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Title: Synthesis Gas Conversion over Rh-Based Catalysts Promoted by Fe and Mn

Abstract

Rh/SiO2 catalysts promoted with Fe and Mn are selective for synthesis gas conversion to oxygenates and light hydrocarbons at 523 K and 580 psi. Selective anchoring of Fe and Mn species on Rh nanoparticles was achieved by controlled surface reactions and was evidenced by ultraviolet–visible absorption spectroscopy, scanning transmission electron microscopy, and inductively coupled plasma absorption emission spectroscopy. The interaction between Rh and Fe promotes the selective production of ethanol through hydrogenation of acetaldehyde and enhances the selectivity toward C2 oxygenates, which include ethanol and acetaldehyde. The interaction between Rh and Mn increases the overall reaction rate and the selectivity toward C2+ hydrocarbons. The combination of Fe and Mn on Rh/SiO2 results in trimetallic Rh-Fe-Mn catalysts that surpass the performance of their bimetallic counterparts. The highest selectivities toward ethanol (36.9%) and C2 oxygenates (39.6%) were achieved over the Rh-Fe-Mn ternary system with a molar ratio of 1:0.15:0.10, as opposed to the selectivities obtained over Rh/SiO2, which were 3.5% and 20.4%, respectively. The production of value-added oxygenates and C2+ hydrocarbons over this trimetallic catalyst accounted for 55% of the total products. X-ray photoelectron spectroscopy measurements suggest that significant fractions of the Fe and Mn species exist as metallic iron and manganesemore » oxides on the Rh surface upon reduction. These findings are rationalized by density functional theory (DFT) calculations, which reveal that the exact state of metals on the surfaces is condition-dependent, with Mn present as Mn(I) and Mn(II) oxide on the Rh (211) step edges and Fe present as Fe(I) oxide on the step edge and metallic subsurface iron on both Rh steps and terraces. CO Fourier transform infrared spectroscopy and DFT calculations suggest that the binding of CO to Rh (211) step edges modified by Fe and/or manganese oxide is altered in comparison to CO adsorption on a clean Rh (211) surface. These results suggest that Mn2Ox species and Fe and Fe2O modify bonding at Rh step edges and shift reaction selectivity away from CH4.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [2]; ORCiD logo [3];  [1]; ORCiD logo [1]; ORCiD logo [4]
  1. Department of Chemical and Biological Engineering, University of Wisconsin—Madison, 1415 Engineering Drive, Madison, Wisconsin 53706, United States
  2. Department of Chemical and Biological Engineering, University of Wisconsin—Madison, 1415 Engineering Drive, Madison, Wisconsin 53706, United States; Institute of Chemistry, University of Campinas (UNICAMP), P.O. Box 6154, 13083-970 Campinas, São Paulo, Brazil
  3. Institute of Chemistry, University of Campinas (UNICAMP), P.O. Box 6154, 13083-970 Campinas, São Paulo, Brazil
  4. Department of Chemical and Biological Engineering, University of Wisconsin—Madison, 1415 Engineering Drive, Madison, Wisconsin 53706, United States
Publication Date:
Research Org.:
Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Contributing Org.:
Wisconsin Materials Research Science and Engineering Center; Environmental Molecular Sciences Laboratory (EMSL); the Center for Nanoscale Materials (CNM) at Argonne National Laboratory; and the National Energy Research Scientific Computing Center (NERSC); Center for Nanoscale Materials (CNM) at Argonne National Laboratory; National Energy Research Scientific Computing Center (NERSC)
OSTI Identifier:
1396167
Alternate Identifier(s):
OSTI ID: 1396009
Grant/Contract Number:
EE0006878; SC0014058; FG02-05ER15731; AC02-06CH11357; AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 7; Journal Issue: 7; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
ethanol; iron; manganese; oxygenates; rhodium; synthesis gas; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Liu, Yifei, Göeltl, Florian, Ro, Insoo, Ball, Madelyn R., Sener, Canan, Aragão, Isaias Barbosa, Zanchet, Daniela, Huber, George W., Mavrikakis, Manos, and Dumesic, James A. Synthesis Gas Conversion over Rh-Based Catalysts Promoted by Fe and Mn. United States: N. p., 2017. Web. doi:10.1021/acscatal.7b01381.
Liu, Yifei, Göeltl, Florian, Ro, Insoo, Ball, Madelyn R., Sener, Canan, Aragão, Isaias Barbosa, Zanchet, Daniela, Huber, George W., Mavrikakis, Manos, & Dumesic, James A. Synthesis Gas Conversion over Rh-Based Catalysts Promoted by Fe and Mn. United States. doi:10.1021/acscatal.7b01381.
