Molecular structure and sour gas surface chemistry of supported K2O/WO3/Al2O3 catalysts

Zhu, Minghui; Li, Bin; Jehng, Jih-Mirn; Sharma, Lohit; Taborda, Julian; Zhang, Lihua; Stach, Eric; Wachs, Israel E.; Wu, Zili; Baltrusaitis, Jonas

doi:10.1016/j.apcatb.2018.03.044

Title: Molecular structure and sour gas surface chemistry of supported K₂O/WO₃/Al₂O₃ catalysts

Journal Article · 16 March 2018 · Applied Catalysis B: Environmental

DOI: https://doi.org/10.1016/j.apcatb.2018.03.044 · OSTI ID:1466585

Zhu, Minghui ^[1]; Li, Bin ^[1]; Jehng, Jih-Mirn ^[1]; Sharma, Lohit ^[1]; Taborda, Julian ^[1]; Zhang, Lihua ^[2]; Stach, Eric ^[3]; Wachs, Israel E. ^[1];

^[4]; Baltrusaitis, Jonas ^[1]

Lehigh Univ., Bethlehem, PA (United States). Dept. of Chemical and Biomolecular Engineering
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN); Univ. of Pennsylvania, Philadelphia, PA (United States). Materials Science and Engineering
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)

Molecular structures of the unprompted and K₂O-promoted supported WO₃/Al₂O₃ catalysts were studied with in situ Raman and UV-vis spectroscopy. In situ Raman spectra revealed that supported 20% WO₃/Al₂O₃ corresponds to near monolayer coverage of isolated and oligomeric surface WOx species on Al₂O₃. Above monolayer surface WO_x coverage (21% WO₃/Al₂O₃), crystalline WO₃ nanoparticles are also present. The addition of K₂O to the supported WO₃/Al₂O₃ catalyst increased the concentration of isolated surface WO_x species and did not form K₂WO₄ nanoparticles. The reducibility of the tungsten oxide structures depends on their structures (2D or 3D) and the K₂O promoter. Their interaction with acidic CO₂ and SO₂ gases was also investigated. Adsorption of CO₂ creates several surface carbonate species of varying acidity that were detected using a combination of in situ IR and mass spectroscopy. Adsorbed bicarbonate form on weakly basic surface sites on tungsten oxide monolayer WO₃/Al₂O₃ catalyst as well as in the presence of low 2.5% K₂O loading. At high 5% K₂O loading, the presence of the strong surface basic sites yields adsorbed carbonates. In conclusion, after SO₂ pretreatment, however, new strongly adsorbed sulfate appears on the surface that inhibit CO₂ adsorption.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Understanding and Control of Acid Gas-induced Evolution of Materials for Energy (UNCAGE-ME); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704; AC05-00OR22725

OSTI ID:: 1466585

Alternate ID(s):: OSTI ID: 1468086

Report Number(s):: BNL-207989-2018-JAAM

Journal Information:: Applied Catalysis B: Environmental, Vol. 232, Issue C; ISSN 0926-3373

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 18 works

Citation information provided by
Web of Science

References (51)

