes nanocomposite was synthesized. Black-Right-Pointing-Pointer Co-Al mixed metal oxides consisted of cobalt oxide and Co-containing spinels. Black-Right-Pointing-Pointer Nanocomposite exhibited excellent catalytic activity for the decomposition of AP. Black-Right-Pointing-Pointer The superior catalytic property is related to novel heterostructure and composition.

  2. Behavior of the Ru-bda water oxidation catalyst covalently anchored on glassy carbon electrodes

    SciTech Connect (OSTI)

    Matheu, Roc; Francs, Laia; Chernev, Petko; Ertem, Mehmed Z.; Batista, Victor; Haumann, Michael; Sala, Xavier; Llobet, Antoni

    2015-05-07

    Electrochemical reduction of the dizaonium complex, [RuII(bda)(NO)(NN2)2]3+, 23+ (NN22+ is 4-(pyridin-4-yl) benzenediazonium and bda2 is [2,2'-bipyridine]-6,6'-dicarboxylate), in acetone produces the covalent grafting of this molecular complex onto glassy carbon (GC) electrodes. Multiple cycling voltammetric experiments on the GC electrode generates hybrid materials labeled as GC-4, with the corresponding Ru-aqua complex anchored on the graphite surface. GC-4 has been characterized at pH = 7.0 by electrochemical techniques and X-ray absorption spectroscopy (XAS) and has been shown to act as an active catalyst for the oxidation of water to dioxygen. This new hybrid material has a lower catalytic performance than its counterpart in homogeneous phase and progressively decomposes to form RuO2 at the electrode surface. The resulting metal oxide attached at the GC electrode surface, GC-RuO2, is a very fast and rugged heterogeneous water oxidation catalyst with TOFis of 300 s1 and TONs >45000. The observed performance is comparable to the best electrocatalysts reported so far, at neutral pH.

  3. Behavior of the Ru-bda water oxidation catalyst covalently anchored on glassy carbon electrodes

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Matheu, Roc; Francàs, Laia; Chernev, Petko; Ertem, Mehmed Z.; Batista, Victor; Haumann, Michael; Sala, Xavier; Llobet, Antoni

    2015-05-07

    Electrochemical reduction of the dizaonium complex, [RuII(bda)(NO)(N–N2)2]3+, 23+ (N–N22+ is 4-(pyridin-4-yl) benzenediazonium and bda2– is [2,2'-bipyridine]-6,6'-dicarboxylate), in acetone produces the covalent grafting of this molecular complex onto glassy carbon (GC) electrodes. Multiple cycling voltammetric experiments on the GC electrode generates hybrid materials labeled as GC-4, with the corresponding Ru-aqua complex anchored on the graphite surface. GC-4 has been characterized at pH = 7.0 by electrochemical techniques and X-ray absorption spectroscopy (XAS) and has been shown to act as an active catalyst for the oxidation of water to dioxygen. This new hybrid material has a lower catalytic performance than its counterpartmore » in homogeneous phase and progressively decomposes to form RuO2 at the electrode surface. The resulting metal oxide attached at the GC electrode surface, GC-RuO2, is a very fast and rugged heterogeneous water oxidation catalyst with TOFis of 300 s–1 and TONs >45000. The observed performance is comparable to the best electrocatalysts reported so far, at neutral pH.« less

  4. Behavior of the Ru-bda water oxidation catalyst covalently anchored on glassy carbon electrodes

    SciTech Connect (OSTI)

    Matheu, Roc; Francàs, Laia; Chernev, Petko; Ertem, Mehmed Z.; Batista, Victor; Haumann, Michael; Sala, Xavier; Llobet, Antoni

    2015-05-07

    Electrochemical reduction of the dizaonium complex, [RuII(bda)(NO)(N–N2)2]3+, 23+ (N–N22+ is 4-(pyridin-4-yl) benzenediazonium and bda2– is [2,2'-bipyridine]-6,6'-dicarboxylate), in acetone produces the covalent grafting of this molecular complex onto glassy carbon (GC) electrodes. Multiple cycling voltammetric experiments on the GC electrode generates hybrid materials labeled as GC-4, with the corresponding Ru-aqua complex anchored on the graphite surface. GC-4 has been characterized at pH = 7.0 by electrochemical techniques and X-ray absorption spectroscopy (XAS) and has been shown to act as an active catalyst for the oxidation of water to dioxygen. This new hybrid material has a lower catalytic performance than its counterpart in homogeneous phase and progressively decomposes to form RuO2 at the electrode surface. The resulting metal oxide attached at the GC electrode surface, GC-RuO2, is a very fast and rugged heterogeneous water oxidation catalyst with TOFis of 300 s–1 and TONs >45000. The observed performance is comparable to the best electrocatalysts reported so far, at neutral pH.

  5. Plasma Reforming And Partial Oxidation Of Hydrocarbon Fuel Vapor To Produce Synthesis Gas And/Or Hydrogen Gas

    DOE Patents [OSTI]

    Kong, Peter C.; Detering, Brent A.

    2004-10-19

    Methods and systems are disclosed for treating vapors from fuels such as gasoline or diesel fuel in an internal combustion engine, to form hydrogen gas or synthesis gas, which can then be burned in the engine to produce more power. Fuel vapor, or a mixture of fuel vapor and exhaust gas and/or air, is contacted with a plasma, to promote reforming reactions between the fuel vapor and exhaust gas to produce carbon monoxide and hydrogen gas, partial oxidation reactions between the fuel vapor and air to produce carbon monoxide and hydrogen gas, or direct hydrogen and carbon particle production from the fuel vapor. The plasma can be a thermal plasma or a non-thermal plasma. The plasma can be produced in a plasma generating device which can be preheated by contact with at least a portion of the hot exhaust gas stream, thereby decreasing the power requirements of the plasma generating device.

  6. Plasma reforming and partial oxidation of hydrocarbon fuel vapor to produce synthesis gas and/or hydrogen gas

    DOE Patents [OSTI]

    Kong, Peter C.; Detering, Brent A.

    2003-08-19

    Methods and systems for treating vapors from fuels such as gasoline or diesel fuel in an internal combustion engine, to form hydrogen gas or synthesis gas, which can then be burned in the engine to produce more power. Fuel vapor, or a mixture of fuel vapor and exhaust gas and/or air, is contacted with a plasma, to promote reforming reactions between the fuel vapor and exhaust gas to produce carbon monoxide and hydrogen gas, partial oxidation reactions between the fuel vapor and air to produce carbon monoxide and hydrogen gas, or direct hydrogen and carbon particle production from the fuel vapor. The plasma can be a thermal plasma or a non-thermal plasma. The plasma can be produced in a plasma generating device which can be preheated by contact with at least a portion of the hot exhaust gas stream, thereby decreasing the power requirements of the plasma generating device.

  7. Pre-Combustion Carbon Capture Research | Department of Energy

    Energy Savers [EERE]

    This synthesis gas, or syngas, is a mixture of hydrogen, carbon monoxide, CO2, and smaller ... closely with the gasification and hydrogen turbine programs to ensure that ...

  8. Final Report: The Impact of Carbonate on Surface Protonation, Electron Transfer and Crystallization Reactions in Iron Oxide Nanoparticles and Colloids

    SciTech Connect (OSTI)

    Dixon, David Adams

    2013-07-02

    This project addresses key issues of importance in the geochemical behavior of iron oxides and in the geochemical cycling of carbon and iron. For Fe, we are specifically studying the influence of carbonate on electron transfer reactions, solid phase transformations, and the binding of carbonate to reactive sites on the edges of particles. The emphasis on carbonate arises because it is widely present in the natural environment, is known to bind strongly to oxide surfaces, is reactive on the time scales of interest, and has a speciation driven by acid-base reactions. The geochemical behavior of carbonate strongly influences global climate change and CO{sub 2} sequestration technologies. Our goal is to answer key questions with regards to specific site binding, electron transfer reactions, and crystallization reactions of iron oxides that impact both the geochemical cycling of iron and CO{sub 2} species. Our work is focused on the molecular level description of carbonate chemistry in solution including the prediction of isotope fractionation factors. We have also done work on critical atmospheric species.

  9. Recovery of manganese oxides from spent alkaline and zinc–carbon batteries. An application as catalysts for VOCs elimination

    SciTech Connect (OSTI)

    Gallegos, María V.; Falco, Lorena R.; Peluso, Miguel A.; Sambeth, Jorge E.; Thomas, Horacio J.

    2013-06-15

    Highlights: • Manganese oxides were synthesized using spent batteries as raw materials. • Spent alkaline and zinc–carbon size AA batteries were used. • A biohydrometallurgical process was employed to bio-lixiviate batteries. • Manganese oxides were active in the oxidation of VOCs (ethanol and heptane). - Abstract: Manganese, in the form of oxide, was recovered from spent alkaline and zinc–carbon batteries employing a biohydrometallurgy process, using a pilot plant consisting in: an air-lift bioreactor (containing an acid-reducing medium produced by an Acidithiobacillus thiooxidans bacteria immobilized on elemental sulfur); a leaching reactor (were battery powder is mixed with the acid-reducing medium) and a recovery reactor. Two different manganese oxides were recovered from the leachate liquor: one of them by electrolysis (EMO) and the other by a chemical precipitation with KMnO{sub 4} solution (CMO). The non-leached solid residue was also studied (RMO). The solids were compared with a MnO{sub x} synthesized in our laboratory. The characterization by XRD, FTIR and XPS reveal the presence of Mn{sub 2}O{sub 3} in the EMO and the CMO samples, together with some Mn{sup 4+} cations. In the solid not extracted by acidic leaching (RMO) the main phase detected was Mn{sub 3}O{sub 4}. The catalytic performance of the oxides was studied in the complete oxidation of ethanol and heptane. Complete conversion of ethanol occurs at 200 °C, while heptane requires more than 400 °C. The CMO has the highest oxide selectivity to CO{sub 2}. The results show that manganese oxides obtained using spent alkaline and zinc–carbon batteries as raw materials, have an interesting performance as catalysts for elimination of VOCs.

  10. Synthesis of free-standing carbon nanohybrid by directly growing carbon nanotubes on air-sprayed graphene oxide paper and its application in supercapacitor

    SciTech Connect (OSTI)

    Wei, Li; Jiang, Wenchao; Yuan, Yang; Goh, Kunli; Yu, Dingshan; Wang, Liang; Chen, Yuan

    2015-04-15

    We report the synthesis of a free-standing two dimensional carbon nanotube (CNT)-reduced graphene oxide (rGO) hybrid by directly growing CNTs on air-sprayed GO paper. As a result of the good integration between CNTs and thermally reduced GO film during chemical vapor deposition, excellent electrical conductivity (2.6×10{sup 4} S/m), mechanical flexibility (electrical resistance only increases 1.1% after bent to 90° for 500 times) and a relatively large surface area (335.3 m{sup 2}/g) are achieved. Two-electrode supercapacitor assembled using the CNT–rGO hybrids in ionic liquid electrolyte (1-ethyl-3-methylimidazolium tetrafluoroborate) shows excellent stability upon 500 bending cycles with the gravimetric energy density measuring 23.7 Wh/kg and a power density of 2.0 kW/kg. Furthermore, it shows an impedance phase angle of −64.4° at a frequency of 120 Hz, suggesting good potentials for 120 Hz alternating current line filtering applications. - Graphical abstract: Flexible and highly conductive carbon nanotube-reduced graphene oxide nanohybrid. - Highlights: • Direct growth of carbon nanotubes by chemical vapor deposition on air-sprayed graphene oxide paper. • Two-dimensional carbon nanohybrid with excellent conductivity and mechanical flexibility. • Supercapacitor with excellent performance stability upon mechanical deformation for flexible electronics applications. • Supercapacitor with high impedance phase angle for 120 Hz alternating current line filtering applications.

  11. Platinum Nickel Nanowires as Methanol Oxidation Electrocatalysts

    SciTech Connect (OSTI)

    Alia, Shaun M.; Pylypenko, Svitlana; Neyerlin, Kenneth C.; Kocha, Shyam S.; Pivovar, Bryan S.

    2015-08-27

    We investigated platinum(Pt) nickel (Ni) nanowires (PtNiNWs) as methanol oxidation reaction (MOR) catalysts in rotating disk electrode (RDE) half-cells under acidic conditions. Pt-ruthenium (Ru) nanoparticles have long been the state of the art MOR catalyst for direct methanol fuel cells (DMFCs) where Ru provides oxophilic sites, lowering the potential for carbon monoxide oxidation and the MOR onset. Ru, however, is a precious metal that has long term durability concerns. Ni/Ni oxide species offer a potential to replace Ru in MOR electrocatalysis. PtNiNWs were investigated for MOR and oxygen annealing was investigated as a route to improve catalyst performance (mass activity 65% greater) and stability to potential cycling. Our results presented show that PtNiNWs offer significant promise in the area, but also result in Ni ion leaching that is a concern requiring further evaluation in fuel cells.

  12. Platinum Nickel Nanowires as Methanol Oxidation Electrocatalysts

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Alia, Shaun M.; Pylypenko, Svitlana; Neyerlin, Kenneth C.; Kocha, Shyam S.; Pivovar, Bryan S.

    2015-08-27

    We investigated platinum(Pt) nickel (Ni) nanowires (PtNiNWs) as methanol oxidation reaction (MOR) catalysts in rotating disk electrode (RDE) half-cells under acidic conditions. Pt-ruthenium (Ru) nanoparticles have long been the state of the art MOR catalyst for direct methanol fuel cells (DMFCs) where Ru provides oxophilic sites, lowering the potential for carbon monoxide oxidation and the MOR onset. Ru, however, is a precious metal that has long term durability concerns. Ni/Ni oxide species offer a potential to replace Ru in MOR electrocatalysis. PtNiNWs were investigated for MOR and oxygen annealing was investigated as a route to improve catalyst performance (mass activitymore » 65% greater) and stability to potential cycling. Our results presented show that PtNiNWs offer significant promise in the area, but also result in Ni ion leaching that is a concern requiring further evaluation in fuel cells.« less

  13. Low-surface-area hard carbon anode for Na-ion batteries via graphene oxide as a dehydration agent

    SciTech Connect (OSTI)

    Luo, Wei; Bommier, Clement; Jian, Zelang; Li, Xin; Carter, Rich; Vail, Sean; Lu, Yuhao; Lee, Jong -Jan; Ji, Xiulei

    2015-02-04

    Na-ion batteries are emerging as one of the most promising energy storage technologies, particularly for grid-level applications. Among anode candidate materials, hard carbon is very attractive due to its high capacity and low cost. However, hard carbon anodes often suffer a low first-cycle Coulombic efficiency and fast capacity fading. In this study, we discover that doping graphene oxide into sucrose, the precursor for hard carbon, can effectively reduce the specific surface area of hard carbon to as low as 5.4 m²/g. We further reveal that such doping can effectively prevent foaming during caramelization of sucrose and extend the pyrolysis burn-off of sucrose caramel over a wider temperature range. Thus, the obtained low-surface-area hard carbon greatly improves the first-cycle Coulombic efficiency from 74% to 83% and delivers a very stable cyclic life with 95% of capacity retention after 200 cycles.

