Identifying different types of catalysts for CO2 reduction by ethane through dry reforming and oxidative dehydrogenation

Chen, Jingguang G.; Myint, Myat Noe Zin; Kattel, Shyam; Xie, Zhenhua; Gomez, Elaine; Liu, Ping

doi:10.1002/anie.201508128

Identifying different types of catalysts for CO₂ reduction by ethane through dry reforming and oxidative dehydrogenation

Journal Article · Tue Nov 10 00:00:00 EST 2015 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201508128· OSTI ID:1246794

Chen, Jingguang G. ^[1]; Myint, Myat Noe Zin ^[2]; Kattel, Shyam ^[3]; Xie, Zhenhua ^[4]; Gomez, Elaine ^[4]; Liu, Ping ^[3]

Columbia Univ., New York, NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
Univ. of Delaware, Newark, DE (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Columbia Univ., New York, NY (United States)

In this study, the recent shale gas boom combined with the requirement to reduce atmospheric CO₂ have created an opportunity for using both raw materials (shale gas and CO₂) in a single process. Shale gas is primarily made up of methane, but ethane comprises about 10 % and reserves are underutilized. Two routes have been investigated by combining ethane decomposition with CO₂ reduction to produce products of higher value. The first reaction is ethane dry reforming which produces synthesis gas (CO+H₂). The second route is oxidative dehydrogenation which produces ethylene using CO₂ as a soft oxidant. The results of this study indicate that the Pt/CeO₂ catalyst shows promise for the production of synthesis gas, while Mo₂C-based materials preserve the C—C bond of ethane to produce ethylene. These findings are supported by density functional theory (DFT) calculations and X-ray absorption near-edge spectroscopy (XANES) characterization of the catalysts under in situ reaction conditions.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-05CH11231; SC0012704

OSTI ID:: 1246794

Alternate ID(s):: OSTI ID: 1813885

Report Number(s):: BNL--111965-2016-JA; KC0302010

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 51 Vol. 54; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (66)