Sweetening of sour natural gases by mixed-solvent absorption: Solubilities of ethane, carbon dioxide, and hydrogen sulfide in mixtures of physical and chemical solvents Rivas, O. R.; Prausnitz, J. M. AIChE Journal, Vol. 25, Issue 6 https://doi.org/10.1002/aic.690250608	journal	November 1979
On the modelling and simulation of sour gas absorption by aqueous amine solutions Kucka, Lars; Müller, Ivo; Kenig, Eugeny Y. Chemical Engineering Science, Vol. 58, Issue 16 https://doi.org/10.1016/S0009-2509(03)00255-0	journal	August 2003
Minireview: direct catalytic conversion of sour natural gas (CH ₄ + H ₂ S + CO ₂ ) components to high value chemicals and fuels Taifan, William; Baltrusaitis, Jonas Catalysis Science & Technology, Vol. 7, Issue 14 https://doi.org/10.1039/C7CY00272F	journal	January 2017
CH ₄ and H ₂ S reforming to CH ₃ SH and H ₂ catalyzed by metal-promoted Mo ₆ S ₈ clusters: a first-principles micro-kinetic study Taifan, William; Arvidsson, Adam A.; Nelson, Eric Catalysis Science & Technology, Vol. 7, Issue 16 https://doi.org/10.1039/C7CY00857K	journal	January 2017
CH 4 conversion to value added products: Potential, limitations and extensions of a single step heterogeneous catalysis Taifan, William; Baltrusaitis, Jonas Applied Catalysis B: Environmental, Vol. 198 https://doi.org/10.1016/j.apcatb.2016.05.081	journal	December 2016
Conversion of CS2 and COS over alumina and titania under Claus process conditions: reaction with H2O and SO2 Clark, P. Applied Catalysis B: Environmental, Vol. 31, Issue 2 https://doi.org/10.1016/S0926-3373(00)00272-1	journal	May 2001
Computational Studies of CO ₂ Activation via Photochemical Reactions with Reduced Sulfur Compounds Baltrusaitis, Jonas; Patterson, Eric V.; Hatch, Courtney The Journal of Physical Chemistry A, Vol. 116, Issue 37 https://doi.org/10.1021/jp3051092	journal	September 2012
Conversion of methyl mercaptan and methanol to hydrocarbons over solid acid catalysts – A comparative study Hulea, Vasile; Huguet, Edouard; Cammarano, Claudia Applied Catalysis B: Environmental, Vol. 144 https://doi.org/10.1016/j.apcatb.2013.07.056	journal	January 2014
Selective transformation of methyl and ethyl mercaptans mixture to hydrocarbons and H2S on solid acid catalysts Cammarano, Claudia; Huguet, Edouard; Cadours, Renaud Applied Catalysis B: Environmental, Vol. 156-157 https://doi.org/10.1016/j.apcatb.2014.03.026	journal	September 2014
A highly efficient process for transforming methyl mercaptan into hydrocarbons and H2S on solid acid catalysts Huguet, Edouard; Coq, Bernard; Durand, Robert Applied Catalysis B: Environmental, Vol. 134-135 https://doi.org/10.1016/j.apcatb.2013.01.037	journal	May 2013
The conversion of methanol and other O-compounds to hydrocarbons over zeolite catalysts Chang, C. Journal of Catalysis, Vol. 47, Issue 2 https://doi.org/10.1016/0021-9517(77)90172-5	journal	May 1977
Catalytic methyl mercaptan coupling to ethylene in chabazite: DFT study of the first C C bond formation Baltrusaitis, J.; Bučko, T.; Michaels, W. Applied Catalysis B: Environmental, Vol. 187 https://doi.org/10.1016/j.apcatb.2016.01.021	journal	June 2016
Formaldehyde production from methanol and methyl mercaptan over titania and vanadia based catalysts Koivikko, Niina; Laitinen, Tiina; Ojala, Satu Applied Catalysis B: Environmental, Vol. 103, Issue 1-2 https://doi.org/10.1016/j.apcatb.2011.01.010	journal	March 2011