  14. Low-surface-area hard carbon anode for Na-ion batteries via graphene oxide as a dehydration agent

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Luo, Wei; Bommier, Clement; Jian, Zelang; Li, Xin; Carter, Rich; Vail, Sean; Lu, Yuhao; Lee, Jong -Jan; Ji, Xiulei

    2015-02-04

    Na-ion batteries are emerging as one of the most promising energy storage technologies, particularly for grid-level applications. Among anode candidate materials, hard carbon is very attractive due to its high capacity and low cost. However, hard carbon anodes often suffer a low first-cycle Coulombic efficiency and fast capacity fading. In this study, we discover that doping graphene oxide into sucrose, the precursor for hard carbon, can effectively reduce the specific surface area of hard carbon to as low as 5.4 m²/g. We further reveal that such doping can effectively prevent foaming during caramelization of sucrose and extend the pyrolysis burn-offmore » of sucrose caramel over a wider temperature range. Thus, the obtained low-surface-area hard carbon greatly improves the first-cycle Coulombic efficiency from 74% to 83% and delivers a very stable cyclic life with 95% of capacity retention after 200 cycles.« less

  15. Low-surface-area hard carbon anode for Na-ion batteries via graphene oxide as a dehydration agent

    SciTech Connect (OSTI)

    Luo, Wei; Bommier, Clement; Jian, Zelang; Li, Xin; Carter, Rich; Vail, Sean; Lu, Yuhao; Lee, Jong -Jan; Ji, Xiulei

    2015-02-04

    Na-ion batteries are emerging as one of the most promising energy storage technologies, particularly for grid-level applications. Among anode candidate materials, hard carbon is very attractive due to its high capacity and low cost. However, hard carbon anodes often suffer a low first-cycle Coulombic efficiency and fast capacity fading. In this study, we discover that doping graphene oxide into sucrose, the precursor for hard carbon, can effectively reduce the specific surface area of hard carbon to as low as 5.4 m/g. We further reveal that such doping can effectively prevent foaming during caramelization of sucrose and extend the pyrolysis burn-off of sucrose caramel over a wider temperature range. Thus, the obtained low-surface-area hard carbon greatly improves the first-cycle Coulombic efficiency from 74% to 83% and delivers a very stable cyclic life with 95% of capacity retention after 200 cycles.

  16. Reduced graphene oxide and vertically aligned carbon nanotubes superhydrophilic films for supercapacitors devices

    SciTech Connect (OSTI)

    Zanin, H.; Saito, E.; Ceragioli, H.J.; Baranauskas, V.; Corat, E.J.

    2014-01-01

    Graphical abstract: - Highlights: Graphene nanosheets were produced onto wire rods. RGO and VACNT-O were evaluated and compared as supercapacitor electrode. RGO and VACNT-O have structural and electrochemical properties quite similars. The materials present good specific capacitance, energy storage and power delivery. - Abstract: Reduced graphene oxide (RGO) and vertically aligned carbon nanotubes (VACNT) superhydrophilic films were prepared by chemical vapor deposition techniques for electrical energy storage investigations. These electrodes were characterized in terms of their material and electrochemical properties by scanning electron microscopy (SEM), surface wettability, Fourier transform infrared spectroscopy (FTIR), energy dispersive and Raman spectroscopies, cyclic voltammetry (CV) and galvanostatic chargedischarge. We observed several physical structural and electrochemical similarities between these carbon-based materials with particular attention to very good specific capacitance, ultra-high energy storage and fast power delivery. Our results showed that the main difference between specific capacitance values is attributed to pseudocapacitive contribution and high density of multiwall nanotubes tips. In this work we have tested a supercapacitor device using the VACNT electrodes.

  17. Carbon microspheres from ethanol at low temperature: Fabrication, characterization and their use as an electrocatalyst support for methanol oxidation

    SciTech Connect (OSTI)

    Lian, Suoyuan; School of Light Industry and Chemical Engineering, Dalian Polytechnic University, Dalian 116034 ; Ming, Hai; Huang, Hui; Kang, Zhenhui; Liu, Yang

    2012-11-15

    Highlights: ► Carbon microbeads were prepared by the carbonization of ethanol at low temperature. ► The low temperature carbonization of ethanol was catalyzed by iodine. ► Carbon microbeads can serve as ideal candidate for catalyst supports. -- Abstract: Carbon microspheres (CMSs) with a diameter range of 2–3 μm were prepared by the iodine-catalyzed carbonization of ethanol at low temperatures by solvothermal synthesis. The reaction time, concentrations of reactants, temperatures, different alcohols as carbon precursors and reaction environments were systematically altered to determine the optimal synthesis conditions. The size and shape were characterized by scanning and transmission electron microscopy and their structure was characterized by X-ray powder diffraction and Raman spectroscopy. Energy dispersive X-ray spectroscopy, Fourier transform infrared and X-ray photoelectron spectroscopy showed that abundant oxygen-containing functional groups remain on the surface of the carbon spheres. The formation mechanism involves iodine promotion of the oxidation of ethanol, which results in formation of the CMSs. The specific activity of the CMS-supported Pt catalyst is higher than that of a commercial Pt catalyst from E-TEK or the unsupported Pt catalyst.

  18. High-performance carbon-nanotube-based complementary field-effect-transistors and integrated circuits with yttrium oxide

    SciTech Connect (OSTI)

    Liang, Shibo; Zhang, Zhiyong Si, Jia; Zhong, Donglai; Peng, Lian-Mao

    2014-08-11

    High-performance p-type carbon nanotube (CNT) transistors utilizing yttrium oxide as gate dielectric are presented by optimizing oxidization and annealing processes. Complementary metal-oxide-semiconductor (CMOS) field-effect-transistors (FETs) are then fabricated on CNTs, and the p- and n-type devices exhibit symmetrical high performances, especially with low threshold voltage near to zero. The corresponding CMOS CNT inverter is demonstrated to operate at an ultra-low supply voltage down to 0.2?V, while displaying sufficient voltage gain, high noise margin, and low power consumption. Yttrium oxide is proven to be a competitive gate dielectric for constructing high-performance CNT CMOS FETs and integrated circuits.

  19. Geochemical Impacts of Leaking CO2 from Subsurface Storage Reservoirs to an Unconfined Oxidizing Carbonate Aquifer

    SciTech Connect (OSTI)

    Wang, Guohui; Qafoku, Nikolla; Lawter, Amanda R.; Bowden, Mark E.; Harvey, Omar; Sullivan, E. C.; Brown, Christopher F.

    2015-07-15

    A series of batch and column experiments combined with solid phase characterization studies (i.e., quantitative x-ray diffraction and wet chemical extractions) were conducted to address a variety of scientific issues and evaluate the impacts of the potential leakage of carbon dioxide (CO2) from deep subsurface storage reservoirs. The main objective was to gain an understanding of how CO2 gas influences: 1) the aqueous phase pH; and 2) mobilization of major, minor, and trace elements from minerals present in an aquifer overlying potential CO2 sequestration subsurface repositories. Rocks and slightly weathered rocks representative of an unconfined, oxidizing carbonate aquifer within the continental US, i.e., the Edwards aquifer in Texas, were used in these studies. These materials were exposed to a CO2 gas stream or were leached with a CO2-saturated influent solution to simulate different CO2 gas leakage scenarios, and changes in aqueous phase pH and chemical composition were measured in the liquid samples collected at pre-determined experimental times (batch experiments) or continuously (column experiments). The results from the strong acid extraction tests confirmed that in addition to the usual elements present in most soils, rocks, and sediments, the Edward aquifer samples contain As, Cd, Pb, Cu, and occasionally Zn, which may potentially be mobilized from the solid to the aqueous phase during or after exposure to CO2. The results from the batch and column experiments confirmed the release of major chemical elements into the contacting aqueous phase (such as Ca, Mg, Ba, Sr, Si, Na, and K); the mobilization and possible rapid immobilization of minor elements (such as Fe, Al, and Mn), which are able to form highly reactive secondary phases; and sporadic mobilization of only low concentrations of trace elements (such as As, Cd, Pb, Cu, Zn, Mo, etc.). The results from this experimental research effort will help in developing a systematic understanding of how CO2

  20. Photocatalytic and chemical oxidation of organic compounds in supercritical carbon dioxide. Progress report for FY97

    SciTech Connect (OSTI)

    Blake, D.M.; Bryant, D.L.; Reinsch, V.

    1997-09-30

    and using makeup scCO{sub 2}. A chemical polishing operation can reduce the release of CO{sub 2} from the process. It can also reduce the consumption of reagents that may be used in the process to enhance extraction and cleaning. A polishing operation will also reduce or avoid formation of an additional waste stream. Photocatalytic and other photochemical oxidation chemistry have not been investigated in scCO{sub 2}. The large base of information for these reactions in water, organic solvents, or air suggest that the chemistry will work in carbon dioxide. There are compelling reasons to believe that the properties of scCO{sub 2} should increase the performance of photocatalytic chemistry over that found in more conventional fluid phases.'

  1. Amperometric Biosensors Based on Carbon Paste Electrodes Modified with Nanostructured Mixed-valence Manganese Oxides and Glucose Oxidase

    SciTech Connect (OSTI)

    Cui, Xiaoli; Liu, Guodong; Lin, Yuehe

    2005-06-01

    Nanostructured multivalent manganese oxides octahedral molecular sieve (OMS), including cryptomelane-type manganese oxides and todorokite-type manganese oxides, were synthesized and evaluated for chemical sensing and biosensing at low operating potential. Both cryptomelane-type manganese oxides and todorokite-type manganese oxides are nanofibrous crystals with sub-nanometer open tunnels that provide a unique property for sensing applications. The electrochemical and electrocatalytic performance of OMS for the oxidation of H2O2 have been compared. Both cryptomelane-type manganese oxides and todorokite-type manganese oxides can be used to fabricate sensitive H2O2 sensors. Amperometric glucose biosensors are constructed by bulk modification of carbon paste electrodes (CPEs) with glucose oxidase as a biocomponent and nanostructured OMS as a mediator. A Nafion thin film was applied as an immobilization/encapsulation and protective layer. The biosensors were evaluated as an amperometric glucose detector at phosphate buffer solution with a pH 7.4 at an operating potential of 0.3 V (vs. Ag/AgCl). The biosensor is characterized by a well-reproducible amperometric response, linear signal-to-glucose concentration range up to 3.5 mM and 1.75 mM, and detection limits (S/N = 3) of 0.1 mM and 0.05 mM for todorokite-type manganese oxide and cryptomelane-type manganese oxide modified electrodes, respectively. The biosensors based on OMS exhibit considerable good reproducibility and stability, and the construction and renewal are simple and inexpensive.

  2. Graphene oxide/carbon nanoparticle thin film based IR detector: Surface properties and device characterization

    SciTech Connect (OSTI)

    Chowdhury, Farzana Aktar; Hossain, Mohammad Abul; Uchida, Koji; Tamura, Takahiro; Sugawa, Kosuke; Mochida, Tomoaki; Otsuki, Joe; Mohiuddin, Tariq; Boby, Monny Akter; Alam, Mohammad Sahabul

    2015-10-15

    This work deals with the synthesis, characterization, and application of carbon nanoparticles (CNP) adorned graphene oxide (GO) nanocomposite materials. Here we mainly focus on an emerging topic in modern research field presenting GO-CNP nanocomposite as a infrared (IR) radiation detector device. GO-CNP thin film devices were fabricated from liquid phase at ambient condition where no modifying treatments were necessary. It works with no cooling treatment and also for stationary objects. A sharp response of human body IR radiation was detected with time constants of 3 and 36 sec and radiation responsivity was 3 mAW{sup −1}. The current also rises for quite a long time before saturation. This work discusses state-of-the-art material developing technique based on near-infrared photon absorption and their use in field deployable instrument for real-world applications. GO-CNP-based thin solid composite films also offer its potentiality to be utilized as p-type absorber material in thin film solar cell, as well.

  3. Synthesis of few-walled carbon nanotube-Rh nanoparticles by arc discharge: Effect of selective oxidation

    SciTech Connect (OSTI)

    Zhang Yanfeng

    2012-06-15

    Highly crystalline rhodium (Rh) nanoparticles supported on carbon nanotubes were prepared by selective oxidation method. Carbon nanotubes and FeRh nanoparticles were simultaneously generated in hydrogen arc plasma. The as-grown nanomaterials can be purified by heat treatment in open air and by soaking in HCl. X-ray diffraction and selected area electron diffraction results reveal that as-grown FeRh nanoparticles have a typical chemical CsCl-type structure which can be transformed into a face-centered cubic structure by thermal annealing in the purification process. The purification process is selective toward the removal of the amorphous carbon coating the nanoparticles, and transforms Fe to Fe{sub 2}O{sub 3}. Fe{sub 2}O{sub 3} can be easily dissolved in hydrochloric acid, leaving carbon nanotubes-Rh nanoparticles. Rh nanoparticles with diameters of 2-60 nm are deposited uniformly on the surface of the carbon nanotube bundles. This simple and selective chemistry offers a new process for synthesizing and controlling Fe content in carbon nanotube-FeRh nanoparticles. Highlights: Black-Right-Pointing-Pointer High-crystallinity CNTs and FeRh nanoparticles were simultaneously generated in arc plasma. Black-Right-Pointing-Pointer The diameter distribution of CNTs depends on different gases. Black-Right-Pointing-Pointer Heat treatment in open air and soaking in HCl can convert CNTs-FeRh to CNTs-Rh. Black-Right-Pointing-Pointer The selective oxidation mechanisms of metal nanoparticles and carbon materials differ.

  4. Comparative electron paramagnetic resonance investigation of reduced graphene oxide and carbon nanotubes with different chemical functionalities for quantum dot attachment

    SciTech Connect (OSTI)

    Pham, Chuyen V.; Krueger, Michael E-mail: emre.erdem@physchem.uni-freiburg.de; Eck, Michael; Weber, Stefan; Erdem, Emre E-mail: emre.erdem@physchem.uni-freiburg.de

    2014-03-31

    Electron paramagnetic resonance (EPR) spectroscopy has been applied to different chemically treated reduced graphene oxide (rGO) and multiwalled carbon nanotubes (CNTs). A narrow EPR signal is visible at g?=?2.0029 in both GO and CNT-Oxide from carbon-related dangling bonds. EPR signals became broader and of lower intensity after oxygen-containing functionalities were reduced and partially transformed into thiol groups to obtain thiol-functionalized reduced GO (TrGO) and thiol-functionalized CNT (CNT-SH), respectively. Additionally, EPR investigation of CdSe quantum dot-TrGO hybrid material reveals complete quenching of the TrGO EPR signal due to direct chemical attachment and electronic coupling. Our work confirms that EPR is a suitable tool to detect spin density changes in different functionalized nanocarbon materials and can contribute to improved understanding of electronic coupling effects in nanocarbon-nanoparticle hybrid nano-composites promising for various electronic and optoelectronic applications.

  5. Oxide

    SciTech Connect (OSTI)

    2014-07-15

    Oxide is a modular framework for feature extraction and analysis of executable files. Oxide is useful in a variety of reverse engineering and categorization tasks relating to executable content.

  6. Influence of pH on the adsorption of uranium ions by oxidized activated carbon and chitosan

    SciTech Connect (OSTI)

    Park, G.I.; Park, H.S.; Woo, S.I.