Liu, Yifei, Göeltl, Florian, Ro, Insoo, Ball, Madelyn R., Sener, Canan, Aragão, Isaias Barbosa, Zanchet, Daniela, Huber, George W., Mavrikakis, Manos, and Dumesic, James A. Tue . "Synthesis Gas Conversion over Rh-Based Catalysts Promoted by Fe and Mn". United States. doi:10.1021/acscatal.7b01381. https://www.osti.gov/servlets/purl/1396167.
@article{osti_1396167,
title = {Synthesis Gas Conversion over Rh-Based Catalysts Promoted by Fe and Mn},
author = {Liu, Yifei and Göeltl, Florian and Ro, Insoo and Ball, Madelyn R. and Sener, Canan and Aragão, Isaias Barbosa and Zanchet, Daniela and Huber, George W. and Mavrikakis, Manos and Dumesic, James A.},
abstractNote = {Rh/SiO2 catalysts promoted with Fe and Mn are selective for synthesis gas conversion to oxygenates and light hydrocarbons at 523 K and 580 psi. Selective anchoring of Fe and Mn species on Rh nanoparticles was achieved by controlled surface reactions and was evidenced by ultraviolet–visible absorption spectroscopy, scanning transmission electron microscopy, and inductively coupled plasma absorption emission spectroscopy. The interaction between Rh and Fe promotes the selective production of ethanol through hydrogenation of acetaldehyde and enhances the selectivity toward C2 oxygenates, which include ethanol and acetaldehyde. The interaction between Rh and Mn increases the overall reaction rate and the selectivity toward C2+ hydrocarbons. The combination of Fe and Mn on Rh/SiO2 results in trimetallic Rh-Fe-Mn catalysts that surpass the performance of their bimetallic counterparts. The highest selectivities toward ethanol (36.9%) and C2 oxygenates (39.6%) were achieved over the Rh-Fe-Mn ternary system with a molar ratio of 1:0.15:0.10, as opposed to the selectivities obtained over Rh/SiO2, which were 3.5% and 20.4%, respectively. The production of value-added oxygenates and C2+ hydrocarbons over this trimetallic catalyst accounted for 55% of the total products. X-ray photoelectron spectroscopy measurements suggest that significant fractions of the Fe and Mn species exist as metallic iron and manganese oxides on the Rh surface upon reduction. These findings are rationalized by density functional theory (DFT) calculations, which reveal that the exact state of metals on the surfaces is condition-dependent, with Mn present as Mn(I) and Mn(II) oxide on the Rh (211) step edges and Fe present as Fe(I) oxide on the step edge and metallic subsurface iron on both Rh steps and terraces. CO Fourier transform infrared spectroscopy and DFT calculations suggest that the binding of CO to Rh (211) step edges modified by Fe and/or manganese oxide is altered in comparison to CO adsorption on a clean Rh (211) surface. These results suggest that Mn2Ox species and Fe and Fe2O modify bonding at Rh step edges and shift reaction selectivity away from CH4.},
doi = {10.1021/acscatal.7b01381},
journal = {ACS Catalysis},
number = 7,
volume = 7,
place = {United States},
year = {Tue Jun 13 00:00:00 EDT 2017},
month = {Tue Jun 13 00:00:00 EDT 2017}
}

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Cited by: 4works
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  • Rh/SiO2 catalysts promoted with Fe and Mn are selective for synthesis gas conversion to oxygenates and light hydrocarbons at 523 K and 580 psi. Selective anchoring of Fe and Mn species on Rh nanoparticles was achieved by controlled surface reactions and was evidenced by ultraviolet–visible absorption spectroscopy, scanning transmission electron microscopy, and inductively coupled plasma absorption emission spectroscopy. The interaction between Rh and Fe promotes the selective production of ethanol through hydrogenation of acetaldehyde and enhances the selectivity toward C2 oxygenates, which include ethanol and acetaldehyde. The interaction between Rh and Mn increases the overall reaction rate and the selectivitymore » toward C2+ hydrocarbons. The combination of Fe and Mn on Rh/SiO2 results in trimetallic Rh-Fe-Mn catalysts that surpass the performance of their bimetallic counterparts. The highest selectivities toward ethanol (36.9%) and C2 oxygenates (39.6%) were achieved over the Rh-Fe-Mn ternary system with a molar ratio of 1:0.15:0.10, as opposed to the selectivities obtained over Rh/SiO2, which were 3.5% and 20.4%, respectively. The production of value-added oxygenates and C2+ hydrocarbons over this trimetallic catalyst accounted for 55% of the total products. X-ray photoelectron spectroscopy