Direct synthesis of methyl mercaptan from H 2 /CO/H 2 S using tungsten based supported catalysts: Investigation of the active phase Cordova, A.; Blanchard, P.; Salembier, H. Catalysis Today, Vol. 292 https://doi.org/10.1016/j.cattod.2016.10.032	journal	September 2017
Influence of Potassium on the Synthesis of Methanethiol from Carbonyl Sulfide on Sulfided Mo/Al2O3 Catalyst Gutiérrez, Oliver Y.; Kaufmann, Christoph; Lercher, Johannes A. ChemCatChem, Vol. 3, Issue 9 https://doi.org/10.1002/cctc.201100124	journal	July 2011
Direct synthesis of methanethiol from H2S-rich syngas over sulfided Mo-based catalysts Chen, Aiping; Wang, Qi; Li, Qiaoling Journal of Molecular Catalysis A: Chemical, Vol. 283, Issue 1-2 https://doi.org/10.1016/j.molcata.2007.12.014	journal	March 2008
Synthesis of methyl mercaptan from carbon oxides and H2S with tungsten—alumina catalysts Barrault, J.; Boulinguiez, M.; Forquy, C. Applied Catalysis, Vol. 33, Issue 2 https://doi.org/10.1016/S0166-9834(00)83064-X	journal	September 1987
Alumina supported tungsten hydrides, new efficient catalysts for alkane metathesis Taoufik, Mostafa; Roux, Erwan Le; Thivolle-Cazat, Jean Topics in Catalysis, Vol. 40, Issue 1-4 https://doi.org/10.1007/s11244-006-0108-4	journal	November 2006
Olefin Metathesis by Supported Metal Oxide Catalysts Lwin, Soe; Wachs, Israel E. ACS Catalysis, Vol. 4, Issue 8 https://doi.org/10.1021/cs500528h	journal	June 2014
Alumina-supported tungsten catalysts for the hydrogenation of carbon monoxide Oades, R. D.; Morris, S. R.; Moyes, R. B. Catalysis Today, Vol. 10, Issue 3 https://doi.org/10.1016/0920-5861(91)80019-6	journal	September 1991
Kinetic study of the partial hydrogenation of 1-heptyne on tungsten oxide supported on alumina Maccarrone, María; Torres, Gerardo; Lederhos, Cecilia Journal of Chemical Technology & Biotechnology, Vol. 87, Issue 11 https://doi.org/10.1002/jctb.3778	journal	March 2012
Gas-phase dehydration of glycerol to acrolein over Al2O3-, SiO2-, and TiO2-supported Nb- and W-oxide catalysts Massa, Mariano; Andersson, Arne; Finocchio, Elisabetta Journal of Catalysis, Vol. 307 https://doi.org/10.1016/j.jcat.2013.07.022	journal	November 2013
Genesis of Brønsted Acid Sites during Dehydration of 2-Butanol on Tungsten Oxide Catalysts Baertsch, Chelsey D.; Komala, Kenny T.; Chua, Yong-Hwee Journal of Catalysis, Vol. 205, Issue 1 https://doi.org/10.1006/jcat.2001.3426	journal	January 2002
Hydrodesulfurization and hydrogenation on alumina-supported tungsten and nickel-promoted tungsten catalysts Kabe, Toshiaki; Qian, Weihua; Funato, Asumi Physical Chemistry Chemical Physics, Vol. 1, Issue 5 https://doi.org/10.1039/a807913g	journal	January 1999
Preparation of highly dispersed W/Al2O3 hydrodesulfurization catalysts via a microwave hydrothermal method: Effect of oxalic acid Wang, Hao; Liu, Zhenwei; Wu, Yan Arabian Journal of Chemistry, Vol. 9, Issue 1 https://doi.org/10.1016/j.arabjc.2014.11.023	journal	January 2016
Effect of WO3 loading on the surface acidity of WO3/Al2O3 composite oxides Zhang, R.; Jagiello, J.; Hu, J. F. Applied Catalysis A: General, Vol. 84, Issue 2 https://doi.org/10.1016/0926-860X(92)80111-O	journal	May 1992