    1999-03-01

    The adsorption characteristics of uranyl ions on surface-oxidized carbon were compared with those of powdered chitosan over a wide pH range. In particular, an extensive analysis was made on solution pH variation during the adsorption process or after adsorption equilibrium. Uranium adsorption on the two adsorbents was revealed to be strongly dependent on the initial pH of the solution. A quantitative comparison of the adsorption capacities of the two adsorbents was made, based on the isotherm data obtained at initial pH 3, 4, and 5. In order to analyze the adsorption kinetics incorporated with pH effects, batch experiments at various initial pH values were carried out, and solution pH profiles with the adsorption time were also evaluated. The breakthrough behavior in a column packed with oxidized carbon was also characterized with respect to the variation of effluent pH. Based on these experimental results, the practical applicability of oxidized carbon for uranium removal from acidic radioactive liquid waste was suggested.

  7. Electrodeposited Manganese Oxides on Three-Dimensional Carbon Nanotube Substrate: Supercapacitive Behaviour in Aqueous and Organic Electrolytes

    SciTech Connect (OSTI)

    Nam,K.W.; Yang,X.

    2009-03-01

    Thin amorphous manganese oxide layers with a thickness of 3-5nm are electrodeposited on a carbon nanotube (CNT) film substrate that has a three-dimensional nanoporous structure (denoted asMnO2/CNT electrode). For the purpose of comparison, manganese oxide films are also electrodeposited on a flat Pt-coated Si wafer substrate (denoted as MnO2 film electrode). The pseudocapacitive properties of the MnO2 film and MnO2/CNT electrodes are examined in both aqueous electrolyte (1.0M KCl) and nonaqueousorganic electrolyte (1.0M LiClO4 in propylene carbonate). While both types of electrode showpseudocapacitive behaviour in the aqueous electrolyte, only the MnO2/CNT electrode does so in the organic electrolyte, due to its high oxide/electrolyte interfacial area and improved electron conduction through the CNT substrate. Compared with the MnO2 film electrode, the MnO2/CNT electrode shows a much higher specific capacitance and better high-rate capability, regardless of the electrolyte used.Use of the organic electrolyte results in a ?6 times higher specific energy compared with that obtained with the aqueous electrolyte, while maintaining a similar specific power. The construction of a threedimensional nanoporous network structure consisting of a thin oxide layer on a CNT film substrate at the nm scale and the use of an organic electrolyte are promising approaches to improving the specific energyof supercapacitors.

  8. Extraction of rare earth oxides using supercritical carbon dioxide modified with Tri-n-butyl phosphate–nitric acid adducts

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Baek, Donna L.; Fox, Robert V.; Case, Mary E.; Sinclair, Laura K.; Schmidt, Alex B.; McIlwain, Patrick R.; Mincher, Bruce J.; Wai, Chien M.

    2016-06-14

    A new tri-n-butylphosphate–nitric acid (TBP–HNO3) adduct was prepared by combining TBP and fuming (90%) HNO3. The adduct was characterized, and its phase-equilibrium behavior in supercritical carbon dioxide is reported. Supercritical carbon dioxide (sc-CO2) was modified with this new adduct [TBP(HNO3)5.2(H2O)1.7], and the extraction efficacies of selected rare earth oxides (Y, Ce, Eu, Tb, and Dy) at 338 K and 34.5 MPa were compared with those obtained using an adduct formed from concentrated (70%) HNO3 and TBP [TBP(HNO3)1.7(H2O)0.6]. All rare earth oxides tested with both adduct species could be extracted with the exception of cerium oxide. Furthermore, the water and acidmore » concentrations in the different adducts were found to play a significant role in rare earth oxide extraction efficiency.« less

  9. Catalytic production of metal carbonyls from metal oxides

    DOE Patents [OSTI]

    Sapienza, Richard S.; Slegeir, William A.; Foran, Michael T.

    1984-01-01

    This invention relates to the formation of metal carbonyls from metal oxides and specially the formation of molybdenum carbonyl and iron carbonyl from their respective oxides. Copper is used here in admixed form or used in chemically combined form as copper molybdate. The copper/metal oxide combination or combined copper is utilized with a solvent, such as toluene and subjected to carbon monoxide pressure of 25 atmospheres or greater at about 150.degree.-260.degree. C. The reducing metal copper is employed in catalytic concentrations or combined concentrations as CuMoO.sub.4 and both hydrogen and water present serve as promoters. It has been found that the yields by this process have been salutary and that additionally the catalytic metal may be reused in the process to good effect.

  10. Catalytic production of metal carbonyls from metal oxides

    DOE Patents [OSTI]

    Sapienza, R.S.; Slegeir, W.A.; Foran, M.T.

    1984-01-06

    This invention relates to the formation of metal carbonyls from metal oxides and specially the formation of molybdenum carbonyl and iron carbonyl from their respective oxides. Copper is used here in admixed form or used in chemically combined form as copper molybdate. The copper/metal oxide combination or combined copper is utilized with a solvent, such as toluene and subjected to carbon monoxide pressure of 25 atmospheres or greater at about 150 to 260/sup 0/C. The reducing metal copper is employed in catalytic concentrations or combined concentrations as CuMoO/sub 4/ and both hydrogen and water present serve as promoters. It has been found that the yields by this process have been salutary and that additionally the catalytic metal may be reused in the process to good effect. 3 tables.

  11. Use of oxide decompositions in advanced thermochemical hydrogen cycles for solar heat sources. Experimental results on the low-temperature reactions for the tricobalt tetraoxide-cobalt monoxide pair

    SciTech Connect (OSTI)

    Jones, W.M.; Bowman, M.G.

    1982-01-01

    The concept of utilizing oxide decompositions in advanced thermochemical hydrogen cycles for solar heat sources is introduced. It has particular interest in allowing direct transmission of energy to the process through an air window. A cycle for the Co/sub 3/O/sub 4/-CoO pair would be, schematically: (1) Co/sub 3/O/sub 4/ = 3CoO + 1/2 O/sub 2/; (2) I/sub 2/(s,1) + Mg(OH)/sub 2/ + 3CoO = MgI/sub 2/(aq) + Co/sub 3/O/sub 4/ + H/sub 2/O(1); (3) H/sub 2/O + MgI/sub 2/(aq) = MgO + 2HI; (4) 2 HI = H/sub 2/ + I/sub 2/; (5) MgO + H/sub 2/O = Mg(OH)/sub 2/. Reaction (2) should give a high concentration of MgI/sub 2/ that would be favorable for (3). The solutions would also contain iodine dissolved as polyiodide, partly offsetting this advantage. Preliminary results indicate that reaction (2) is slow at 150/sup 0/C. It is surmised that the mechanism of (2) consists of the iodine disproportionation reaction (6), followed by reaction (7). (6) I/sub 2/(s,1) + Mg(OH)/sub 2/ = 5/6 MgI/sub 2/(aq) + 1/6 Mg(IO/sub 3/)/sub 2/(aq) + H/sub 2/O(1); (7) 1/6 Mg(IO/sub 3/)/sub 2/(aq) + 3 CoO = 1/6 MgI/sub 2/(aq) + Co/sub 3/O/sub 4/. Other workers have found (6) to be relatively fast and with a good yield at 150/sup 0/C. We have found the independently studied reaction (7) to be sufficiently slow at 150/sup 0/C to account for the slowness of (2). The yield of (7) was found to be proportional to the square root of the time, which suggests that iodate must diffuse through an adherent, accumulating Co/sub 3/O/sub 4/ layer. Since (7) is much faster when Mg(IO/sub 3/)/sub 2/ is replaced by KIO/sub 3/, the Mg/sup 2 +/ ion may catalyze formation of an adherent Co/sub 3/O/sub 4/ spinel layer. The reactivity of CoO in the KIO/sub 3/ analog of (7) is greatly decreased by exposure to high temperature.

  12. Kinetics of hydrolysis and oxidation of carbon disulfide by hydrogen peroxide in alkaline medium and application to carbonyl sulfide

    SciTech Connect (OSTI)

    Adewuyi, Y.G.; Carmichael, G.R.

    1987-02-01

    Kinetic studies of the oxidation of carbon disulfide by hydrogen peroxide in alkaline medium were made spectrophotometrically. The reaction of CS/sub 2/ with OH/sup -/ ion was found to be rate controlling and proceeded by the formation of a dithiocarbonate complex. The major reaction product was sulfate with sulfur occurring as colloidal suspensions only at pH values less than 8. The formation of sulfate increased exponentially with time and was also found to be dependent on the rate of hydrolysis of CS/sub 2/. In addition, the production of sulfate showed large induction periods, suggesting either a complex mechanism or formation by secondary reactions. The results obtained for carbon disulfide were extended to carbonyl sulfide (OCS) oxidation in alkaline solutions. The removal of OCS (acid gas) from mixtures of gases by alkaline liquid absorbents (e.g. NaOH) and oxidation of subsequent solutions to sulfate is an important industrial practice. 42 references, 14 figures, 2 tables.

  13. Effects of aging and oxidation of palladized iron embedded in activated carbon on the dechlorination of 2-chlorobiphenyl

    SciTech Connect (OSTI)

    Hyeok Choi; Souhail R. Al-Abed; Shirish Agarwal

    2009-06-15

    Reactive activated carbon (RAC) impregnated with palladized iron has been developed to effectively treat polychlorinated biphenyls (PCBs) in the environment by coupling adsorption and dechlorination of PCBs. In this study, we addressed the dechlorination reactivity and capacity of RAC toward aqueous 2-chlorobiphenyl (2-ClBP), and its aging and longevity under various oxidizing environments. RAC containing 14.4% Fe and 0.68% Pd used in this study could adsorb 122.6 mg 2-ClBP/g RAC, and dechlorinate 56.5 mg 2-ClBP/g RAC which corresponds to 12% (yield) of its estimated dechlorination capacity. Due to Fe0 oxidation to form oxide passivating layers, Fe{sub 2}O{sub 3}/Fe{sub 3}O{sub 4} (oxide-water interface) and FeOOH/FeO (oxide-metal interface), RAC reactivity decreased progressively over aging under N{sub 2} < H{sub 2}O + N{sub 2} < H{sub 2}O + O{sub 2} conditions. Considering nanoscale Fe/Pd corrosion chemistry, the decline was quite slow at only 5.6%, 19.5%, and 32.5% over one year, respectively. Dissolved oxygen played a crucial role in enhancing 2-ClBP adsorption but inhibiting its dechlorination. The reactivity change could be explained with the properties of the aged RAC including surface area, Fe0 content, and Fe species. During the aging and oxidation, the RAC showed limited dissolution of Fe and Pd. Finally, implementation issues regarding application of RAC system to contaminated sites are discussed. 25 refs., 6 figs., 1 tab.

  14. Surface analysis of Zircaloy-2 implanted with carbon before and after oxidation in air at 500 deg. C

    SciTech Connect (OSTI)

    Peng, D.Q. . E-mail: pdq01@mails.tsinghua.edu.cn; Bai, X.D.; Pan, F.; Sun, H.; Chen, B.S.

    2006-03-15

    Zircaloy-2 specimens were implanted with carbon ions in the fluence range from 1 x 10{sup 16} to 1 x 10{sup 18} ions/cm{sup 2}, using a MEVVA source at an extraction voltage of 40 kV at a maximum temperature of 380 deg. C. The valences and depth profiles of elements in the implanted surface of Zircaloy-2 were analyzed by X-ray photoelectron spectroscopy and Auger electron spectroscopy, respectively. Scanning electron microscopy was used to examine the micro-morphology of samples. The color of the oxidized samples was checked with an optical scanner. Glancing-angle X-ray diffraction at 0.3{sup o} incident angles was employed to examine the phase transformations of implanted samples before and after oxidation in the air at 500 deg. C for 2 h. Before oxidation, at fluences less than 5 x 10{sup 16} ions/cm{sup 2}, hexagonal zirconia (H-ZrO{sub 0.35}) was present. At a fluence of 1 x 10{sup 17} ions/cm{sup 2}, rhombohedral zirconia (R-Zr{sub 3}O) appeared. When the fluence reached 1 x 10{sup 18} ions/cm{sup 2}, cubic zirconium carbide was produced. There are many pits, both deep and shallow, in the sample surfaces, both prior to oxidation and after oxidation. Oxidation in the air at 500 deg. C gave rise to black surfaces on all samples. The X-ray diffraction results showed that monoclinic and tetragonal zirconia were present in the surface of as-received sample. For implanted samples, monoclinic and tetragonal zirconia are still present, while cubic zirconium carbide is produced at all fluences. The presence of ZrC is attributed to the high-temperature, long-time (2 h) exposure.

  15. Tungsten carbide/porous carbon composite as superior support for platinum catalyst toward methanol electro-oxidation

    SciTech Connect (OSTI)

    Jiang, Liming; Fu, Honggang; Wang, Lei; Mu, Guang; Jiang, Baojiang; Zhou, Wei; Wang, Ruihong

    2014-01-01

    Graphical abstract: The WC nanoparticles are well dispersed in the carbon matrix. The size of WC nanoparticles is about 30 nm. It can be concluded that tungsten carbide and carbon composite was successfully prepared by the present synthesis conditions. - Highlights: The WC/PC composite with high specific surface area was prepared by a simple way. The Pt/WC/PC catalyst has superior performance toward methanol electro-oxidation. The current density for methanol electro-oxidation is as high as 595.93 A g{sup ?1} Pt. The Pt/WC/PC catalyst shows better durability and stronger CO electro-oxidation. The performance of Pt/WC/PC is superior to the commercial Pt/C (JM) catalyst. - Abstract: Tungsten carbide/porous carbon (WC/PC) composites have been successfully synthesized through a surfactant assisted evaporation-induced-assembly method, followed by a thermal treatment process. In particular, WC/PC-35-1000 composite with tungsten content of 35% synthesized at the carbonized temperature of 1000 C, exhibited a specific surface area (S{sub BET}) of 457.92 m{sup 2} g{sup ?1}. After loading Pt nanoparticles (NPs), the obtained Pt/WC/PC-35-1000 catalyst exhibits the highest unit mass electroactivity (595.93 A g{sup ?1} Pt) toward methanol electro-oxidation, which is about 2.6 times as that of the commercial Pt/C (JM) catalyst. Furthermore, the Pt/WC/PC-35-1000 catalyst displays much stronger resistance to CO poisoning and better durability toward methanol electrooxidation compared with the commercial Pt/C (JM) catalyst. The high electrocatalytic activity, strong poison-resistivity and good stability of Pt/WC/PC-35-1000 catalyst are attributed to the porous structures and high specific surface area of WC/PC support could facilitate the rapid mass transportation. Moreover, synergistic effect between WC and Pt NPs is favorable to the higher catalytic performance.

  16. Development of a selective oxidation CO removal reactor for methanol reformate gas

    SciTech Connect (OSTI)

    Okada, Shunji; Takatani, Yoshiaki; Terada, Seijo; Ohtani, Shinichi

    1996-12-31

    This report forms part of a joint study on a PEFC propulsion system for surface ships, summarized in a presentation to this Seminar, entitled {open_quotes}Study on a Polymer Electrolyte Fuel Cell (PEFC) Propulsion System for Surface Ships{close_quotes}, and which envisages application to a 1,500 DWT cargo vessel. The aspect treated here concerns laboratory-scale tests aimed at reducing by selective oxidation to a level below 10 ppm the carbon monoxide (CO) contained to a concentration of around 1% in reformate gas.