Molybdenum Carbide as Alternative Catalysts to Precious Metals for Highly Selective Reduction of CO ₂ to CO Porosoff, Marc D.; Yang, Xiaofang; Boscoboinik, J. Anibal Angewandte Chemie, Vol. 126, Issue 26 https://doi.org/10.1002/ange.201404109	journal	May 2014
Molybdenum Carbide as Alternative Catalysts to Precious Metals for Highly Selective Reduction of CO ₂ to CO Porosoff, Marc D.; Yang, Xiaofang; Boscoboinik, J. Anibal Angewandte Chemie International Edition, Vol. 53, Issue 26 https://doi.org/10.1002/anie.201404109	journal	May 2014
Catalytic Technology for Carbon Dioxide Reforming of Methane to Synthesis Gas Fan, Mun-Sing; Abdullah, Ahmad Zuhairi; Bhatia, Subhash ChemCatChem, Vol. 1, Issue 2 https://doi.org/10.1002/cctc.200900025	journal	October 2009
Studies on Dehydrogenation of Ethane in the Presence of CO ₂ over Octahedral Molecular Sieve (OMS-2) Catalysts Jin, Lei; Reutenauer, Justin; Opembe, Naftali ChemCatChem, Vol. 1, Issue 4 https://doi.org/10.1002/cctc.200900149	journal	December 2009
Oxidative Dehydrogenation of Ethane: Common Principles and Mechanistic Aspects Gärtner, Christian A.; van Veen, André C.; Lercher, Johannes A. ChemCatChem, Vol. 5, Issue 11 https://doi.org/10.1002/cctc.201200966	journal	March 2013
Selective Hydrodeoxygenation of Biomass-Derived Oxygenates to Unsaturated Hydrocarbons using Molybdenum Carbide Catalysts Ren, Hui; Yu, Weiting; Salciccioli, Michael ChemSusChem, Vol. 6, Issue 5 https://doi.org/10.1002/cssc.201200991	journal	April 2013
Effect of Catalyst Structure on Oxidative Dehydrogenation of Ethane and Propane on Alumina-Supported Vanadia Argyle, Morris D.; Chen, Kaidong; Bell, Alexis T. Journal of Catalysis, Vol. 208, Issue 1 https://doi.org/10.1006/jcat.2002.3570	journal	May 2002
On the influence of the acid-base character of catalysts on the oxidative dehydrogenation of alkanes Concepción, P.; Galli, A.; Nieto, J. M. López Topics in Catalysis, Vol. 3, Issue 3-4 https://doi.org/10.1007/BF02113867	journal	August 1996
Non-catalytic pyrolysis of ethane to ethylene in the presence of CO2 with or without limited O2 Choudhary, Vasant R.; Mondal, Kartick C.; Mulla, Shafeek A. R. Journal of Chemical Sciences, Vol. 118, Issue 3 https://doi.org/10.1007/BF02708286	journal	May 2006
On the influence of the acid-base character of catalysts on the oxidative dehydrogenation of alkanes Concepción, P.; Galli, A.; Nieto, J. M. López Topics in Catalysis, Vol. 3, Issue 3-4 https://doi.org/10.1007/bf02113867	journal	August 1996
Non-catalytic pyrolysis of ethane to ethylene in the presence of CO2 with or without limited O2 Choudhary, Vasant R.; Mondal, Kartick C.; Mulla, Shafeek A. R. Journal of Chemical Sciences, Vol. 118, Issue 3 https://doi.org/10.1007/bf02708286	journal	May 2006
Dehydrogenation of isobutane in the presence of carbon dioxide over supported vanadium oxide catalysts Ogonowski, Jan; Skrzyńska, Elżbieta Reaction Kinetics and Catalysis Letters, Vol. 88, Issue 2 https://doi.org/10.1007/s11144-006-0064-9	journal	August 2006
Kinetics of the reverse-Boudouard reaction over supported nickel catalysts Osaki, Toshihiko; Mori, Toshiaki Reaction Kinetics and Catalysis Letters, Vol. 89, Issue 2 https://doi.org/10.1007/s11144-006-0145-9	journal	August 2006
Selective Conversion of Ethane to Ethene via Oxidative Dehydrogenation Over Ca-doped ThO2 Using CO2 as Oxidant Baidya, Tinku; van Vegten, Niels; Baiker, Alfons Topics in Catalysis, Vol. 54, Issue 13-15 https://doi.org/10.1007/s11244-011-9696-8	journal	August 2011
Replacing Precious Metals with Carbide Catalysts for Hydrogenation Reactions Hou, Ruijun; Chang, Kuan; Chen, Jingguang G. Topics in Catalysis, Vol. 58, Issue 4-6 https://doi.org/10.1007/s11244-015-0365-1	journal	March 2015