Catalysis science of the solid acidity of model supported tungsten oxide catalysts Wachs, Israel E.; Kim, Taejin; Ross, Elizabeth I. Catalysis Today, Vol. 116, Issue 2 https://doi.org/10.1016/j.cattod.2006.02.085	journal	August 2006
Structure of surface tungsten oxide species in the tungsten trioxide/alumina supported oxide system from x-ray absorption near-edge spectroscopy and Raman spectroscopy Horsley, J. A.; Wachs, I. E.; Brown, J. M. The Journal of Physical Chemistry, Vol. 91, Issue 15 https://doi.org/10.1021/j100299a018	journal	July 1987
Surface structures of supported tungsten oxide catalysts under dehydrated conditions Kim, Du Soung; Ostromecki, Marlene; Wachs, Israel E. Journal of Molecular Catalysis A: Chemical, Vol. 106, Issue 1-2 https://doi.org/10.1016/1381-1169(95)00186-7	journal	March 1996
Molecular/electronic structure–surface acidity relationships of model-supported tungsten oxide catalysts Kim, T.; Burrows, A.; Kiely, C. Journal of Catalysis, Vol. 246, Issue 2 https://doi.org/10.1016/j.jcat.2006.12.018	journal	March 2007
Kinetics of the Catalytic Reaction between Methanol and Hydrogen Sulfide Mashkin, Viktor Yu.; Kudenkov, Valerii M.; Mashkina, Anna V. Industrial & Engineering Chemistry Research, Vol. 34, Issue 9 https://doi.org/10.1021/ie00048a006	journal	September 1995
Monitoring Solid Oxide CO ₂ Capture Sorbents in Action Keturakis, Christopher J.; Ni, Fan; Spicer, Michelle ChemSusChem, Vol. 7, Issue 12 https://doi.org/10.1002/cssc.201402474	journal	October 2014
Cation synergies affect ammonia adsorption over VOX and (V,W)OX dispersed on α-Al2O3 (0001) and α-Fe2O3 (0001) McBriarty, Martin E.; Ellis, Donald E. Surface Science, Vol. 651 https://doi.org/10.1016/j.susc.2016.03.015	journal	September 2016
Structural Determination of Bulk and Surface Tungsten Oxides with UV−vis Diffuse Reflectance Spectroscopy and Raman Spectroscopy Ross-Medgaarden, Elizabeth I.; Wachs, Israel E. The Journal of Physical Chemistry C, Vol. 111, Issue 41 https://doi.org/10.1021/jp074219c	journal	September 2007
The influence of metal oxide additives on the molecular structures of surface tungsten oxide species on alumina: I. Ambient conditions Ostromecki, Marlene M.; Burcham, Loyd J.; Wachs, Israel E. Journal of Molecular Catalysis A: Chemical, Vol. 132, Issue 1 https://doi.org/10.1016/S1381-1169(97)00226-4	journal	May 1998
Atomic-Scale View of VO _X –WO _X Coreduction on the α-Al ₂ O ₃ (0001) Surface McBriarty, Martin E.; Campbell, Gavin P.; Drake, Tasha L. The Journal of Physical Chemistry C, Vol. 119, Issue 28 https://doi.org/10.1021/acs.jpcc.5b04802	journal	June 2015
Clean synthesis of alkyl levulinates from levulinic acid over one pot synthesized WO3-SBA-16 catalyst Enumula, Siva Sankar; Gurram, Venkata Ramesh Babu; Chada, Raji Reddy Journal of Molecular Catalysis A: Chemical, Vol. 426 https://doi.org/10.1016/j.molcata.2016.10.032	journal	January 2017
Enhanced Catalyst Activity of W O 3 Using Polypyrrole as Support for Acidic Esterification of Glycerol with Acetic Acid Ghoreishi, Khadijeh Beigom; Yarmo, Mohd Ambar; Nordin, Norasikin Mohamad Journal of Chemistry, Vol. 2013 https://doi.org/10.1155/2013/264832	journal	January 2013