  17. Photochemical dimerization and functionalization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and silanes

    DOE Patents [OSTI]

    Crabtree, R.H.; Brown, S.H.

    1989-10-17

    The space-time yield and/or the selectivity of the photochemical dimerization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and primary, secondary and tertiary silanes with Hg and U.V. light is enhanced by refluxing the substrate in the irradiated reaction zone at a temperature at which the dimer product condenses and remains condensed promptly upon its formation. Cross-dimerization of the alkanes, ethers and silanes with primary alcohols is disclosed, as is the functionalization to aldehydes of the alkanes with carbon monoxide.

  18. Photochemical dimerization and functionalization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and silanes

    DOE Patents [OSTI]

    Crabtree, Robert H. (Bethany, CT); Brown, Stephen H. (East Haven, CT)

    1989-01-01

    The space-time yield and/or the selectivity of the photochemical dimerization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and primary, secondary and tertiary silanes with Hg and U.V. light is enhanced by refluxing the substrate in the irradiated reaction zone at a temperature at which the dimer product condenses and remains condensed promptly upon its formation. Cross-dimerization of the alkanes, ethers and silanes with primary alcohols is disclosed, as is the functionalization to aldehydes of the alkanes with carbon monoxide.

  19. Transient oxidative stress and inflammation after intraperitoneal administration of multiwalled carbon nanotubes functionalized with single strand DNA in rats

    SciTech Connect (OSTI)

    Clichici, Simona; Biris, Alexandru Radu; Tabaran, Flaviu; Filip, Adriana

    2012-03-15

    Multi-walled carbon nanotubes (MWCNTs) are widely used for nanotechnology. Their impact on living organisms is, however, not entirely clarified. Oxidative stress and inflammation seem to be the key mechanisms involved in MWCNTs' cytotoxicity. Until present, pulmonary and skin models were the main tested experimental designs to assess carbon nanotubes' toxicity. The systemic administration of MWCNTs is essential, with respect for future medical applications. Our research is performed on Wistar rats and is focused on the dynamics of oxidative stress parameters in blood and liver and pro-inflammatory cytokines in liver, after single dose (270 mg l{sup −1}) ip administration of MWCNTs (exterior diameter 15–25 nm, interior diameter 10–15 nm, surface 88 m{sup 2} g{sup −1}) functionalized with single strand DNA (ss-DNA). The presence of MWCNTs in blood was assessed by Raman spectroscopy, while in liver histological examination and confocal microscopy were used. It was found that ss-DNA-MWCNTs induce oxidative stress in plasma and liver, with the return of the tested parameters to normal values, 6 h after ip injection of nanotubes, with the exception of reduced glutathione in plasma. The inflammatory cytokines (TNF-α, IL-1β) had a similar pattern of evolution. We also assessed the level of ERK1/2 and the phosphorylation of p65 subunit of NF-kB in liver that had a transient increase and returned to normal at the end of the tested period. Our results demonstrate that ss-DNA-MWCNTs produce oxidative stress and inflammation, but with a transient pattern. Given the fact that antioxidants modify the profile not only for oxidative stress, but also of inflammation, the dynamics of these alterations may be of practical importance for future protective strategies. -- Highlights: ► ss-DNA-MWCNTs ip administration induce oxidative stress in plasma and liver. ► ss-DNA-MWCNTs ip administration determine liver inflammation. ► ERK1/2 and p65 phosphorylated NF-KB increase

  20. The impact of carbon sp{sup 2} fraction of reduced graphene oxide on the performance of reduced graphene oxide contacted organic transistors

    SciTech Connect (OSTI)

    Kang, Narae; Khondaker, Saiful I.

    2014-12-01

    One of the major bottlenecks in fabricating high performance organic field effect transistors (OFETs) is a large interfacial contact barrier between metal electrodes and organic semiconductors (OSCs) which makes the charge injection inefficient. Recently, reduced graphene oxide (RGO) has been suggested as an alternative electrode material for OFETs. RGO has tunable electronic properties and its conductivity can be varied by several orders of magnitude by varying the carbon sp{sup 2} fraction. However, whether the sp{sup 2} fraction of RGO in the electrode affects the performance of the fabricated OFETs is yet to be investigated. In this study, we demonstrate that the performance of OFETs with pentacene as OSC and RGO as electrode can be continuously improved by increasing the carbon sp{sup 2} fraction of RGO. When compared to control palladium electrodes, the mobility of the OFETs shows an improvement of ∼200% for 61% sp{sup 2} fraction RGO, which further improves to ∼500% for 80% RGO electrode. Similar improvements were also observed in current on-off ratio, on-current, and transconductance. Our study suggests that, in addition to π-π interaction at RGO/pentacene interface, the tunable electronic properties of RGO electrode have a significant role in OFETs performance.

  1. Methanol Decomposition over Palladium Particles Supported on Silica: Role of Particle Size and Co-Feeding Carbon Dioxide on the Catalytic Properties

    SciTech Connect (OSTI)

    Hokenek, Selma; Kuhn, John N. (USF)

    2012-10-23

    Monodisperse palladium particles of six distinct and controlled sizes between 4-16 nm were synthesized in a one-pot polyol process by varying the molar ratios of the two palladium precursors used, which contained palladium in different oxidation states. This difference permitted size control by regulation of the nucleation rate because low oxidation state metals ions nucleate quickly relative to high oxidation state ions. After immobilization of the Pd particles on silica by mild sonication, the catalysts were characterized by X-ray absorption spectroscopy and applied toward catalytic methanol decomposition. This reaction was determined as structure sensitive with the intrinsic activity (turnover frequency) increasing with increasing particle size. Moreover, observed catalytic deactivation was linked to product (carbon monoxide) poisoning. Co-feeding carbon dioxide caused the activity and the amount of deactivation to decrease substantially. A reaction mechanism based on the formation of the {pi}-bond between carbon and oxygen as the rate-limiting step is in agreement with antipathetic structure sensitivity and product poisoning by carbon monoxide.

  2. High surface area, electrically conductive nanocarbon-supported metal oxide

    DOE Patents [OSTI]

    Worsley, Marcus A.; Han, Thomas Yong-Jin; Kuntz, Joshua D.; Cervantes, Octavio; Gash, Alexander E.; Baumann, Theodore F.; Satcher, Jr., Joe H.

    2015-07-14

    A metal oxide-carbon composite includes a carbon aerogel with an oxide overcoat. The metal oxide-carbon composite is made by providing a carbon aerogel, immersing the carbon aerogel in a metal oxide sol under a vacuum, raising the carbon aerogel with the metal oxide sol to atmospheric pressure, curing the carbon aerogel with the metal oxide sol at room temperature, and drying the carbon aerogel with the metal oxide sol to produce the metal oxide-carbon composite. The step of providing a carbon aerogel can provide an activated carbon aerogel or provide a carbon aerogel with carbon nanotubes that make the carbon aerogel mechanically robust.

  3. High surface area, electrically conductive nanocarbon-supported metal oxide

    DOE Patents [OSTI]

    Worsley, Marcus A; Han, Thomas Yong-Jin; Kuntz, Joshua D; Cervanted, Octavio; Gash, Alexander E; Baumann, Theodore F; Satcher, Jr., Joe H

    2014-03-04

    A metal oxide-carbon composite includes a carbon aerogel with an oxide overcoat. The metal oxide-carbon composite is made by providing a carbon aerogel, immersing the carbon aerogel in a metal oxide sol under a vacuum, raising the carbon aerogel with the metal oxide sol to atmospheric pressure, curing the carbon aerogel with the metal oxide sol at room temperature, and drying the carbon aerogel with the metal oxide sol to produce the metal oxide-carbon composite. The step of providing a carbon aerogel can provide an activated carbon aerogel or provide a carbon aerogel with carbon nanotubes that make the carbon aerogel mechanically robust.

  4. Advanced Diesel Combustion with Low Hydrocarbon and Carbon Monoxide...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Ratio Particulate Produced from Advanced Combustion Operation in a Compression Ignition Engine Performance Characteristics of Coal-to-Liquids (CTL) Diesel in a 50-State ...

  5. Heterologous production of an energy-conserving carbon monoxide...

    Office of Scientific and Technical Information (OSTI)

    ... GrantContract Number: SC0012518 Type: Accepted Manuscript Journal Name: Frontiers in Microbiology Additional Journal Information: Journal Volume: 7; Journal ID: ISSN 1664-302X ...

  6. Heterologous production of an energy-conserving carbon monoxide...

    Office of Scientific and Technical Information (OSTI)

    GrantContract Number: SC0012518 Type: Accepted Manuscript Journal Name: Frontiers in Microbiology Additional Journal Information: Journal Volume: 7; Journal ID: ISSN 1664-302X ...

  7. Advanced Diesel Combustion with Low Hydrocarbon and Carbon Monoxide Emissions

    Broader source: Energy.gov [DOE]

    Poster presented at the 16th Directions in Engine-Efficiency and Emissions Research (DEER) Conference in Detroit, MI, September 27-30, 2010.

  8. Effects of temperature and acidic pre-treatment on Fenton-driven oxidation of MTBE-spent granular activated carbon

    SciTech Connect (OSTI)

    Kan, E.; Huling, S.G.

    2009-03-01

    The effects of temperature and acidic pretreatment on Fenton-driven chemical oxidation of methyl tert-butyl ether (MTBE)-spent granular activated carbon (GAC, derived from bituminous coal) were investigated. Limiting factors in MTBE removal in GAC include the heterogeneous distribution of amended Fe, and slow intraparticle diffusive transport of MTBE and hydrogen peroxide (H{sub 2}O{sub 2}) into the 'reactive zone'. Acid pretreatment of GAC before Fe amendment altered the surface chemistry of the GAC, lowered the pH point of zero charge, and resulted in greater penetration and more uniform distribution of Fe in GAC. This led to a condition where Fe, MTBE, and H{sub 2}O{sub 2} coexisted over a larger volume of the GAC contributing to greater MTBE oxidation and removal. H{sub 2}O{sub 2} reaction and MTBE removal in GAC increased with temperature. Modeling H{sub 2}O{sub 2} transport and reaction in GAC indicated that H{sub 2}O{sub 2} penetration was inversely proportional with temperature and tortuosity, and occurred over a larger fraction of the total volume of small GAC particles (0.3 mm diameter) relative to large particles (1.2 mm diameter). Acidic pretreatment of GAC, Fe-amendment, elevated reaction temperature, and use of small GAC particles are operational parameters that improve Fenton-driven oxidation of MTBE in GAC. 29 refs., 6 figs., 1 tab.

  9. Conversion of alkali metal sulfate to the carbonate

    DOE Patents [OSTI]

    Sheth, Atul C. (Woodridge, IL)

    1982-01-01

    A process for converting potassium sulfate to potassium carbonate in which a mixture of potassium sulfate and calcium oxide are reacted at a temperature in the range of between about 700.degree. C. and about 800.degree. C. with a gaseous mixture having a minor amount of hydrogen and/or carbon monoxide in a diluent with the calcium oxide being present in an amount not greater than about 20 percent by weight of the potassium sulfate to produce an aqueous mixture of potassium sulfide, potassium bisulfide, potassium hydroxide and calcium sulfide and a gaseous mixture of steam and hydrogen sulfide. The potassium and calcium salts are quenched to produce an aqueous slurry of soluble potassium salts and insoluble calcium salts and a gaseous mixture of steam and hydrogen sulfide. The insoluble calcium salts are then separated from the aqueous solution of soluble potassium salts. The calcium salts are dried to produce calcium sulfide, calcium bisulfide and steam, and then, the calcium sulfide and calcium bisulfide are converted to the oxide and recycled. The soluble potassium salts are carbonated to produce potassium carbonate which is concentrated and the precipitated crystals separated. The sulfur-containing compounds are further treated.

  10. Geochemical Impacts of Carbon Dioxide, Brine, Trace Metal and Organic Leakage into an Unconfined, Oxidizing Limestone Aquifer

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Bacon, Diana H.; Dai, Zhenxue; Zheng, Liange

    2014-12-31

    An important risk at CO2 storage sites is the potential for groundwater quality impacts. As part of a system to assess the potential for these impacts a geochemical scaling function has been developed, based on a detailed reactive transport model of CO2 and brine leakage into an unconfined, oxidizing carbonate aquifer. Stochastic simulations varying a number of geochemical parameters were used to generate a response surface predicting the volume of aquifer that would be impacted with respect to regulated contaminants. The brine was assumed to contain several trace metals and organic contaminants. Aquifer pH and TDS were influenced by CO2more » leakage, while trace metal concentrations were most influenced by the brine concentrations rather than adsorption or desorption on calcite. Organic plume sizes were found to be strongly influenced by biodegradation.« less

  11. Control of carbon balance in a silicon smelting furnace

    DOE Patents [OSTI]

    Dosaj, V.D.; Haines, C.M.; May, J.B.; Oleson, J.D.

    1992-12-29

    The present invention is a process for the carbothermic reduction of silicon dioxide to form elemental silicon. Carbon balance of the process is assessed by measuring the amount of carbon monoxide evolved in offgas exiting the furnace. A ratio of the amount of carbon monoxide evolved and the amount of silicon dioxide added to the furnace is determined. Based on this ratio, the carbon balance of the furnace can be determined and carbon feed can be adjusted to maintain the furnace in carbon balance.

  12. Studies of Scale Formation and Kinetics of Crofer 22 APU and Haynes 230 in Carbon Oxide-Containing Environment for SOFC Applications

    SciTech Connect (OSTI)

    Ziomek-Moroz, M.; Covino, B.S., Jr.; Holcomb, G.R.; Bullard, S.J.; Penner, L.R.

    2006-01-01

    Significant progress in reducing the operating temperature of SOFCs below 800oC may allow the use of chromia-forming metallic interconnects at a substantial cost savings. Hydrogen is the main fuel for all types of fuel cells except direct methanol fuel cells. Hydrogen can be generated from fossil fuels, including coal, natural gas, diesel, gasoline, other hydrocarbons, and oxygenates (e.g., methanol, ethanol, butanol, etc.). Carbon oxides present in the hydrogen fuel can cause significant performance problems due to carbon formation (coking). Also, literature data indicate that in CO/CO2 gaseous environments, metallic materials that gain their corrosion resistance due to formation of Cr2O3, could form stable chromium carbides. The chromium carbide formation causes depletion of chromium in these alloys. If the carbides oxidize, they form non-protective scales. Considering a potential detrimental effect of carbon oxides on iron- and nickel-base alloy stability, determining corrosion performance of metallic interconnect candidates in carbon oxide-containing environments at SOFC operating temperatures is a must. In this research, the corrosion behavior of Crofer 22 APU and Haynes 230 was studied in a CO-rich atmosphere at 750°C. Chemical composition of the gaseous environment at the outlet was determined using gas chromatography (GC). After 800 h of exposure to the gaseous environment the surfaces of the corroded samples were studied by scanning electron microscopy (SEM) equipped with microanalytical capabilities. X-ray diffraction (XRD) analysis was also used in this study.