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Oxidative Dehydrogenation of Light (C₂ to C₄) Alkanes Kung, Harold H. Advances in Catalysis https://doi.org/10.1016/S0360-0564(08)60655-0	book	January 1994
Fundamental insights into the oxidative dehydrogenation of ethane to ethylene over catalytic materials discovered by an evolutionary approach Grubert, G.; Kondratenko, E.; Kolf, S. Catalysis Today, Vol. 81, Issue 3 https://doi.org/10.1016/S0920-5861(03)00132-9	journal	June 2003
Dehydrogenation and oxydehydrogenation of paraffins to olefins Bhasin, M. M.; McCain, J. H.; Vora, B. V. Applied Catalysis A: General, Vol. 221, Issue 1-2, p. 397-419 https://doi.org/10.1016/S0926-860X(01)00816-X	journal	November 2001
Dehydrogenation of ethane with carbon dioxide over supported chromium oxide catalysts Wang, Shaobin; Murata, K.; Hayakawa, T. Applied Catalysis A: General, Vol. 196, Issue 1 https://doi.org/10.1016/S0926-860X(99)00450-0	journal	March 2000
High-performance Cr/H-ZSM-5 catalysts for oxidative dehydrogenation of ethane to ethylene with CO2 as an oxidant Mimura, Naoki; Takahara, Isao; Inaba, Megumu Catalysis Communications, Vol. 3, Issue 6 https://doi.org/10.1016/S1566-7367(02)00117-6	journal	June 2002
Ni–Nb–O mixed oxides as highly active and selective catalysts for ethene production via ethane oxidative dehydrogenation. Part II: Mechanistic aspects and kinetic modeling Heracleous, E.; Lemonidou, A. Journal of Catalysis, Vol. 237, Issue 1 https://doi.org/10.1016/j.jcat.2005.11.003	journal	January 2006
Ceria reoxidation by CO2: A model study Staudt, T.; Lykhach, Y.; Tsud, N. Journal of Catalysis, Vol. 275, Issue 1 https://doi.org/10.1016/j.jcat.2010.07.032	journal	September 2010
Trends in the catalytic reduction of CO2 by hydrogen over supported monometallic and bimetallic catalysts Porosoff, Marc D.; Chen, Jingguang G. Journal of Catalysis, Vol. 301 https://doi.org/10.1016/j.jcat.2013.01.022	journal	May 2013
Activity and characterization of modified Cr2O3/ZrO2 nano-composite catalysts for oxidative dehydrogenation of ethane to ethylene with CO2 Deng, Shuang; Li, Huiquan; Li, Songgeng Journal of Molecular Catalysis A: Chemical, Vol. 268, Issue 1-2 https://doi.org/10.1016/j.molcata.2006.12.033	journal	May 2007
Oxidative Dehydrogenation of Light (C₂ to C₄) Alkanes Kung, Harold H. Advances in Catalysis https://doi.org/10.1016/s0360-0564(08)60655-0	book	January 1994
Fundamental insights into the oxidative dehydrogenation of ethane to ethylene over catalytic materials discovered by an evolutionary approach Grubert, G.; Kondratenko, E.; Kolf, S. Catalysis Today, Vol. 81, Issue 3 https://doi.org/10.1016/s0920-5861(03)00132-9	journal	June 2003
Dehydrogenation and oxydehydrogenation of paraffins to olefins Bhasin, M. M.; McCain, J. H.; Vora, B. V. Applied Catalysis A: General, Vol. 221, Issue 1-2, p. 397-419 https://doi.org/10.1016/s0926-860x(01)00816-x	journal	November 2001
Dehydrogenation of ethane with carbon dioxide over supported chromium oxide catalysts Wang, Shaobin; Murata, K.; Hayakawa, T. Applied Catalysis A: General, Vol. 196, Issue 1 https://doi.org/10.1016/s0926-860x(99)00450-0	journal	March 2000
High-performance Cr/H-ZSM-5 catalysts for oxidative dehydrogenation of ethane to ethylene with CO2 as an oxidant Mimura, Naoki; Takahara, Isao; Inaba, Megumu Catalysis Communications, Vol. 3, Issue 6 https://doi.org/10.1016/s1566-7367(02)00117-6	journal	June 2002
In Situ X-ray Absorption Fine Structure Studies on the Effect of pH on Pt Electronic Density during Aqueous Phase Reforming of Glycerol Karim, Ayman M.; Howard, Christopher; Roberts, Benjamin ACS Catalysis, Vol. 2, Issue 11 https://doi.org/10.1021/cs3005049	journal	September 2012