Conversion of glycerol to acrolein in the presence of WO3/TiO2 catalysts Ulgen, Arda; Hoelderich, Wolfgang F. Applied Catalysis A: General, Vol. 400, Issue 1-2 https://doi.org/10.1016/j.apcata.2011.04.005	journal	June 2011
A decade+ of operando spectroscopy studies Chakrabarti, Anisha; Ford, Michael E.; Gregory, Daniel Catalysis Today, Vol. 283 https://doi.org/10.1016/j.cattod.2016.12.012	journal	April 2017
Characterization of tungsta-titania catalysts Ramis, G.; Busca, G.; Cristiani, C. Langmuir, Vol. 8, Issue 7 https://doi.org/10.1021/la00043a010	journal	July 1992
Infrared Spectroscopy of Ammonia on Iron: Thermal Stability and the Influence of Potassium Iyngaran, P.; Madden, D. C.; King, D. A. The Journal of Physical Chemistry C, Vol. 118, Issue 23 https://doi.org/10.1021/jp409718x	journal	May 2014
Infrared spectroscopic identification of species arising from reactive adsorption of carbon oxides on metal oxide surfaces Busca, G.; Lorenzelli, V. Materials Chemistry, Vol. 7, Issue 1 https://doi.org/10.1016/0390-6035(82)90059-1	journal	January 1982
Surface chemistry of carbon dioxide revisited Taifan, William; Boily, Jean-François; Baltrusaitis, Jonas Surface Science Reports, Vol. 71, Issue 4 https://doi.org/10.1016/j.surfrep.2016.09.001	journal	December 2016
The chemistry of the dinuclear carbonyls anions VI. Anionic metal carbonyl carboxylates Schlientz, W. Joseph; Lavender, Y.; Welcman, N. Journal of Organometallic Chemistry, Vol. 33, Issue 3 https://doi.org/10.1016/S0022-328X(00)87419-7	journal	December 1971
Synthesis and Characterization of CO2-Bridged Bimetallic Compounds Derived from a Rhenium Metallocarboxylate. Correlation of IR Spectral Data with Coordination Geometry and Bonding Type Gibson, Dorothy H.; Franco, Jaime O.; Mehta, Jayesh M. Organometallics, Vol. 14, Issue 11 https://doi.org/10.1021/om00011a028	journal	November 1995
Carbon dioxide coordination chemistry: metal complexes and surface-bound species. What relationships? Gibson, Dorothy H. Coordination Chemistry Reviews, Vol. 185-186 https://doi.org/10.1016/S0010-8545(99)00021-1	journal	May 1999
Claus catalysis. 1. Adsorption of sulfur dioxide on the alumina catalyst studied by FTIR and EPR spectroscopy Datta, Arunabha; Cavell, Ronald G.; Tower, Robert W. The Journal of Physical Chemistry, Vol. 89, Issue 3 https://doi.org/10.1021/j100249a014	journal	January 1985
SO ₂ Adsorption and Transformations on γ-Al ₂ O ₃ Surfaces: A Density Functional Theory Study Lo, John M. H.; Ziegler, Tom; Clark, Peter D. The Journal of Physical Chemistry C, Vol. 114, Issue 23 https://doi.org/10.1021/jp910895g	journal	May 2010
Elucidation of structures of surface sulfate species on sulfated titania and mechanism of improved activity Lin, Xuan Hao; Yin, Xue Jiao; Liu, Jun Yi Applied Catalysis B: Environmental, Vol. 203 https://doi.org/10.1016/j.apcatb.2016.10.068	journal	April 2017
The Organometallic Chemistry of Carbon Suboxide Paiaro, Gastone; Pandolfo, Luciano Comments on Inorganic Chemistry, Vol. 12, Issue 4 https://doi.org/10.1080/02603599108053475	journal	August 1991

Cited By (1)

Mesoporous amorphous Al ₂ O ₃ /crystalline WO ₃ heterophase hybrids for electrocatalysis and gas sensing applications Zou, Yidong; Xi, Shibo; Bo, Tao Journal of Materials Chemistry A, Vol. 7, Issue 38 https://doi.org/10.1039/c9ta08633a	journal	January 2019