Deciphering Dynamic Structural and Mechanistic Complexity in Cu/CeO2/ZSM-5 Catalysts for the Reverse Water-Gas Shift Reaction

Vovchok, Dimitriy; Zhang, Cheng; Hwang, Sooyeon; Jiao, Luyun; Zhang, Feng; Liu, Zongyuan; Senanayake, Sanjaya D.; Rodriguez, Jose A.

doi:10.1021/acscatal.0c01584

Deciphering Dynamic Structural and Mechanistic Complexity in Cu/CeO₂/ZSM-5 Catalysts for the Reverse Water-Gas Shift Reaction

Journal Article · Thu Aug 13 00:00:00 EDT 2020 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.0c01584· OSTI ID:1677671

^[1]; ^[2]; ^[1]; Jiao, Luyun ^[2]; Zhang, Feng ^[3]; ^[1]; ^[1]; ^[1]

Brookhaven National Lab. (BNL), Upton, NY (United States)
Long Island Univ. (Post), Greenvale, NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States)

In this paper, we have prepared and investigated the structural and mechanistic properties of an array of active Cu/CeO₂/ZSM-5 catalysts for the reverse water-gas shift (RWGS) reaction, where the roles of Cu and CeO₂ as a promoter were studied under reaction conditions. The concentration of copper was varied between 0 and 10 wt %, while the concentration of CeO₂ was varied between 0 and 48 wt % in several permutations of Cu/CeO₂/ZSM-5 catalysts. RWGS reactivity trends revealed that all three components of the catalyst system are essential for promoting and sustaining the optimum catalytic activity. The dynamic chemical states of copper and cerium were probed using in situ X-ray absorption spectroscopy (X-ray absorption near-edge structure and extended X-ray absorption fine structure), revealing reduced copper and mostly oxidized ceria in the active state. In situ X-ray diffraction data revealed the presence of copper aggregates, as well as copper within the ZSM-5 lattice. In situ and isotopic switching diffuse reflectance infrared Fourier transform spectroscopy analyses were used to unambiguously establish copper speciation within the ZSM-5 lattice and CeO₂ surface sites as participatory in the RWGS mechanism, with surface formate species on CeO₂ being a reaction intermediate. Based on a robust set of real-time structural, electronic, and surface chemical data, we proposed a reaction mechanism that involves the participation of all three components of this catalyst system.

View Accepted Manuscript (DOE)

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

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

Grant/Contract Number:: SC0012704

OSTI ID:: 1677671

Alternate ID(s):: OSTI ID: 1659295
OSTI ID: 1690202

Report Number(s):: BNL-219966-2020--JAAM

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 17 Vol. 10; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (65)