  13. Chemical changes in carbon Nanotube-Nickel/Nickel Oxide Core/Shell nanoparticle heterostructures treated at high temperatures

    SciTech Connect (OSTI)

    Chopra, Nitin; McWhinney, Hylton G.; Shi Wenwu

    2011-06-15

    Heterostructures composed of carbon nanotube (CNT) coated with Ni/NiO core/shell nanoparticles (denoted as CNC heterostructures) were synthesized in a wet-chemistry and single-step synthesis route involving direct nucleation of nanoparticles on CNT surface. Two different aspects of CNC heterostructures were studied here. First, it was observed that the nanoparticle coatings were more uniform on the as-produced and non-purified CNTs compared to purified (or acid treated) CNTs. These heterostructures were characterized using electron microscopy, Raman spectroscopy, and energy dispersive spectroscopy. Second, thermal stability of CNC heterostructures was studied by annealing them in N{sub 2}-rich (O{sub 2}-lean) environment between 125 and 750 deg. C for 1 h. A detailed X-ray photoelectron spectroscopy and Raman spectroscopy analysis was performed to evaluate the effects of annealing temperatures on chemical composition, phases, and stability of the heterostructures. It was observed that the CNTs present in the heterostructures completely decomposed and core Ni nanoparticle oxidized significantly between 600 and 750 deg. C. - Research Highlights: {yields} Heterostructures composed of CNTs coated with Ni/NiO core/shell nanoparticles. {yields} Poor nanoparticle coverage on purified CNT surface compared to non-purified CNTs. {yields} CNTs in heterostructures decompose between 600 and 750 deg. C in N{sub 2}-rich atmosphere. {yields} Metallic species in heterostructures were oxidized at higher temperatures.

  14. Modeling global atmospheric CO2 with improved emission inventories and CO2 production from the oxidation of other carbon species

    SciTech Connect (OSTI)

    Nassar, Ray; Jones, DBA; Suntharalingam, P; Chen, j.; Andres, Robert Joseph; Wecht, K. J.; Yantosca, R. M.; Kulawik, SS; Bowman, K; Worden, JR; Machida, T; Matsueda, H

    2010-01-01

    The use of global three-dimensional (3-D) models with satellite observations of CO2 in inverse modeling studies is an area of growing importance for understanding Earth s carbon cycle. Here we use the GEOS-Chem model (version 8-02-01) CO2 mode with multiple modifications in order to assess their impact on CO2 forward simulations. Modifications include CO2 surface emissions from shipping (0.19 PgC yr 1), 3-D spatially-distributed emissions from aviation (0.16 PgC yr 1), and 3-D chemical production of CO2 (1.05 PgC yr 1). Although CO2 chemical production from the oxidation of CO, CH4 and other carbon gases is recognized as an important contribution to global CO2, it is typically accounted for by conversion from its precursors at the surface rather than in the free troposphere. We base our model 3-D spatial distribution of CO2 chemical production on monthly-averaged loss rates of CO (a key precursor and intermediate in the oxidation of organic carbon) and apply an associated surface correction for inventories that have counted emissions of CO2 precursors as CO2. We also explore the benefit of assimilating satellite observations of CO into GEOS-Chem to obtain an observation-based estimate of the CO2 chemical source. The CO assimilation corrects for an underestimate of atmospheric CO abundances in the model, resulting in increases of as much as 24% in the chemical source during May June 2006, and increasing the global annual estimate of CO2 chemical production from 1.05 to 1.18 Pg C. Comparisons of model CO2 with measurements are carried out in order to investigate the spatial and temporal distributions that result when these new sources are added. Inclusion of CO2 emissions from shipping and aviation are shown to increase the global CO2 latitudinal gradient by just over 0.10 ppm (3%), while the inclusion of CO2 chemical production (and the surface correction) is shown to decrease the latitudinal gradient by about 0.40 ppm (10%) with a complex spatial structure

  15. Method for producing carbon nanotubes

    DOE Patents [OSTI]

    Phillips, Jonathan; Perry, William L.; Chen, Chun-Ku

    2006-02-14

    Method for producing carbon nanotubes. Carbon nanotubes were prepared using a low power, atmospheric pressure, microwave-generated plasma torch system. After generating carbon monoxide microwave plasma, a flow of carbon monoxide was directed first through a bed of metal particles/glass beads and then along the outer surface of a ceramic tube located in the plasma. As a flow of argon was introduced into the plasma through the ceramic tube, ropes of entangled carbon nanotubes, attached to the surface of the tube, were produced. Of these, longer ropes formed on the surface portion of the tube located in the center of the plasma. Transmission electron micrographs of individual nanotubes revealed that many were single-walled.

  16. Steady state and dynamic modeling of a packed bed reactor for the partial oxidation of methanol to formaldehyde: experimental results compared with model predictions

    SciTech Connect (OSTI)

    Schwedock, M.J.; Windes, L.C.; Ray, W.H.

    1985-01-01

    Heterogeneous and pseudohomogeneous models are compared to experimental data from a packed bed reactor for the partical oxidation of methanol to formaldehyde over an iron oxide-molybdenum oxide catalyst. Heat transfer parameters which were successful in matching data from experiments without reaction were not successful in matching temperature data from experiments with reaction. This made it necessary to decrease the fluid radial heat transfer to obtain good fit. A good fit was obtained for steady state composition profiles by optimizing selected frequency factors and the activation energy for methanol. A redox rate expression for the oxidation of formaldehyde to carbon monoxide was proposed since a simple first-order rate expression did not fit the data. The pseudohomogeneous model gave results similar to the heterogeneous model for both steady state and dynamic experiments and has been recommended for future experimental state estimation and control studies. 21 refs., 31 figs., 6 tabs.

  17. Development and Commercialization of Alternative Carbon Fiber...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Vehicle Technologies Office Merit Review 2015: Advanced Oxidation & Stabilization of PAN-Based Carbon Precursor Fibers Advanced Oxidation & Stabilization of PAN-Based Carbon ...

  18. Hydrous ruthenium oxide nanoparticles anchored to graphene and carbon nanotube hybrid foam for supercapacitors

    SciTech Connect (OSTI)

    Wang, Wei; Guo, S.; Lee, I.; Ahmed, K.; Zhong, J.; Favors, Z.; Zaera, F.; Ozkan, M.; Ozkan, C. S

    2014-03-25

    In real life applications, supercapacitors (SCs) often can only be used as part of a hybrid system together with other high energy storage devices due to their relatively lower energy density in comparison to other types of energy storage devices such as batteries and fuel cells. Increasing the energy density of SCs will have a huge impact on the development of future energy storage devices by broadening the area of application for SCs. Here, we report a simple and scalable way of preparing a three-dimensional (3D) sub-5 nm hydrous ruthenium oxide (RuO?) anchored graphene and CNT hybrid foam (RGM) architecture for high-performance supercapacitor electrodes. This RGM architecture demonstrates a novel graphene foam conformally covered with hybrid networks of RuO? nanoparticles and anchored CNTs. SCs based on RGM show superior gravimetric and per-area capacitive performance (specific capacitance: 502.78 F g?, areal capacitance: 1.11 F cm?) which leads to an exceptionally high energy density of 39.28 Wh kg? and power density of 128.01 kW kg?. The electrochemical stability, excellent capacitive performance, and the ease of preparation suggest this RGM system is promising for future energy storage applications.

  19. Oxidation catalyst systems for emission control of LPG-powered forklift trucks

    SciTech Connect (OSTI)

    Majewski, W.A.; Martin, E.P.; Pietrasz, E.

    1994-10-01

    An oxidation catalyst was installed on an industrial LPG-powered forklift truck. For high conversion efficiency in an oxidation system on a rich burning engine a secondary air supply to the catalyst is necessary. Two simple and cost-effective ways of secondary air supply were tested: an air valve and a venturi type injector. The amount of secondary air supplied by both devices was measured under a variety of conditions - different engine speed, load and exhaust system pressure. Carbon monoxide emissions and the catalyst performance were measured and evaluated in terms of the secondary air flow. Advantages and drawbacks of the air valve and venturi injector systems are discussed and compared. 1 refs., 11 figs., 3 tabs.

  20. Boron nitride converted carbon fiber

    DOE Patents [OSTI]

    Rousseas, Michael; Mickelson, William; Zettl, Alexander K.

    2016-04-05

    This disclosure provides systems, methods, and apparatus related to boron nitride converted carbon fiber. In one aspect, a method may include the operations of providing boron oxide and carbon fiber, heating the boron oxide to melt the boron oxide and heating the carbon fiber, mixing a nitrogen-containing gas with boron oxide vapor from molten boron oxide, and converting at least a portion of the carbon fiber to boron nitride.

  1. Ternary Electrocatalysts for Oxidizing Ethanol to Carbon Dioxide: Making Ir Capable of Splitting C-C bond

    SciTech Connect (OSTI)

    Li, Meng; Cullen, David A; Sasaki, Kotaro; Marinkovic, N.; More, Karren Leslie; Adzic, Radoslav R.

    2013-01-01

    Splitting the C-C bond is the main obstacle to electroxidation of ethanol (EOR) to CO2. We recently demonstrated that the ternary PtRhSnO2 electrocatalyst can accomplish that reaction at room temperature with Rh having a unique capability to split the C-C bond. In this article we report the finding that Ir can be induced to split the C-C bond as a component of the ternary catalyst. We synthesized, characterized and compared the properties of several ternary electrocatalysts. Carbon-supported nanoparticle (NP) electrocatalysts comprising a SnO2 NP core decorated with multi-metallic nanoislands (MM = PtIr, PtRh, IrRh, PtIrRh) were prepared using a seeded growth approach. An array of characterization techniques were employed to establish the composition and architecture of the synthesized MM /SnO2 NPs, while electrochemical and in situ infrared reflection absorption spectroscopy studies elucidated trends in activity and the nature of the reaction intermediates and products. Both EOR reactivity and selectivity towards CO2 formation of several of these MM /SnO2/C electrocatalysts are significantly higher compared to conventional Pt/C and Pt/SnO2/C catalysts. We demonstrate that the PtIr/SnO2/C catalyst with high Ir content shows outstanding catalytic property with the most negative EOR onset potential and reasonably good selectivity towards ethanol complete oxidation to CO2. PtRh/SnO2/C catalysts with a moderate Rh content exhibit the highest EOR selectivity, as deduced from infrared studies.

  2. Laser hydrothermal reductive ablation of titanium monoxide: Hydrated TiO particles with modified Ti/O surface

    SciTech Connect (OSTI)

    Blazevska-Gilev, Jadranka; Jandova, Vera; Kupcik, Jaroslav; Bastl, Zdenek; Subrt, Jan; Bezdicka, Petr; Pola, Josef

    2013-01-15

    IR laser- and UV laser-induced ablation of titanium monoxide (TM) in hydrogen (50 Torr) is compared to the same process induced in vacuum and shown to result in deposition of hydrated surface modified nanostructured titanium suboxide films. Complementary analyses of the films deposited in vacuum and in hydrogen by Fourier transform infrared, Raman and X-ray photoelectron spectroscopy, X-ray diffraction and electron microscopy allowed to determine different features of both films and propose a mechanism of surface modification of ejected particles, which involves hydrothermal reduction of TM and subsequent reactions of evolved water. The films exert good adhesion to metal and quartz surfaces and are hydrophobic in spite of having their surface coated with adsorbed water. - Graphical abstract: Laser ablation of titanium monoxide (TiO) in hydrogen involves a sequence of H{sub 2} and H{sub 2}O eliminations and additions and yields hydrated amorphous nanostructured titanium suboxide which is richer in oxygen than TiO. Highlights: Black-Right-Pointing-Pointer IR and UV laser ablated particles of titanium monoxide (TiO) undergo amorphization. Black-Right-Pointing-Pointer Films deposited in vacuum have TiO stoichiometry and are oxidized in atmosphere. Black-Right-Pointing-Pointer Films deposited in hydrogen are hydrated and have more O in topmost layers. Black-Right-Pointing-Pointer Films modification in hydrogen is explained by reactions in hydrogen plasma.

  3. ARM - Measurement - Black carbon concentration

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    of carbon in its very absorbing, elemental, non-organic, non-oxide form (e.g. graphite). Categories Aerosols, Atmospheric Carbon Instruments The above measurement is...

  4. Erosion-oxidation of carbon steel in the convection section of an industrial boiler cofiring coal-water fuel and natural gas

    SciTech Connect (OSTI)

    Xie, J.J.; Walsh, P.M.

    1997-07-01

    Walsh et al. (1994) reported measurements of erosion of carbon steel by fly ash and unburned char particles in the convective heat transfer section of an industrial boiler cofiring coal-water fuel and natural gas. Changes in shape of the surface were measured using a surface profiler. Time-averaged maximum erosion rates were obtained from the differences between the original surface height and the lowest points in the profiles. A model was developed by Xie (1995) to describe wastage of tube material in the presence of erosion by particle impacts and oxidation of the metal. The observed changes in erosion rate with temperature and oxygen concentration were consistent with a mechanism based upon the following assumptions: (1) metal was eroded as a ductile material, at a rate that increased with increasing temperature; (2) oxide was eroded as a brittle material, at a rate independent of temperature; (3) the oxide scale was strongly attached to the metal; (4) the erosion resistance of metal and scale was a linear combination of the resistances of the individual components; (5) oxide formed according to the parabolic rate law, with a rate coefficient proportional to the square root of the oxygen partial pressure; (6) erosion resistance from particles sticking to, or embedded in, the surface was negligible. Using the model and rate coefficients for metal and oxide erosion derived from the measurements, estimates were made of the erosion rate of a boiler tube as functions of impaction angle and gas velocity. Under the conditions of metal temperature, gas composition, particle size, particle concentration, and particle composition investigated, erosion of carbon steel is expected to be slower than 0.05 {micro}m/h when the gas velocity in the convection section is less than approximately 8 m/s.

  5. Fuel Mix and Emissions Disclosure | Department of Energy

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    rates of nitrogen oxides, sulfur oxides, carbon dioxide, carbon monoxide, particulates, heavy metals and other regulated wastes, as well as the estimated percentage of the total...

  6. Effect of carbon on stress corrosion cracking and anodic oxidation of iron in NaOH solutions

    SciTech Connect (OSTI)

    Flis, J.; Ziomek-Moroz, Margaret

    2008-06-01

    Anodic behaviour of decarburised iron and of quenched Fe–C materials with up to 0.875 wt% C was examined in 8.5 M NaOH at 100 °C to explain the role of carbon in caustic stress corrosion cracking (SCC) of plain steels. Removal of carbon from Armco iron strongly reduced its intergranular SCC. Slip steps on grains did not initiate cracks. It has been shown that carbon at low contents deteriorates the passivation of iron, whereas at high contents it promotes the formation of magnetite. High resistance to SCC of high carbon steels can be explained by an intense formation of magnetite on these steels.

  7. Life cycle inventory analysis of regenerative thermal oxidation of air emissions from oriented strand board facilities in Minnesota - a perspective of global climate change

    SciTech Connect (OSTI)

    Nicholson, W.J.

    1997-12-31

    Life cycle inventory analysis has been applied to the prospective operation of regenerative thermal oxidation (RTO) technology at oriented strand board plants at Bemidji (Line 1) and Cook, Minnesota. The net system destruction of VOC`s and carbon monoxide, and at Cook a small quantity of particulate, has a very high environmental price in terms of energy and water use, global warming potential, sulfur and nitrogen oxide emissions, solids discharged to water, and solid waste deposited in landfills. The benefit of VOC destruction is identified as minor in terms of ground level ozone at best and possibly slightly detrimental. Recognition of environmental tradeoffs associated with proposed system changes is critical to sound decision-making. There are more conventional ways to address carbon monoxide emissions than combustion in RTO`s. In an environment in which global warming is a concern, fuel supplemental combustion for environmental control does not appear warranted. Consideration of non-combustion approaches to address air emission issues at the two operations is recommended. 1 ref., 5 tabs.