Theoretical and Experimental Studies of C–C versus C–O Bond Scission of Ethylene Glycol Reaction Pathways via Metal-Modified Molybdenum Carbides Yu, Weiting; Salciccioli, Michael; Xiong, Ke ACS Catalysis, Vol. 4, Issue 5 https://doi.org/10.1021/cs500124n	journal	April 2014
Mitigation of CO₂ by Chemical Conversion: Plausible Chemical Reactions and Promising Products Xiaoding, Xu; Moulijn, J. A. Energy & Fuels, Vol. 10, Issue 2, p. 305-325 https://doi.org/10.1021/ef9501511	journal	March 1996
Two-Stage Kinetic Model of Primary Coal Liquefaction Xu, Bin; Kandiyoti, Rafael Energy & Fuels, Vol. 10, Issue 5 https://doi.org/10.1021/ef9600265	journal	January 1996
Study on a kinetic model of atmospheric gas oil pyrolysis and coke deposition Zou, Renjun; Lou, Qiangkun; Mo, Sihong Industrial & Engineering Chemistry Research, Vol. 32, Issue 5 https://doi.org/10.1021/ie00017a011	journal	May 1993
A New Type of Strong Metal–Support Interaction and the Production of H ₂ through the Transformation of Water on Pt/CeO ₂ (111) and Pt/CeO _x /TiO ₂ (110) Catalysts Bruix, Albert; Rodriguez, José A.; Ramírez, Pedro J. Journal of the American Chemical Society, Vol. 134, Issue 21 https://doi.org/10.1021/ja302070k	journal	May 2012
Oxidative Dehydrogenation of Ethane over Cr/ZSM-5 Catalysts Using CO ₂ as an Oxidant Mimura, Naoki; Okamoto, Masaki; Yamashita, Hiromi The Journal of Physical Chemistry B, Vol. 110, Issue 43 https://doi.org/10.1021/jp061966l	journal	November 2006
The oxidative dehydrogenation of ethane with CO₂ over Mo₂C/SiO2 catalyst Solymosi, F.; Németh, R. Catalysis Letters, Vol. 62, Issue 2/4, p. 197-200 https://doi.org/10.1023/A:1019027912597	journal	October 1999
The oxidative dehydrogenation of ethane with CO₂ over Mo₂C/SiO2 catalyst Solymosi, F.; Németh, R. Catalysis Letters, Vol. 62, Issue 2/4, p. 197-200 https://doi.org/10.1023/a:1019027912597	journal	October 1999
Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets Chen, Ruyi; Cui, Qirui; Liao, Liyang Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-23414-3	journal	May 2021
High-resolution X-ray luminescence extension imaging Ou, Xiangyu; Qin, Xian; Huang, Bolong Nature, Vol. 590, Issue 7846 https://doi.org/10.1038/s41586-021-03251-6	journal	February 2021
Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect Tatemizo, Nobuyuki; Imada, Saki; Okahara, Kizuna Scientific Reports, Vol. 10, Issue 1 https://doi.org/10.1038/s41598-020-58835-5	journal	February 2020
The bending machine: CO ₂ activation and hydrogenation on δ-MoC(001) and β-Mo ₂ C(001) surfaces Posada-Pérez, Sergio; Viñes, Francesc; Ramirez, Pedro J. Phys. Chem. Chem. Phys., Vol. 16, Issue 28 https://doi.org/10.1039/C4CP01943A	journal	January 2014
Identifying trends and descriptors for selective CO ₂ conversion to CO over transition metal carbides Porosoff, Marc D.; Kattel, Shyam; Li, Wenhui Chemical Communications, Vol. 51, Issue 32 https://doi.org/10.1039/C5CC01545F	journal	January 2015
Dehydrogenation of ethane over gallium oxide in the presence of carbon dioxide Nakagawa, Kiyoharu; Okamura, Masato; Ikenaga, Naoki Chemical Communications, Issue 9 https://doi.org/10.1039/a800184g	journal	January 1998
A first principles study of oxygen reduction reaction on a Pt(111) surface modified by a subsurface transition metal M (M = Ni, Co, or Fe) Duan, Zhiyao; Wang, Guofeng Physical Chemistry Chemical Physics, Vol. 13, Issue 45 https://doi.org/10.1039/c1cp21687b	journal	January 2011
The bending machine: CO ₂ activation and hydrogenation on δ-MoC(001) and β-Mo ₂ C(001) surfaces Posada-Pérez, Sergio; Viñes, Francesc; Ramirez, Pedro J. Phys. Chem. Chem. Phys., Vol. 16, Issue 28 https://doi.org/10.1039/c4cp01943a	journal	January 2014