Shape and Crystal-Plane Effects of Nanoscale Ceria on the Activity of Au-CeO₂ Catalysts for the Water–Gas Shift Reaction Si, Rui; Flytzani-Stephanopoulos, Maria Angewandte Chemie International Edition, Vol. 47, Issue 15, p. 2884-2887 https://doi.org/10.1002/anie.200705828	journal	March 2008
Photocatalytic Conversion of Carbon Dioxide with Water into Methane: Platinum and Copper(I) Oxide Co-catalysts with a Core-Shell Structure Zhai, Qingge; Xie, Shunji; Fan, Wenqing Angewandte Chemie International Edition, Vol. 52, Issue 22 https://doi.org/10.1002/anie.201301473	journal	April 2013
Water-Gas-Shift over Metal-Free Nanocrystalline Ceria: An Experimental and Theoretical Study Guild, Curtis J.; Vovchok, Dimitriy; Kriz, David A. ChemCatChem, Vol. 9, Issue 8 https://doi.org/10.1002/cctc.201700081	journal	March 2017
A DRIFTS Study of Cu–ZSM-5 Prior to and during Its Use for N2O Decomposition Fanning, Paul E.; Vannice, M. Albert Journal of Catalysis, Vol. 207, Issue 2 https://doi.org/10.1006/jcat.2002.3518	journal	April 2002
Nature, distribution and reactivity of copper species in over-exchanged Cu-ZSM-5 catalysts: an XPS/XAES study Shpiro, Efim S.; Gr�nert, Wolfgang; Joyner, Richard W. Catalysis Letters, Vol. 24, Issue 1-2 https://doi.org/10.1007/BF00807386	journal	January 1994
High-temperature thermal expansion of six metallic elements measured by dilatation method and X-ray diffraction Suh, In-Kook; Ohta, H.; Waseda, Y. Journal of Materials Science, Vol. 23, Issue 2 https://doi.org/10.1007/BF01174717	journal	February 1988
Conversion of CO2 into biomass by microalgae: how realistic a contribution may it be to significant CO2 removal? Acién Fernández, F. Gabriel; González-López, C. V.; Fernández Sevilla, J. M. Applied Microbiology and Biotechnology, Vol. 96, Issue 3 https://doi.org/10.1007/s00253-012-4362-z	journal	August 2012
Mechanism of the reverse water gas shift reaction over Cu/ZnO catalyst*1 Fujita, S. Journal of Catalysis, Vol. 134, Issue 1 https://doi.org/10.1016/0021-9517(92)90223-5	journal	March 1992
Cu(I)-ZSM-5 zeolites prepared by reaction of H-ZSM-5 with gaseous CuCl: Spectroscopic characterization and reactivity towards carbon monoxide and nitric oxide Spoto, G.; Zecchina, A.; Bordiga, S. Applied Catalysis B: Environmental, Vol. 3, Issue 2-3 https://doi.org/10.1016/0926-3373(93)E0032-7	journal	February 1994
IR study of polycrystalline ceria properties in oxidised and reduced states Binet, Claude; Daturi, Marco; Lavalley, Jean-Claude Catalysis Today, Vol. 50, Issue 2 https://doi.org/10.1016/S0920-5861(98)00504-5	journal	April 1999
Experimental methods in catalytic kinetics Perego, C. Catalysis Today, Vol. 52, Issue 2-3 https://doi.org/10.1016/S0920-5861(99)00071-1	journal	September 1999
Development of ZnO/Al2O3 catalyst for reverse-water-gas-shift reaction of CAMERE (carbon dioxide hydrogenation to form methanol via a reverse-water-gas-shift reaction) process Park, Sang-Woo; Joo, Oh-Shim; Jung, Kwang-Deog Applied Catalysis A: General, Vol. 211, Issue 1 https://doi.org/10.1016/S0926-860X(00)00840-1	journal	March 2001
A comparative study of water-gas-shift reaction over ceria supported metallic catalysts Hilaire, S.; Wang, X.; Luo, T. Applied Catalysis A: General, Vol. 215, Issue 1-2 https://doi.org/10.1016/S0926-860X(01)00535-X	journal	July 2001
Study of reverse water gas shift reaction by TPD, TPR and CO2 hydrogenation over potassium-promoted Cu/SiO2 catalyst Chen, Ching-Shiun; Cheng, Wu-Hsun; Lin, Shou-Shiun Applied Catalysis A: General, Vol. 238, Issue 1 https://doi.org/10.1016/S0926-860X(02)00221-1	journal	January 2003
Reverse water gas shift reaction over Co-precipitated Ni-CeO2 catalysts Wang, Luhui; Zhang, Shaoxing; Liu, Yuan Journal of Rare Earths, Vol. 26, Issue 1 https://doi.org/10.1016/S1002-0721(08)60039-3	journal	February 2008
Low temperature water–gas shift: Applications of a modified SSITKA–DRIFTS method under conditions of H2 co-feeding over metal/ceria and related oxides Jacobs, Gary; Davis, Burtron H. Applied Catalysis A: General, Vol. 333, Issue 2 https://doi.org/10.1016/j.apcata.2007.07.029	journal	December 2007