measurements suggest that significant fractions of the Fe and Mn species exist as metallic iron and manganese oxides on the Rh surface upon reduction. These findings are rationalized by density functional theory (DFT) calculations, which reveal that the exact state of metals on the surfaces is condition-dependent, with Mn present as Mn(I) and Mn(II) oxide on the Rh (211) step edges and Fe present as Fe(I) oxide on the step edge and metallic subsurface iron on both Rh steps and terraces. CO Fourier transform infrared spectroscopy and DFT calculations suggest that the binding of CO to Rh (211) step edges modified by Fe and/or manganese oxide is altered in comparison to CO adsorption on a clean Rh (211) surface. These results suggest that Mn2Ox species and Fe and Fe2O modify bonding at Rh step edges and shift reaction selectivity away from CH4.« less
    Cited by 4
  • The synthesis of acetaldehyde and propionaldehyde from CO hydrogenation over Na-Mn-Ni catalysts has been studied. Coprecipitated Na-Mn-Ni catalysts exhibited high activities for the synthesis of acetaldehyde from CO hydrogenation and the synthesis of propionaldehyde from addition of ethylene to CO hydrogenation. In contrast, Na-Mn-Ni/SiO{sub 2} catalysts prepared from coimpregnation showed mainly methanation and ethylene hydrogenation activities. The selectivities to acetaldehyde in CO hydrogenation were found to parallel the selectivities to propionaldehyde in ethylene addition. X-ray photoelectron spectroscopic studies revealed that reduction of the coprecipitated Na-Mn-Ni catalyst at 350{degree}C led to the migration of Na ions onto the surface of themore » catalyst resulting in the suppression of hydrogen chemisorption on the catalyst.« less
  • Zn-Mn promoted Cu-Fe based catalyst was synthesized by the co-precipitation method. Mixed alcohols synthesis from syngas was studied in a half-inch tubular reactor system after the catalyst was reduced. Zn-Mn promoted Cu-Fe based catalyst was characterized by SEM-EDS, TEM, XRD, and XPS. The liquid phase products (alcohol phase and hydrocarbon phase) were analyzed by GC-MS and the gas phase products were analyzed by GC. The results showed that Zn-Mn promoted Cu-Fe based catalyst had high catalytic activity and high alcohol selectivity. The maximal CO conversion rate was 72%, and the yield of alcohol and hydrocarbons were also very high. Cumore » (111) was the active site for mixed alcohols synthesis, Fe 2C (101) was the active site for olefin and paraffin synthesis. The reaction mechanism of mixed alcohols synthesis from syngas over Zn-Mn promoted Cu-Fe based catalyst was proposed. Here, Zn-Mn promoted Cu-Fe based catalyst can be regarded as a potential candidate for catalytic conversion of biomass-derived syngas to mixed alcohols.« less
  • The kinetics of the synthesis of ammonia from its elements over Fe/TiO{sub 2}, and hydrazine-pretreated alkali-promoted Fe/TiO{sub 2} catalysts was studied in a flow microreactor at 101 kPa pressure. The kinetic model was modified to account for deactivation of supported catalyst particles by Ostwald ripening. Pretreatment of Fe/TiO{sub 2} with hydrazine increased the ammonia synthesis turnover frequency by more than an order of magnitude over unpretreated Fe/TiO{sub 2}. The ammonia partial pressure dependence and apparent activation energy over hydrazine-pretreated Fe/TiO{sub 2} were more representative of iron uninfluenced by the strong metal-support interaction (SMSI) which occurs in Metal-titania systems. In situmore » CO chemisorption measurements following the ammonia synthesis kinetics measurements showed higher CO uptake with hydrazine-pretreated Fe/TiO{sub 2} then with unpretreated Fe/TiO{sub 2}. The increased turnover frequency, altered kinetic parameters, and higher CO uptake suggest that hydrazine pretreatment inhibited the onset of SMSI, which is attributed to titanium nitride formation on the support surface. Addition of the alkali promoters K and Cs to the catalysts not only increased the turnover frequency and decreased the apparent activation energy and ammonia partial pressure dependence, but acted to stabilize supported iron particles against growth by Ostwald ripening. The data suggest that physical covering of the surface by alkali inhibits Ostwald ripening of iron particles by blocking dissociation of iron atoms from supported particles thus suppressing their migration over the support surface to form larger particles.« less