  8. A Sensor System Based on Semi-Conductor Metal Oxide Technology for In Situ Detection of Coal Fired Combustion Gases

    SciTech Connect (OSTI)

    Brent Marquis

    2007-05-31

    Sensor Research and Development Corporation (SRD) proposed a two-phase program to develop a robust, autonomous prototype analyzer for in situ, real-time detection, identification, and measurement of coal-fired combustion gases and perform field-testing at an approved power generation facility. SRD developed and selected sensor materials showing selective responses to carbon monoxide, carbon dioxide, nitric oxide, nitrogen dioxide, ammonia, sulfur dioxide and hydrogen chloride. Sensor support electronics were also developed to enable prototype to function in elevated temperatures without any issues. Field-testing at DOE approved facility showed the ability of the prototype to detect and estimate the concentration of combustion by-products accurately with relatively low false-alarm rates at very fast sampling intervals.

  9. Molecular Characterization of Brown Carbon (BrC) Chromophores in Secondary Organic Aerosol Generated From Photo-Oxidation of Toluene

    SciTech Connect (OSTI)

    Lin, Peng; Liu, Jiumeng; Shilling, John E.; Kathmann, Shawn M.; Laskin, Julia; Laskin, Alexander

    2015-09-28

    Atmospheric Brown carbon (BrC) is a significant contributor to light absorption and climate forcing. However, little is known about a fundamental relationship between the chemical composition of BrC and its optical properties. In this work, light-absorbing secondary organic aerosol (SOA) was generated in the PNNL chamber from toluene photo-oxidation in the presence of NOx (Tol-SOA). Molecular structures of BrC components were examined using nanospray desorption electrospray ionization (nano-DESI) and liquid chromatography (LC) combined with UV/Vis spectroscopy and electrospray ionization (ESI) high-resolution mass spectrometry (HRMS). The chemical composition of BrC chromophores and the light absorption properties of toluene SOA (Tol-SOA) depend strongly on the initial NOx concentration. Specifically, Tol-SOA generated under high-NOx conditions (defined here as initial NOx/toluene of 5/1) appears yellow and mass absorption coefficient of the bulk sample (MACbulk@365nm = 0.78 m2 g-1) is nearly 80 fold higher than that measured for the Tol-SOA sample generated under low-NOx conditions (NOx/toluene < 1/300). Fifteen compounds, most of which are nitrophenols, are identified as major BrC chromophores responsible for the enhanced light absorption of Tol-SOA material produced in the presence of NOx. The integrated absorbance of these fifteen chromophores accounts for 40-60% of the total light absorbance by Tol-SOA at wavelengths between 300 nm and 500 nm. The combination of tandem LC-UV/Vis-ESI/HRMS measurements provides an analytical platform for predictive understanding of light absorption properties by BrC and their relationship to the structure of individual chromophores. General trends in the UV/vis absorption by plausible isomers of the BrC chromophores were evaluated using theoretical chemistry calculations. The molecular-level understanding of BrC chemistry is helpful for better understanding the evolution and behavior of light absorbing aerosols in the atmosphere.

  10. Carbon investment funds

    SciTech Connect (OSTI)

    2007-01-15

    The report is a study of the development of funds to invest in the purchase of carbon credits. It takes a look at the growing market for carbon credits, the rise of carbon investment funds, and the current state of carbon investing. Topics covered in the report include: Overview of climate change, greenhouse gases, and the Kyoto Protocols. Analysis of the alternatives for reducing carbon emissions including nitrous oxide reduction, coal mine methane capture and carbon capture and storage; Discussion of the different types of carbon credits; Discussion of the basics of carbon trading; Evaluation of the current status of carbon investing; and Profiles of 37 major carbon investment funds worldwide.

  11. High surface area silicon carbide-coated carbon aerogel

    DOE Patents [OSTI]

    Worsley, Marcus A; Kuntz, Joshua D; Baumann, Theodore F; Satcher, Jr, Joe H

    2014-01-14

    A metal oxide-carbon composite includes a carbon aerogel with an oxide overcoat. The metal oxide-carbon composite is made by providing a carbon aerogel, immersing the carbon aerogel in a metal oxide sol under a vacuum, raising the carbon aerogel with the metal oxide sol to atmospheric pressure, curing the carbon aerogel with the metal oxide sol at room temperature, and drying the carbon aerogel with the metal oxide sol to produce the metal oxide-carbon composite. The step of providing a carbon aerogel can provide an activated carbon aerogel or provide a carbon aerogel with carbon nanotubes that make the carbon aerogel mechanically robust. Carbon aerogels can be coated with sol-gel silica and the silica can be converted to silicone carbide, improved the thermal stability of the carbon aerogel.

  12. Cobalt carbonyl catalyzed olefin hydroformylation in supercritical carbon dioxide

    DOE Patents [OSTI]

    Rathke, Jerome W. (Lockport, IL); Klingler, Robert J. (Westmount, IL)

    1993-01-01

    A method of olefin hydroformylation is provided wherein an olefin reacts with a carbonyl catalyst and with reaction gases such as hydrogen and carbon monoxide in the presence of a supercritical reaction solvent, such as carbon dioxide. The invention provides higher yields of n-isomer product without the gas-liquid mixing rate limitation seen in conventional Oxo processes using liquid media.

  13. Cobalt carbonyl catalyzed olefin hydroformylation in supercritical carbon dioxide

    DOE Patents [OSTI]

    Rathke, J.W.; Klingler, R.J.

    1993-03-30

    A method of olefin hydroformylation is provided wherein an olefin reacts with a carbonyl catalyst and with reaction gases such as hydrogen and carbon monoxide in the presence of a supercritical reaction solvent, such as carbon dioxide. The invention provides higher yields of n-isomer product without the gas-liquid mixing rate limitation seen in conventional Oxo processes using liquid media.

  14. Octahedral core–shell cuprous oxide/carbon with enhanced electrochemical activity and stability as anode for lithium ion batteries

    SciTech Connect (OSTI)

    Xiang, Jiayuan; Chen, Zhewei; Wang, Jianming

    2015-10-15

    Highlights: • Core–shell octahedral Cu{sub 2}O/C is prepared by a one-step method. • Carbon shell is amorphous and uniformly decorated at the Cu{sub 2}O octahedral core. • Core–shell Cu{sub 2}O/C exhibits markedly enhanced capability and reversibility. • Carbon shell provides fast ion/electron transfer channel. • Core–shell structure is stable during cycling. - Abstract: Core–shell Cu{sub 2}O/C octahedrons are synthesized by a simple hydrothermal method with the help of carbonization of glucose, which reduces Cu(II) to Cu(I) at low temperature and further forms carbon shell coating at high temperature. SEM and TEM images indicate that the carbon shell is amorphous with thickness of ∼20 nm wrapping the Cu{sub 2}O octahedral core perfectly. As anode of lithium ion batteries, the core–shell Cu{sub 2}O/C composite exhibits high and stable columbic efficiency (98%) as well as a reversible capacity of 400 mAh g{sup −1} after 80 cycles. The improved electrochemical performance is attributed to the novel core–shell structure, in which the carbon shell reduces the electrode polarization and promotes the charge transfer at active material/electrolyte interface, and also acts as a stabilizer to keep the octahedral structure integrity during discharge–charge processes.

  15. Solid oxide fuel cell generator with removable modular fuel cell stack configurations

    DOE Patents [OSTI]

    Gillett, J.E.; Dederer, J.T.; Zafred, P.R.; Collie, J.C.

    1998-04-21

    A high temperature solid oxide fuel cell generator produces electrical power from oxidation of hydrocarbon fuel gases such as natural gas, or conditioned fuel gases, such as carbon monoxide or hydrogen, with oxidant gases, such as air or oxygen. This electrochemical reaction occurs in a plurality of electrically connected solid oxide fuel cells bundled and arrayed in a unitary modular fuel cell stack disposed in a compartment in the generator container. The use of a unitary modular fuel cell stack in a generator is similar in concept to that of a removable battery. The fuel cell stack is provided in a pre-assembled self-supporting configuration where the fuel cells are mounted to a common structural base having surrounding side walls defining a chamber. Associated generator equipment may also be mounted to the fuel cell stack configuration to be integral therewith, such as a fuel and oxidant supply and distribution systems, fuel reformation systems, fuel cell support systems, combustion, exhaust and spent fuel recirculation systems, and the like. The pre-assembled self-supporting fuel cell stack arrangement allows for easier assembly, installation, maintenance, better structural support and longer life of the fuel cells contained in the fuel cell stack. 8 figs.

  16. Solid oxide fuel cell generator with removable modular fuel cell stack configurations

    DOE Patents [OSTI]

    Gillett, James E.; Dederer, Jeffrey T.; Zafred, Paolo R.; Collie, Jeffrey C.

    1998-01-01

    A high temperature solid oxide fuel cell generator produces electrical power from oxidation of hydrocarbon fuel gases such as natural gas, or conditioned fuel gases, such as carbon monoxide or hydrogen, with oxidant gases, such as air or oxygen. This electrochemical reaction occurs in a plurality of electrically connected solid oxide fuel cells bundled and arrayed in a unitary modular fuel cell stack disposed in a compartment in the generator container. The use of a unitary modular fuel cell stack in a generator is similar in concept to that of a removable battery. The fuel cell stack is provided in a pre-assembled self-supporting configuration where the fuel cells are mounted to a common structural base having surrounding side walls defining a chamber. Associated generator equipment may also be mounted to the fuel cell stack configuration to be integral therewith, such as a fuel and oxidant supply and distribution systems, fuel reformation systems, fuel cell support systems, combustion, exhaust and spent fuel recirculation systems, and the like. The pre-assembled self-supporting fuel cell stack arrangement allows for easier assembly, installation, maintenance, better structural support and longer life of the fuel cells contained in the fuel cell stack.

  17. Modeling the Impact of Carbon Dioxide Leakage into an Unconfined...

    Office of Scientific and Technical Information (OSTI)

    the Impact of Carbon Dioxide Leakage into an Unconfined, Oxidizing Carbonate Aquifer Citation Details In-Document Search Title: Modeling the Impact of Carbon Dioxide Leakage ...

  18. Method for converting hydrocarbon fuel into hydrogen gas and carbon dioxide

    DOE Patents [OSTI]

    Clawson, Lawrence G.; Mitchell, William L.; Bentley, Jeffrey M.; Thijssen, Johannes H. J.

    2000-01-01

    A method for converting hydrocarbon fuel into hydrogen gas and carbon dioxide within a reformer 10 is disclosed. According to the method, a stream including an oxygen-containing gas is directed adjacent to a first vessel 18 and the oxygen-containing gas is heated. A stream including unburned fuel is introduced into the oxygen-containing gas stream to form a mixture including oxygen-containing gas and fuel. The mixture of oxygen-containing gas and unburned fuel is directed tangentially into a partial oxidation reaction zone 24 within the first vessel 18. The mixture of oxygen-containing gas and fuel is further directed through the partial oxidation reaction zone 24 to produce a heated reformate stream including hydrogen gas and carbon monoxide. Steam may also be mixed with the oxygen-containing gas and fuel, and the reformate stream from the partial oxidation reaction zone 24 directed into a steam reforming zone 26. High- and low-temperature shift reaction zones 64,76 may be employed for further fuel processing.

  19. High Catalytic Activity of Au/CeOx/TiO2(110) Controlled by the Nature of the Mixed Metal Oxide at the Nanometer Level

    SciTech Connect (OSTI)

    Park, J.; Graciani, J; Evans, J; Stacchiola, D; Ma, S; Liu, P; Nambu, A; Sanz, J; Hrbek, J; et. al.

    2009-01-01

    Mixed-metal oxides play a very important role in many areas of chemistry, physics, materials science, and geochemistry. Recently, there has been a strong interest in understanding phenomena associated with the deposition of oxide nanoparticles on the surface of a second (host) oxide. Here, scanning tunneling microscopy, photoemission, and density-functional calculations are used to study the behavior of ceria nanoparticles deposited on a TiO2(110) surface. The titania substrate imposes nontypical coordination modes on the ceria nanoparticles. In the CeOx/TiO2(110) systems, the Ce cations adopt an structural geometry and an oxidation state (+3) that are quite different from those seen in bulk ceria or for ceria nanoparticles deposited on metal substrates. The increase in the stability of the Ce3+ oxidation state leads to an enhancement in the chemical and catalytic activity of the ceria nanoparticles. The codeposition of ceria and gold nanoparticles on a TiO2(110) substrate generates catalysts with an extremely high activity for the production of hydrogen through the water-gas shift reaction (H2O + CO ? H2 + CO2) or for the oxidation of carbon monoxide (2CO + O2 ? 2CO2). The enhanced stability of the Ce3+ state is an example of structural promotion in catalysis described here on the atomic level. The exploration of mixed-metal oxides at the nanometer level may open avenues for optimizing catalysts through stabilization of unconventional surface structures with special chemical activity.

  20. Reduced-Order Model for the Geochemical Impacts of Carbon Dioxide, Brine and Trace Metal Leakage into an Unconfined, Oxidizing Carbonate Aquifer, Version 2.1

    SciTech Connect (OSTI)

    Bacon, Diana H.

    2013-03-31

    The National Risk Assessment Partnership (NRAP) consists of 5 U.S DOE national laboratories collaborating to develop a framework for predicting the risks associated with carbon sequestration. The approach taken by NRAP is to divide the system into components, including injection target reservoirs, wellbores, natural pathways including faults and fractures, groundwater and the atmosphere. Next, develop a detailed, physics and chemistry-based model of each component. Using the results of the detailed models, develop efficient, simplified models, termed reduced order models (ROM) for each component. Finally, integrate the component ROMs into a system model that calculates risk profiles for the site. This report details the development of the Groundwater Geochemistry ROM for the Edwards Aquifer at PNNL. The Groundwater Geochemistry ROM for the Edwards Aquifer uses a Wellbore Leakage ROM developed at LANL as input. The detailed model, using the STOMP simulator, covers a 5x8 km area of the Edwards Aquifer near San Antonio, Texas. The model includes heterogeneous hydraulic properties, and equilibrium, kinetic and sorption reactions between groundwater, leaked CO2 gas, brine, and the aquifer carbonate and clay minerals. Latin Hypercube sampling was used to generate 1024 samples of input parameters. For each of these input samples, the STOMP simulator was used to predict the flux of CO2 to the atmosphere, and the volume, length and width of the aquifer where pH was less than the MCL standard, and TDS, arsenic, cadmium and lead exceeded MCL standards. In order to decouple the Wellbore Leakage ROM from the Groundwater Geochemistry ROM, the response surface was transformed to replace Wellbore Leakage ROM input parameters with instantaneous and cumulative CO2 and brine leakage rates. The most sensitive parameters proved to be the CO2 and brine leakage rates from the well, with equilibrium coefficients for calcite and dolomite, as well as the number of illite and kaolinite

  1. The electric dipole moment of cobalt monoxide, CoO

    SciTech Connect (OSTI)

    Zhuang, Xiujuan; Steimle, Timothy C.