Reverse water–gas shift reaction over ceria nanocube synthesized by hydrothermal method Liu, Yongjun; Li, Zhifeng; Xu, Hongbo Catalysis Communications, Vol. 76 https://doi.org/10.1016/j.catcom.2015.12.011	journal	February 2016
On the need to use steady-state or operando techniques to investigate reaction mechanisms: An in situ DRIFTS and SSITKA-based study example Tibiletti, Daniele; Goguet, Alexandre; Reid, David Catalysis Today, Vol. 113, Issue 1-2 https://doi.org/10.1016/j.cattod.2005.11.013	journal	March 2006
A review of research progress on heterogeneous catalysts for methanol synthesis from carbon dioxide hydrogenation Dang, Shanshan; Yang, Haiyan; Gao, Peng Catalysis Today, Vol. 330 https://doi.org/10.1016/j.cattod.2018.04.021	journal	June 2019
Location and chemical speciation of Cu in ZSM-5 during the water-gas shift reaction Vovchok, Dimitriy; Tata, James; Orozco, Ivan Catalysis Today, Vol. 323 https://doi.org/10.1016/j.cattod.2018.07.049	journal	February 2019
Recent advances in the homogeneous hydrogenation of carbon dioxide Jessop, Philip G.; Joó, Ferenc; Tai, Chih-Cheng Coordination Chemistry Reviews, Vol. 248, Issue 21-24, p. 2425-2442 https://doi.org/10.1016/j.ccr.2004.05.019	journal	December 2004
Interfaces in heterogeneous catalytic reactions: Ambient pressure XPS as a tool to unravel surface chemistry Palomino, Robert M.; Hamlyn, Rebecca; Liu, Zongyuan Journal of Electron Spectroscopy and Related Phenomena, Vol. 221 https://doi.org/10.1016/j.elspec.2017.04.006	journal	November 2017
Study of the origin of the deactivation of a Pt/CeO catalyst during reverse water gas shift (RWGS) reaction Goguet, A.; Meunier, F.; Breen, J. Journal of Catalysis, Vol. 226, Issue 2 https://doi.org/10.1016/j.jcat.2004.06.011	journal	September 2004
Comparative study on redox properties of nanosized CeO2 and CuO/CeO2 under CO/O2 Martinezarias, A.; Gamarra, D.; Fernandezgarcia, M. Journal of Catalysis, Vol. 240, Issue 1 https://doi.org/10.1016/j.jcat.2006.02.026	journal	May 2006
Quantitative analysis of the reactivity of formate species seen by DRIFTS over a Au/Ce(La)O2 water–gas shift catalyst: First unambiguous evidence of the minority role of formates as reaction intermediates Meunier, F.; Reid, D.; Goguet, A. Journal of Catalysis, Vol. 247, Issue 2 https://doi.org/10.1016/j.jcat.2007.02.013	journal	April 2007
CO2 hydrogenation on Au/TiC, Cu/TiC, and Ni/TiC catalysts: Production of CO, methanol, and methane Rodriguez, José A.; Evans, Jaime; Feria, Leticia Journal of Catalysis, Vol. 307 https://doi.org/10.1016/j.jcat.2013.07.023	journal	November 2013
CO2 valorisation via Reverse Water-Gas Shift reaction using advanced Cs doped Fe-Cu/Al2O3 catalysts Pastor-Pérez, L.; Baibars, F.; Le Sache, E. Journal of CO2 Utilization, Vol. 21 https://doi.org/10.1016/j.jcou.2017.08.009	journal	October 2017
On the curve-fitting of XPS Ce(3d) spectra of cerium oxides Paparazzo, Ernesto Materials Research Bulletin, Vol. 46, Issue 2 https://doi.org/10.1016/j.materresbull.2010.11.009	journal	February 2011
Over-loaded Cu-ZSM-5 upon heating treatment: A time resolved X-ray diffraction study Dalconi, Maria Chiara; Cruciani, Giuseppe; Alberti, Alberto Microporous and Mesoporous Materials, Vol. 94, Issue 1-3 https://doi.org/10.1016/j.micromeso.2006.03.047	journal	September 2006
Preparation and characterization of copper nanoparticles encapsulated inside ZSM-5 zeolite and NO adsorption Othman Ali, Ibraheem Materials Science and Engineering: A, Vol. 459, Issue 1-2 https://doi.org/10.1016/j.msea.2007.01.100	journal	June 2007
Mechanisms and kinetics of CO 2 hydrogenation to value-added products: A detailed review on current status and future trends Saeidi, Samrand; Najari, Sara; Fazlollahi, Farhad Renewable and Sustainable Energy Reviews, Vol. 80 https://doi.org/10.1016/j.rser.2017.05.204	journal	December 2017
The surface chemistry of cerium oxide Mullins, David R. Surface Science Reports, Vol. 70, Issue 1 https://doi.org/10.1016/j.surfrep.2014.12.001	journal	March 2015