Identifying trends and descriptors for selective CO ₂ conversion to CO over transition metal carbides Porosoff, Marc D.; Kattel, Shyam; Li, Wenhui Chemical Communications, Vol. 51, Issue 32 https://doi.org/10.1039/c5cc01545f	journal	January 2015
Global temperature change Hansen, J.; Sato, M.; Ruedy, R. Proceedings of the National Academy of Sciences, Vol. 103, Issue 39 https://doi.org/10.1073/pnas.0606291103	journal	September 2006
Inhomogeneous Electron Gas Hohenberg, P.; Kohn, W. Physical Review, Vol. 136, Issue 3B, p. B864-B871 https://doi.org/10.1103/PhysRev.136.B864	journal	November 1964
Self-Consistent Equations Including Exchange and Correlation Effects Kohn, W.; Sham, L. J. Physical Review, Vol. 140, Issue 4A, p. A1133-A1138 https://doi.org/10.1103/PhysRev.140.A1133	journal	November 1965
Special points for Brillouin-zone integrations Monkhorst, Hendrik J.; Pack, James D. Physical Review B, Vol. 13, Issue 12, p. 5188-5192 https://doi.org/10.1103/PhysRevB.13.5188	journal	June 1976
Accurate and simple analytic representation of the electron-gas correlation energy Perdew, John P.; Wang, Yue Physical Review B, Vol. 45, Issue 23, p. 13244-13249 https://doi.org/10.1103/PhysRevB.45.13244	journal	June 1992
Ab initio molecular dynamics for open-shell transition metals Kresse, G.; Hafner, J. Physical Review B, Vol. 48, Issue 17 https://doi.org/10.1103/PhysRevB.48.13115	journal	November 1993
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Self-Consistent Equations Including Exchange and Correlation Effects Kohn, W.; Sham, L. J. Physical Review, Vol. 140, Issue 4A, p. A1133-A1138 https://doi.org/10.1103/physrev.140.a1133	journal	November 1965
Special points for Brillouin-zone integrations Monkhorst, Hendrik J.; Pack, James D. Physical Review B, Vol. 13, Issue 12, p. 5188-5192 https://doi.org/10.1103/physrevb.13.5188	journal	June 1976
Accurate and simple analytic representation of the electron-gas correlation energy Perdew, John P.; Wang, Yue Physical Review B, Vol. 45, Issue 23, p. 13244-13249 https://doi.org/10.1103/physrevb.45.13244	journal	June 1992
Ab initio molecular dynamics for open-shell transition metals Kresse, G.; Hafner, J. Physical Review B, Vol. 48, Issue 17 https://doi.org/10.1103/physrevb.48.13115	journal	November 1993
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/physrevb.50.17953	journal	December 1994
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/physrevb.59.1758	journal	January 1999
Inhomogeneous Electron Gas Rajagopal, A. K.; Callaway, J. Physical Review B, Vol. 7, Issue 5 https://doi.org/10.1103/physrevb.7.1912	journal	March 1973
Impact of CO ₂ -Induced Warming on Simulated Hurricane Intensity and Precipitation: Sensitivity to the Choice of Climate Model and Convective Parameterization Knutson, Thomas R.; Tuleya, Robert E. Journal of Climate, Vol. 17, Issue 18 https://doi.org/10.1175/1520-0442(2004)017<3477:IOCWOS>2.0.CO;2	journal	September 2004
Impact of CO ₂ -Induced Warming on Simulated Hurricane Intensity and Precipitation: Sensitivity to the Choice of Climate Model and Convective Parameterization Knutson, Thomas R.; Tuleya, Robert E. Journal of Climate, Vol. 17, Issue 18 https://doi.org/10.1175/1520-0442(2004)017<3477:iocwos>2.0.co;2	journal	September 2004
Selective Conversion of Ethane to Ethene via Oxidative Dehydrogenation Over Ca-doped ThO2 Using CO2 as Oxidant Tinku, Baidya,; Niels, van Vegten,; Alfons, Baiker, ETH Zurich https://doi.org/10.3929/ethz-b-000046541	text	January 2011

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