    2014-03-28

    A number of low-rotational lines of the E{sup 4}?{sub 7/2}???X{sup 4}?{sub 7/2} (1,0) band system of cobalt monoxide, CoO, were recorded field free and in the presence of a static electric field. The magnetic hyperfine parameter, h{sub 7/2}, and the electron quadrupole parameter, eQq{sub 0}, for the E{sup 4}?{sub 7/2}(? = 1) state were optimized from the analysis of the field-free spectrum. The permanent electric dipole moment, ?{sup -vector}{sub el}, for the X{sup 4}?{sub 7/2} (? = 0) and E{sup 4}?{sub 7/2} (? = 1) states were determined to be 4.18 0.05 D and 3.28 0.05 D, respectively, from the analysis of the observed Stark spectra of F? = 7???F? = 6 branch feature in the Q(7/2) line and the F? = 8???F? = 7 branch feature in the R(7/2) line. The measured dipole moments of CoO are compared to those from theoretical predictions and the trend across the 3d-metal monoxide series discussed.

  2. Surface water and atmospheric carbon dioxide and nitrous oxide observations by shipboard automated gas chromatography: Results from expeditions between 1977 and 1990

    SciTech Connect (OSTI)

    Weiss, R.F.; Van Woy, F.A.; Salameh, P.K.; Sepanski, R.J.

    1992-12-01

    This document presents the results of surface water and atmospheric carbon dioxide (CO{sub 2}) and nitrous oxide (N{sub 2}O) measurements carried out by shipboard gas chromatography over the period 1977--1990. These data include results from 11 different oceanic surveys for a total of 41 expedition legs. Collectively, they represent a globally distributed sampling that includes locations in the Atlantic, Pacific, Indian, and Southern Oceans, as well as the Mediterranean and Red Seas. The measurements were made by an automated high-precision shipboard gas chromatographic system developed during the late 1970s and used extensively over the intervening years. This instrument measures CO{sub 2} by flame ionization after quantitative reaction to methane in a stream of hydrogen. Nitrous oxide is measured by a separate electron capture detector. The chromatographic system measures 196 dry-gas samples a day, divided equally among the atmosphere, gas equilibrated with surface water, a low-range gas standard, and a high-range gas standard.

  3. Surface water and atmospheric carbon dioxide and nitrous oxide observations by shipboard automated gas chromatography: Results from expeditions between 1977 and 1990

    SciTech Connect (OSTI)

    Weiss, R.F.; Van Woy, F.A.; Salameh, P.K. ); Sepanski, R.J. . Energy, Environment and Resources Center)

    1992-12-01

    This document presents the results of surface water and atmospheric carbon dioxide (CO[sub 2]) and nitrous oxide (N[sub 2]O) measurements carried out by shipboard gas chromatography over the period 1977--1990. These data include results from 11 different oceanic surveys for a total of 41 expedition legs. Collectively, they represent a globally distributed sampling that includes locations in the Atlantic, Pacific, Indian, and Southern Oceans, as well as the Mediterranean and Red Seas. The measurements were made by an automated high-precision shipboard gas chromatographic system developed during the late 1970s and used extensively over the intervening years. This instrument measures CO[sub 2] by flame ionization after quantitative reaction to methane in a stream of hydrogen. Nitrous oxide is measured by a separate electron capture detector. The chromatographic system measures 196 dry-gas samples a day, divided equally among the atmosphere, gas equilibrated with surface water, a low-range gas standard, and a high-range gas standard.

  4. Carbon emissions and sequestration in forests: Case studies from seven developing countries

    SciTech Connect (OSTI)

    Makundi, W.; Sathaye, J. ); Fearnside, P.M. , Manaus, AM . Departmento de Ecologia)

    1992-08-01

    Deforestation in Brazilian Amazonia in 1990 was releasing approximately 281--282 X 10{sup 6} metric tons (MT) of carbon on conversion to a landscape of agriculture, productive pasture, degraded pasture, secondary forest and regenerated forest in the proportions corresponding to the equilibrium condition implied by current land-use patterns. Emissions are expressed as committed carbon,'' or the carbon released over a period of years as the carbon stock in each hectare deforested approaches a new equilibrium in the landscape that replaces the original forest. To the extent that deforestation rates have remained constant, current releases from the areas deforested in previous years will be equal to the future releases from the areas being cleared now. Considering the quantities of carbon dioxide, carbon monoxide, methane, nitrous oxide, NO{sub x} and non-methane hydrocarbons released raises the impact by 22--37%. The relative impact on the greenhouse effect of each gas is based on the Intergovernmental Panel on Climate Change (IPCC) calculations over a 20-year time period (including indirect effects). The six gases considered have a combined global warming impact equivalent to 343 to 386 million MT of C0{sub 2}-equivalent carbon, depending on assumptions regarding the release of methane and other gases from the various sources such as burning and termites. These emissions represent 7--8 times the 50 million MT annual carbon release from Brazil's use of fossil fuels, but bring little benefit to the country. Stopping deforestation in Brazil would prevent as much greenhouse emission as tripling the fuel efficiency of all the automobiles in the world. The relatively cheap measures needed to contain deforestation, together with the many complementary benefits of doing so, make this the first priority for funds intended to slow global warming.

  5. Covalent functionalization of metal oxide and carbon nanostructures with polyoctasilsesquioxane (POSS) and their incorporation in polymer composites

    SciTech Connect (OSTI)

    Gomathi, A.; Gopalakrishnan, K.; Rao, C.N.R.

    2010-12-15

    Polyoctasilsesquioxane (POSS) has been employed to covalently functionalize nanostructures of TiO{sub 2}, ZnO and Fe{sub 2}O{sub 3} as well as carbon nanotubes, nanodiamond and graphene to enable their dispersion in polar solvents. Covalent functionalization of these nanostructures with POSS has been established by electron microscopy, EDAX analysis and infrared spectroscopy. On heating the POSS-functionalized nanostructures, silica-coated nanostructures are obtained. POSS-functionalized nanoparticles of TiO{sub 2}, Fe{sub 2}O{sub 3} and graphite were utilized to prepare polymer-nanostructure composites based on PVA and nylon-6,6.

  6. Dispersion toughened silicon carbon ceramics

    DOE Patents [OSTI]

    Wei, G.C.

    1984-01-01

    Fracture resistant silicon carbide ceramics are provided by incorporating therein a particulate dispersoid selected from the group consisting of (a) a mixture of boron, carbon and tungsten, (b) a mixture of boron, carbon and molybdenum, (c) a mixture of boron, carbon and titanium carbide, (d) a mixture of aluminum oxide and zirconium oxide, and (e) boron nitride. 4 figures.

  7. Cellulosic emissions (kg of pollutant per km2 county area) -...

    Open Energy Info (EERE)

    Cellulosic emissions (kg of pollutant per km2 county area) Data reflects projected air emissions of nitrogen oxides (NOX), ammonia (NH3), carbon monoxide (CO), sulfur oxide (SOX),...

  8. Catalytic membranes for CO oxidation in fuel cells

    DOE Patents [OSTI]

    Sandi-Tapia, Giselle; Carrado Gregar, Kathleen; Kizilel, Riza

    2010-06-08

    A hydrogen permeable membrane, which includes a polymer stable at temperatures of about 200 C having clay impregnated with Pt or Au or Ru or Pd particles or mixtures thereof with average diameters of less than about 10 nanometers (nms) is disclosed. The membranes are useful in fuel cells or any device which requires hydrogen to be separated from carbon monoxide.

  9. EERE Success Story-Ford-Dow Partnership Is Linked to Carbon Fiber...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Carbon Fiber Technology Facility Set To Scale Up Industry Plasma oxidation oven. Photo Courtesy: RMX Technologies EERE Success Story-Plasma Oxidation of Carbon Fiber Precursor ...

  10. Method and apparatus for preparation of spherical metal carbonates and lithium metal oxides for lithium rechargeable batteries

    DOE Patents [OSTI]

    Kang, Sun-Ho; Amine, Khalil

    2008-10-14

    A number of materials with the composition Li.sub.1+xNi.sub..alpha.Mn.sub..beta.Co.sub..gamma.M'.sub..delta.O.sub.2-- zF.sub.z (M'=Mg,Zn,Al,Ga,B,Zr,Ti) for use with rechargeable batteries, wherein x is between about 0 and 0.3, .alpha. is between about 0.2 and 0.6, .beta. is between about 0.2 and 0.6, .gamma. is between about 0 and 0.3, .delta. is between about 0 and 0.15, and z is between about 0 and 0.2. Adding the above metal and fluorine dopants affects capacity, impedance, and stability of the layered oxide structure during electrochemical cycling. Another aspect of the invention includes materials with the composition Li.sub.1+xNi.sub..alpha.Co.sub..beta.Mn.sub..gamma.M'.sub..delta.O.sub.yF- .sub.z (M'=Mg,Zn,Al,Ga,B,Zr,Ti), where the x is between 0 and 0.2, the .alpha. between 0 and 1, the .beta. between 0 and 1, the .gamma. between 0 and 2, the .delta. between about 0 and about 0.2, the y is between 2 and 4, and the z is between 0 and 0.5.

  11. Catalytic conversion of hydrocarbons to hydrogen and high-value carbon

    DOE Patents [OSTI]

    Shah, Naresh; Panjala, Devadas; Huffman, Gerald P.

    2005-04-05

    The present invention provides novel catalysts for accomplishing catalytic decomposition of undiluted light hydrocarbons to a hydrogen product, and methods for preparing such catalysts. In one aspect, a method is provided for preparing a catalyst by admixing an aqueous solution of an iron salt, at least one additional catalyst metal salt, and a suitable oxide substrate support, and precipitating metal oxyhydroxides onto the substrate support. An incipient wetness method, comprising addition of aqueous solutions of metal salts to a dry oxide substrate support, extruding the resulting paste to pellet form, and calcining the pellets in air is also discloses. In yet another aspect, a process is provided for producing hydrogen from an undiluted light hydrocarbon reactant, comprising contacting the hydrocarbon reactant with a catalyst as described above in a reactor, and recovering a substantially carbon monoxide-free hydrogen product stream. In still yet another aspect, a process is provided for catalytic decomposition of an undiluted light hydrocarbon reactant to obtain hydrogen and a valuable multi-walled carbon nanotube coproduct.

  12. Formation of rare earth carbonates using supercritical carbon dioxide

    DOE Patents [OSTI]

    Fernando, Quintus; Yanagihara, Naohisa; Dyke, James T.; Vemulapalli, Krishna

    1991-09-03

    The invention relates to a process for the rapid, high yield conversion of select rare earth oxides or hydroxides, to their corresponding carbonates by contact with supercritical carbon dioxide.

  13. Reduction of iron-oxide-carbon composites: part II. Rates of reduction of composite pellets in a rotary hearth furnace simulator

    SciTech Connect (OSTI)

    Halder, S.; Fruehan, R.J.

    2008-12-15

    A new ironmaking concept is being proposed that involves the combination of a rotary hearth furnace (RHF) with an iron-bath smelter. The RHF makes use of iron-oxide-carbon composite pellets as the charge material and the final product is direct-reduced iron (DRI) in the solid or molten state. This part of the research includes the development of a reactor that simulated the heat transfer in an RHF. The external heat-transport and high heating rates were simulated by means of infrared (IR) emitting lamps. The reaction rates were measured by analyzing the off-gas and computing both the amount of CO and CO{sub 2} generated and the degree of reduction. The reduction times were found to be comparable to the residence times observed in industrial RHFs. Both artificial ferric oxide (PAH) and naturally occurring hematite and taconite ores were used as the sources of iron oxide. Coal char and devolatilized wood charcoal were the reductants. Wood charcoal appeared to be a faster reductant than coal char. However, in the PAH-containing pellets, the reverse was found to be true because of heat-transfer limitations. For the same type of reductant, hematite-containing pellets were observed to reduce faster than taconite-containing pellets because of the development of internal porosity due to cracking and fissure formation during the Fe2O{sub 3}-to-Fe3O{sub 4} transition. This is, however, absent during the reduction of taconite, which is primarily Fe3O{sub 4}. The PAH-wood-charcoal pellets were found to undergo a significant amount of swelling at low-temperature conditions, which impeded the external heat transport to the lower layers. If the average degree of reduction targeted in an RHF is reduced from 95 to approximately 70 pct by coupling the RHF with a bath smelter, the productivity of the RHF can be enhanced 1.5 to 2 times. The use of a two- or three-layer bed was found to be superior to that of a single layer, for higher productivities.

  14. Basic Engineering Research for D and D of R Reactor Storage Pond Sludge: Electrokinetics, Carbon Dioxide Extraction, and Supercritical Water Oxidation

    SciTech Connect (OSTI)

    Michael A. Matthews; David A. Bruce,; Thomas A. Davis; Mark C. Thies; John W. Weidner; Ralph E. White

    2002-04-01

    Large quantities of mixed low level waste (MLLW) that fall under the Toxic Substances Control Act (TSCA) exist and will continue to be generated during D and D operations at DOE sites across the country. The standard process for destruction of MLLW is incineration, which has an uncertain future. The extraction and destruction of PCBs from MLLW was the subject of this research Supercritical Fluid Extraction (SFE) with carbon dioxide with 5% ethanol as cosolvent and Supercritical Waster Oxidation (SCWO) were the processes studied in depth. The solid matrix for experimental extraction studies was Toxi-dry, a commonly used absorbent made from plant material. PCB surrogates were 1.2,4-trichlorobenzene (TCB) and 2-chlorobiphenyl (2CBP). Extraction pressures of 2,000 and 4,000 psi and temperatures of 40 and 80 C were studied. Higher extraction efficiencies were observed with cosolvent and at high temperature, but pressure little effect. SCWO treatment of the treatment of the PCB surrogates resulted in their destruction below detection limits.

  15. Effectiveness of Diesel Oxidation Catalyst in Reducing HC and CO Emissions from Reactivity Controlled Compression Ignition

    SciTech Connect (OSTI)

    Prikhodko, Vitaly Y; Curran, Scott; Parks, II, James E; Wagner, Robert M

    2013-01-01

    Reactivity Controlled Compression Ignition (RCCI) has been shown to allow for diesel-like or better brake thermal efficiency with significant reductions in nitrogen oxide (NOX) particulate matter (PM) emissions. Hydrocarbon (HC) and carbon monoxide (CO) emission levels, on the other hand, are similar to those of port fuel injected gasoline engines. The higher HC and CO emissions combined with the lower exhaust temperatures with RCCI operation present a challenge for current exhaust aftertreatments. The reduction of HC and CO emissions in a lean environment is typically achieved with an oxidation catalyst. In this work, several diesel oxidation catalysts (DOC) with different precious metal loadings were evaluated for effectiveness to control HC and CO emissions from RCCI combustion in a light-duty multi-cylinder engine operating on gasoline and diesel fuels. Each catalyst was evaluated in a steady-state engine operation with temperatures ranging from 160 to 260 C. A shift to a higher light-off temperature was observed during the RCCI operation. In addition to the steady-state experiments, the performances of the DOCs were evaluated during multi-mode engine operation by switching from diesel-like combustion at higher exhaust temperature and low HC/CO emissions to RCCI combustion at lower temperature and higher HC/CO emissions. High CO and HC emissions from RCCI generated an exotherm keeping the catalyst above the light-off temperature.