Cerium oxidation state in ceria nanoparticles studied with X-ray photoelectron spectroscopy and absorption near edge spectroscopy Zhang, Feng; Wang, Peng; Koberstein, J. Surface Science, Vol. 563, Issue 1-3 https://doi.org/10.1016/j.susc.2004.05.138	journal	August 2004
Challenges in the Greener Production of Formates/Formic Acid, Methanol, and DME by Heterogeneously Catalyzed CO ₂ Hydrogenation Processes Álvarez, Andrea; Bansode, Atul; Urakawa, Atsushi Chemical Reviews, Vol. 117, Issue 14 https://doi.org/10.1021/acs.chemrev.6b00816	journal	May 2017
In Situ Characterization of Mesoporous Co/CeO ₂ Catalysts for the High-Temperature Water-Gas Shift Vovchok, Dimitriy; Guild, Curtis J.; Dissanayake, Shanka The Journal of Physical Chemistry C, Vol. 122, Issue 16 https://doi.org/10.1021/acs.jpcc.8b01271	journal	April 2018
In Situ Characterization of Cu/CeO ₂ Nanocatalysts for CO ₂ Hydrogenation: Morphological Effects of Nanostructured Ceria on the Catalytic Activity Lin, Lili; Yao, Siyu; Liu, Zongyuan The Journal of Physical Chemistry C, Vol. 122, Issue 24 https://doi.org/10.1021/acs.jpcc.8b03596	journal	May 2018
Metal-Free Low-Temperature Water–Gas Shift Catalysis over Small, Hydroxylated Ceria Nanoparticles Huang, Xing; Beck, Matthew J. ACS Catalysis, Vol. 5, Issue 11 https://doi.org/10.1021/acscatal.5b01227	journal	September 2015
Thermochemical CO ₂ Hydrogenation to Single Carbon Products: Scientific and Technological Challenges Roy, Soumyabrata; Cherevotan, Arjun; Peter, Sebastian C. ACS Energy Letters, Vol. 3, Issue 8 https://doi.org/10.1021/acsenergylett.8b00740	journal	July 2018
Nature and Surface Redox Properties of Copper(II)-Promoted Cerium(IV) Oxide CO-Oxidation Catalysts Harrison, Philip G.; Ball, Ian K.; Azelee, Wan Chemistry of Materials, Vol. 12, Issue 12 https://doi.org/10.1021/cm001113k	journal	December 2000
EXAFS and XANES Studies of Copper in a Solidified Fly Ash Hsiao, M. C.; Wang, H. Paul; Yang, Y. W. Environmental Science & Technology, Vol. 35, Issue 12 https://doi.org/10.1021/es001374v	journal	June 2001
Carbon Dioxide Hydrogenation To Form Methanol via a Reverse-Water-Gas-Shift Reaction (the CAMERE Process) Joo, Oh-Shim; Jung, Kwang-Deog; Moon, Il Industrial & Engineering Chemistry Research, Vol. 38, Issue 5 https://doi.org/10.1021/ie9806848	journal	May 1999
Redox behavior and mobility of copper ions in NaZSM-5 zeolite during oxidation Itho, Y.; Nishiyama, S.; Tsuruya, S. The Journal of Physical Chemistry, Vol. 98, Issue 3 https://doi.org/10.1021/j100054a036	journal	January 1994
Infrared and x-ray photoelectron spectroscopy study of carbon monoxide and carbon dioxide on platinum/ceria Jin, T.; Zhou, Y.; Mains, G. J. The Journal of Physical Chemistry, Vol. 91, Issue 23 https://doi.org/10.1021/j100307a023	journal	November 1987
FT-IR study of the adsorption and transformation of formaldehyde on oxide surfaces Busca, Guido; Lamotte, Jean; Lavalley, Jean Claude Journal of the American Chemical Society, Vol. 109, Issue 17 https://doi.org/10.1021/ja00251a025	journal	August 1987
Spectrokinetic Investigation of Reverse Water-Gas-Shift Reaction Intermediates over a Pt/CeO ₂ Catalyst Goguet, Alexandre; Meunier, Frederic C.; Tibiletti, Daniele The Journal of Physical Chemistry B, Vol. 108, Issue 52 https://doi.org/10.1021/jp047242w	journal	December 2004
Factors Controlling the Interaction of CO ₂ with Transition Metal Surfaces Wang, Sheng-Guang; Liao, Xiao-Yuan; Cao, Dong-Bo The Journal of Physical Chemistry C, Vol. 111, Issue 45 https://doi.org/10.1021/jp074570y	journal	November 2007
Size-Related Lattice Parameter Changes and Surface Defects in Ceria Nanocrystals Chen, Lan; Fleming, Pete; Morris, Virginia The Journal of Physical Chemistry C, Vol. 114, Issue 30 https://doi.org/10.1021/jp1031465	journal	July 2010
CO ₂ Reduction on Transition Metal (Fe, Co, Ni, and Cu) Surfaces: In Comparison with Homogeneous Catalysis Liu, Cong; Cundari, Thomas R.; Wilson, Angela K. The Journal of Physical Chemistry C, Vol. 116, Issue 9 https://doi.org/10.1021/jp210480c	journal	February 2012
Evidence for Weakly Bound Oxygen on Ceria Films Putna, E. S.; Vohs, J. M.; Gorte, R. J. The Journal of Physical Chemistry, Vol. 100, Issue 45 https://doi.org/10.1021/jp960762+	journal	January 1996
Abrupt onset and prolongation of aragonite undersaturation events in the Southern Ocean Hauri, Claudine; Friedrich, Tobias; Timmermann, Axel Nature Climate Change, Vol. 6, Issue 2 https://doi.org/10.1038/nclimate2844	journal	November 2015
Morphological effects of the nanostructured ceria support on the activity and stability of CuO/CeO ₂ catalysts for the water-gas shift reaction Yao, S. Y.; Xu, W. Q.; Johnston-Peck, A. C. Phys. Chem. Chem. Phys., Vol. 16, Issue 32 https://doi.org/10.1039/C4CP02276A	journal	January 2014
CO ₂ conversion by reverse water gas shift catalysis: comparison of catalysts, mechanisms and their consequences for CO ₂ conversion to liquid fuels Daza, Yolanda A.; Kuhn, John N. RSC Advances, Vol. 6, Issue 55 https://doi.org/10.1039/C6RA05414E	journal	January 2016
Cu supported on mesoporous ceria: water gas shift activity at low Cu loadings through metal–support interactions Vovchok, Dimitriy; Guild, Curtis J.; Llorca, Jordi Physical Chemistry Chemical Physics, Vol. 19, Issue 27 https://doi.org/10.1039/C7CP02378B	journal	January 2017
A short review of recent advances in CO 2 hydrogenation to hydrocarbons over heterogeneous catalysts Li, Wenhui; Wang, Haozhi; Jiang, Xiao RSC Advances, Vol. 8, Issue 14 https://doi.org/10.1039/C7RA13546G	journal	January 2018
FTIR study of CO and NOx adsorption and co-adsorption on Cu/silicalite-1 Milushev, Atanas; Hadjiivanov, Konstantin Physical Chemistry Chemical Physics, Vol. 3, Issue 23 https://doi.org/10.1039/b105722g	journal	November 2001
Satellite structure in the X-ray photoelectron spectra of some binary and mixed oxides of lanthanum and cerium Burroughs, Peter; Hamnett, Andrew; Orchard, Anthony F. Journal of the Chemical Society, Dalton Transactions, Issue 17 https://doi.org/10.1039/dt9760001686	journal	January 1976
Catalytic Properties of Ceria and CeO ₂ -Containing Materials Trovarelli, Alessandro Catalysis Reviews, Vol. 38, Issue 4 https://doi.org/10.1080/01614949608006464	journal	November 1996
A versatile sample-environment cell for non-ambient X-ray scattering experiments Chupas, Peter J.; Chapman, Karena W.; Kurtz, Charles Journal of Applied Crystallography, Vol. 41, Issue 4 https://doi.org/10.1107/S0021889808020165	journal	July 2008
GSAS-II : the genesis of a modern open-source all purpose crystallography software package Toby, Brian H.; Von Dreele, Robert B. Journal of Applied Crystallography, Vol. 46, Issue 2 https://doi.org/10.1107/S0021889813003531	journal	March 2013
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
Kubelka-Munk Theory and the Prediction of Reflectance Nobbs, James H. Review of Progress in Coloration and Related Topics, Vol. 15, Issue 1 https://doi.org/10.1111/j.1478-4408.1985.tb03737.x	journal	June 1985
Active Nonmetallic Au and Pt Species on Ceria-Based Water-Gas Shift Catalysts Fu, Q. Science, Vol. 301, Issue 5635 https://doi.org/10.1126/science.1085721	journal	August 2003
Ceria Maintains Smaller Metal Catalyst Particles by Strong Metal-Support Bonding Farmer, J. A.; Campbell, C. T. Science, Vol. 329, Issue 5994 https://doi.org/10.1126/science.1191778	journal	August 2010
Process Advantages of Direct CO2 to Methanol Synthesis Marlin, Dana S.; Sarron, Emeric; Sigurbjörnsson, Ómar Frontiers in Chemistry, Vol. 6 https://doi.org/10.3389/fchem.2018.00446	journal	September 2018
Improving Fe/Al2O3 Catalysts for the Reverse Water-Gas Shift Reaction: On the Effect of Cs as Activity/Selectivity Promoter Pastor-Pérez, Laura; Shah, Mihir; le Saché, Estelle Catalysts, Vol. 8, Issue 12 https://doi.org/10.3390/catal8120608	journal	December 2018

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Deciphering Dynamic Structural and Mechanistic Complexity in Cu/CeO2/ZSM-5 Catalysts for the Reverse Water-Gas Shift Reaction

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