  16. Monoxides of small terbium clusters: A density functional theory investigation

    SciTech Connect (OSTI)

    Zhang, G. L.; Yuan, H. K. Chen, H.; Kuang, A. L.; Li, Y.; Wang, J. Z.; Chen, J.

    2014-12-28

    To investigate the effect of oxygen atom on the geometrical structures, electronic, and magnetic properties of small terbium clusters, we carried out the first-principles calculations on Tb{sub n}O (n = 1-14) clusters. The capping of an oxygen atom on one trigonal-facet of Tb{sub n} structures is always favored energetically, which can significantly improve the structural stability. The far-infrared vibrational spectroscopies are found to be different from those of corresponding bare clusters, providing a distinct signal to detect the characteristic structures of Tb{sub n}O clusters. The primary effect of oxygen atom on magnetic properties is to change the magnetic orderings among Tb atoms and to reduce small of local magnetic moments of the O-coordinated Tb atoms, both of which serve as the key reasons for the experimental magnetic evolution of an oscillating behavior. These calculations are consistent with, and help to account for, the experimentally observed magnetic properties of monoxide Tb{sub n}O clusters [C. N. Van Dijk et al., J. Appl. Phys. 107, 09B526 (2010)].

  17. Staged heating by oxidation of carbonaceous material

    DOE Patents [OSTI]

    Knell, Everett W.; Green, Norman W.

    1978-01-31

    A carbonaceous material is pyrolyzed in the presence of a particulate source of heat obtained by the partial oxidation of a carbon containing solid residue of the carbonaceous material. The heat obtained from the oxidation of the carbon containing solid residue is maximized by preheating the carbon containing solid residue with a hot gas stream obtained by oxidizing the gaseous combustion products of the carbon containing solid residue.

  18. Carbonyl sulfide/carbon chemistry: Interim report, July 1, 1985-February 28, 1986

    SciTech Connect (OSTI)

    Hinckley, C.C.; Shiley, R.H.

    1986-05-01

    This interim report describes work performed during the first eight months of a continuing project, including descriptions of sample preparations and analyses. The objective of the study is to determine the effects of carbonyl sulfide, a product of the carbon monoxide/ethanol desulfurization process, on coal. A coal is first treated with carbon monoxide to reduce pyrite, and is then reacted with OCS and N/sub 2/ under various conditions. OCS is a potent resulfurization agent and appears to affect the formation of mesophase in chars derived from the coal. 8 refs., 1 fig., 8 tabs.

  19. Reduction of Nitrogen Oxide Emissions for lean Burn Engine Technology

    SciTech Connect (OSTI)

    McGill, R.N.

    1998-08-04

    Lean-burn engines offer the potential for significant fuel economy improvements in cars and trucks, perhaps the next great breakthrough in automotive technology that will enable greater savings in imported petroleum. The development of lean-burn engines, however, has been an elusive goal among automakers because of the emissions challenges associated with lead-burn engine technology. Presently, cars operate with sophisticated emissions control systems that require the engine's air-fuel ratio to be carefully controlled around the stoichiometric point (chemically correct mixture). Catalysts in these systems are called "three-way" catalysts because they can reduce hydrocarbon, carbon monoxide, and nitrogen oxide emissions simultaneously, but only because of the tight control of the air-fuel ratio. The purpose of this cooperative effort is to develop advanced catalyst systems, materials, and necessary engine control algorithms for reducing NOX emissions in oxygen-rich automotive exhaust (as with lean-burn engine technology) to meet current and near-future mandated Clean Air Act standards. These developments will represent a breakthrough in both emission control technology and automobile efficiency. The total project is a joint effort among five national laboratories, together with US CAR. The role of Lockheed-Martin Energy Systems in the total project is two fold: characterization of catalyst performance through laboratory evaluations from bench-scale flow reactor tests to engine laboratory tests of full-scale prototype catalysts, and microstructural characterization of catalyst material before and after test stand and/or engine testing.

  20. ARM - Oxides of Nitrogen

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Oxides of Nitrogen Outreach Home Room News Publications Traditional Knowledge Kiosks Barrow, Alaska Tropical Western Pacific Site Tours Contacts Students Study Hall About ARM Global Warming FAQ Just for Fun Meet our Friends Cool Sites Teachers Teachers' Toolbox Lesson Plans Oxides of Nitrogen Oxides of nitrogen, chlorofluorocarbons (CFCs), and ozone have a lesser effect on the atmosphere than carbon dioxide and methane, but as you will see they are important contributors to the greenhouse

  1. Geochemical Impacts of Carbon Dioxide, Brine, Trace Metal and...

    Office of Scientific and Technical Information (OSTI)

    Carbon Dioxide, Brine, Trace Metal and Organic Leakage into an Unconfined, Oxidizing Limestone Aquifer Citation Details In-Document Search Title: Geochemical Impacts of Carbon ...

  2. Iron oxidation kinetics for H-2 and CO production via chemical looping

    SciTech Connect (OSTI)

    Stehle, RC; Bobek, MM; Hahn, DW

    2015-01-30

    Solar driven production of fuels by means of an intermediate reactive metal for species splitting has provided a practical and potentially efficient pathway for disassociating molecules at significantly lower thermal energies. The fuels of interest are of or derive from the separation of oxygen from H2O and CO2 to form hydrogen and carbon monoxide, respectively. The following study focuses on iron oxidation through water and CO2 splitting to explore the fundamental reaction kinetics and kinetic rates that are relevant to these processes. In order to properly characterize the reactive metal potential and to optimize a scaled-up solar reactor system, a monolith-based laboratory reactor was implemented to investigate reaction temperatures over a range from 990 to 1400 K. The presence of a single, solid monolith as a reacting surface allowed for a limitation in mass transport effects in order to monitor kinetically driven reaction steps. The formation of oxide layers on the iron monoliths followed Cabrera-Mott models for oxidation of metals with kinetic rates being measured using real-time mass spectrometry to calculate kinetic constants and estimate oxide layer thicknesses. Activation energies of 47.3 kJ/mol and 32.8 kJ/mol were found for water-splitting and CO2 splitting, respectively, and the conclusions of the independent oxidation reactions where applied to experimental results for syngas (H-2-CO) production to explore ideal process characteristics. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

  3. Peculiarities of high-overtone transition probabilities in carbon monoxide revealed by high-precision calculation

    SciTech Connect (OSTI)

    Medvedev, Emile S.; Meshkov, Vladimir V.; Stolyarov, Andrey V.

    2015-10-21

    In the recent work devoted to the calculation of the rovibrational line list of the CO molecule [G. Li et al., Astrophys. J., Suppl. Ser. 216, 15 (2015)], rigorous validation of the calculated parameters including intensities was carried out. In particular, the Normal Intensity Distribution Law (NIDL) [E. S. Medvedev, J. Chem. Phys. 137, 174307 (2012)] was employed for the validation purposes, and it was found that, in the original CO line list calculated for large changes of the vibrational quantum number up to Δn = 41, intensities with Δn > 11 were unphysical. Therefore, very high overtone transitions were removed from the published list in Li et al. Here, we show how this type of validation is carried out and prove that the quadruple precision is indispensably required to predict the reliable intensities using the conventional 32-bit computers. Based on these calculations, the NIDL is shown to hold up for the 0 → n transitions till the dissociation limit around n = 83, covering 45 orders of magnitude in the intensity. The low-intensity 0 → n transition predicted in the work of Medvedev [Determination of a new molecular constant for diatomic systems. Normal intensity distribution law for overtone spectra of diatomic and polyatomic molecules and anomalies in overtone absorption spectra of diatomic molecules, Institute of Chemical Physics, Russian Academy of Sciences, Chernogolovka, 1984] at n = 5 is confirmed, and two additional “abnormal” intensities are found at n = 14 and 23. Criteria for the appearance of such “anomalies” are formulated. The results could be useful to revise the high-overtone molecular transition probabilities provided in spectroscopic databases.

  4. Technology development for iron Fischer-Tropsch catalysis. [Pretreatment of catalyst in carbon monoxide

    SciTech Connect (OSTI)

    Not Available

    1991-01-01

    The present study shows that activation of a high surface area Fe{sub 2}O{sub 3} catalyst in CO in a (CSTR), continuously stirred tank reactor using tetralin as solvent results in an activated that is three times of material that is activated in H{sub 2} or directly in the syngas.

  5. Quantum yield for carbon monoxide production in the 248 nm photodissociation of carbonyl sulfide (OCS)

    SciTech Connect (OSTI)

    Zhao, Z.; Stickel, R.E.; Wine, P.H. [Georgia Institute of Technology, Atlanta, GA (United States)] [Georgia Institute of Technology, Atlanta, GA (United States)

    1995-03-01

    Tunable diode laser absorption spectroscopy has been coupled with excimer laser flash photolysis to measure the quantum yield for CO production from 248 nm photodissociation of carbonyl sulfide (OCS) relative to the well known quantum yield for CO production from 248 nm photolysis of phosgene (Cl{sub 2}CO). The temporal resolution of the experiments was sufficient to distinguish CO formed directly by photodissociation from that formed by subsequent S({sup 3}P{sub j}) reaction with OCS. Under the experimental conditions employed, CO formation via the fast S({sup 1}D{sub 2})+OCS reaction was minimal. Measurements at 297K and total pressures from 4 to 100 Torr N{sub 2}+N{sub 2}O show the CO yield to be greater than 0.95 and most likely unity. This result suggests that the contribution of OCS as a precursor to the lower stratospheric sulfate aerosol layer is somewhat larger than previously thought. 25 refs., 1 fig., 2 tabs.

  6. Methane, carbon monoxide, and ammonia in brown dwarfs and self-luminous giant planets

    SciTech Connect (OSTI)

    Zahnle, Kevin J.; Marley, Mark S. E-mail: Mark.S.Marley@NASA.gov

    2014-12-10

    We address disequilibrium abundances of some simple molecules in the atmospheres of solar composition brown dwarfs and self-luminous extrasolar giant planets using a kinetics-based one-dimensional atmospheric chemistry model. Our approach is to use the full kinetics model to survey the parameter space with effective temperatures between 500 K and 1100 K. In all of these worlds, equilibrium chemistry favors CH{sub 4} over CO in the parts of the atmosphere that can be seen from Earth, but in most disequilibrium favors CO. The small surface gravity of a planet strongly discriminates against CH{sub 4} when compared to an otherwise comparable brown dwarf. If vertical mixing is like Jupiter's, the transition from methane to CO occurs at 500 K in a planet. Sluggish vertical mixing can raise this to 600 K, but clouds or more vigorous vertical mixing could lower this to 400 K. The comparable thresholds in brown dwarfs are 1100 100 K. Ammonia is also sensitive to gravity, but, unlike CH{sub 4}/CO, the NH{sub 3}/N{sub 2} ratio is insensitive to mixing, which makes NH{sub 3} a potential proxy for gravity. HCN may become interesting in high-gravity brown dwarfs with very strong vertical mixing. Detailed analysis of the CO-CH{sub 4} reaction network reveals that the bottleneck to CO hydrogenation goes through methanol, in partial agreement with previous work. Simple, easy to use quenching relations are derived by fitting to the complete chemistry of the full ensemble of models. These relations are valid for determining CO, CH{sub 4}, NH{sub 3}, HCN, and CO{sub 2} abundances in the range of self-luminous worlds we have studied, but may not apply if atmospheres are strongly heated at high altitudes by processes not considered here (e.g., wave breaking).

  7. Carbon Monoxide Dehydrogenases and Acetyl-CoA Synthases: Light at the End of the Tunnel?

    SciTech Connect (OSTI)

    Paul A. Lindahl

    2002-02-19

    OAK-B135 Metalloenzymes seem to ''come of age'' when their structures are known at atomic resolution, spectroscopic and catalytic properties are basically understood, and genetic expression systems are available. Such foundations allow detailed mechanistic and spectroscopic properties to be probed and correlated to structure. The objective of this article is to summarize what is known about the title group of enzymes, and show that, to a large degree, they have come of age.

  8. Carbon emissions and sequestration in forests: Case studies from seven developing countries. Volume 2, Greenhouse gas emissions from deforestration in the Brazilian Amazon

    SciTech Connect (OSTI)

    Makundi, W.; Sathaye, J.; Fearnside, P.M.

    1992-08-01

    Deforestation in Brazilian Amazonia in 1990 was releasing approximately 281--282 X 10{sup 6} metric tons (MT) of carbon on conversion to a landscape of agriculture, productive pasture, degraded pasture, secondary forest and regenerated forest in the proportions corresponding to the equilibrium condition implied by current land-use patterns. Emissions are expressed as ``committed carbon,`` or the carbon released over a period of years as the carbon stock in each hectare deforested approaches a new equilibrium in the landscape that replaces the original forest. To the extent that deforestation rates have remained constant, current releases from the areas deforested in previous years will be equal to the future releases from the areas being cleared now. Considering the quantities of carbon dioxide, carbon monoxide, methane, nitrous oxide, NO{sub x} and non-methane hydrocarbons released raises the impact by 22--37%. The relative impact on the greenhouse effect of each gas is based on the Intergovernmental Panel on Climate Change (IPCC) calculations over a 20-year time period (including indirect effects). The six gases considered have a combined global warming impact equivalent to 343 to 386 million MT of C0{sub 2}-equivalent carbon, depending on assumptions regarding the release of methane and other gases from the various sources such as burning and termites. These emissions represent 7--8 times the 50 million MT annual carbon release from Brazil`s use of fossil fuels, but bring little benefit to the country. Stopping deforestation in Brazil would prevent as much greenhouse emission as tripling the fuel efficiency of all the automobiles in the world. The relatively cheap measures needed to contain deforestation, together with the many complementary benefits of doing so, make this the first priority for funds intended to slow global warming.

  9. The Role of Organic Capping Layers of Platinum Nanoparticles in Catalytic Activity of CO Oxidation

    SciTech Connect (OSTI)

    Park, Jeong Y.; Aliaga, Cesar; Renzas, J. Russell; Lee, Hyunjoo; Somorjai, Gabor A.

    2008-12-17

    We report the catalytic activity of colloid platinum nanoparticles synthesized with different organic capping layers. On the molecular scale, the porous organic layers have open spaces that permit the reactant and product molecules to reach the metal surface. We carried out CO oxidation on several platinum nanoparticle systems capped with various organic molecules to investigate the role of the capping agent on catalytic activity. Platinum colloid nanoparticles with four types of capping layer have been used: TTAB (Tetradecyltrimethylammonium Bromide), HDA (hexadecylamine), HDT (hexadecylthiol), and PVP (poly(vinylpyrrolidone)). The reactivity of the Pt nanoparticles varied by 30%, with higher activity on TTAB coated nanoparticles and lower activity on HDT, while the activation energy remained between 27-28 kcal/mol. In separate experiments, the organic capping layers were partially removed using ultraviolet light-ozone generation techniques, which resulted in increased catalytic activity due to the removal of some of the organic layers. These results indicate that the nature of chemical bonding between organic capping layers and nanoparticle surfaces plays a role in determining the catalytic activity of platinum colloid nanoparticles for carbon monoxide oxidation.

  10. DOE/EA-2005 Final Environmental Assessment for Chromium Plume...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    ... conveyance through a pipeline may eventually be ... (40 CFR 50): ozone, carbon monoxide, nitrogen dioxide, sulfur oxides, ... creation of sketch maps, collection of ...