Hydrogenation of CO2 to methanol on CeOx/Cu(111) and ZnO/Cu(111) catalysts: Role of the metal-oxide interface and importance of Ce3+ sites

Senanayake, Sanjaya D.; Ramirez, Pedro J.; Waluyo, Iradwikanari; Kundu, Shankhamala; Mudiyanselage, Kumudu; Liu, Zongyuan; Liu, Zhi; Axnanda, Stephanus; Stacchiola, Dario J.; Evans, Jaime; Rodriguez, Jose A.

doi:10.1021/acs.jpcc.5b12012

Hydrogenation of CO₂ to methanol on CeO_x/Cu(111) and ZnO/Cu(111) catalysts: Role of the metal-oxide interface and importance of Ce³⁺ sites

Journal Article · Wed Jan 06 00:00:00 EST 2016 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.5b12012· OSTI ID:1246804

Senanayake, Sanjaya D. ^[1]; Ramirez, Pedro J. ^[2]; Waluyo, Iradwikanari ^[1]; Kundu, Shankhamala ^[1]; Mudiyanselage, Kumudu ^[1]; Liu, Zongyuan ^[3]; Liu, Zhi ^[4]; Axnanda, Stephanus ^[4]; Stacchiola, Dario J. ^[1]; Evans, Jaime ^[2]; Rodriguez, Jose A. ^[5]

Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Dept.
Central Univ. of Venezuela, Caracas (Venezuela). Faculty of Science
Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Dept.; SUNY Stony Brook, Stony Brook, NY (United States). Dept. of Chemistry
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Brookhaven National Lab. (BNL). Chemistry Dept. , Upton, NY (United States); SUNY Stony Brook, Stony Brook, NY (United States). Dept. of Chemistry

The role of the interface between a metal and oxide (CeO_x–Cu and ZnO–Cu) is critical to the production of methanol through the hydrogenation of CO₂ (CO₂ + 3H₂ → CH₃OH + H₂O). The deposition of nanoparticles of CeO_x or ZnO on Cu(111), θ_oxi < 0.3 monolayer, produces highly active catalysts for methanol synthesis. The catalytic activity of these systems increases in the sequence: Cu(111) < ZnO/Cu(111) < CeO_x/Cu(111). The apparent activation energy for the CO₂ → CH₃OH conversion decreases from 25 kcal/mol on Cu(111) to 16 kcal/mol on ZnO/Cu(111) and 13 kcal/mol on CeO_x/Cu(111). The surface chemistry of the highly active CeO_x–Cu(111) interface was investigated using ambient pressure X-ray photoemission spectroscopy (AP-XPS) and infrared reflection absorption spectroscopy (AP-IRRAS). Both techniques point to the formation of formates (HCOO^–) and carboxylates (CO₂^δ–) during the reaction. Our results show an active state of the catalyst rich in Ce³⁺ sites which stabilize a CO₂^δ– species that is an essential intermediate for the production of methanol. Furthermore, the inverse oxide/metal configuration favors strong metal–oxide interactions and makes possible reaction channels not seen in conventional metal/oxide catalysts.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1246804

Alternate ID(s):: OSTI ID: 1456931

Report Number(s):: BNL--111983-2016-JA; KC0302010

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 3 Vol. 120; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (34)

Feature: There’s too much carbon dioxide in the air. Why not turn it back into fuel? Service, Robert Science https://doi.org/10.1126/science.aad1735	journal	September 2015
Carbon Dioxide as Chemical Feedstock Aresta, Michele https://doi.org/10.1002/9783527629916	book	January 2010
Importance of the Metal-Oxide Interface in Catalysis: In Situ Studies of the Water-Gas Shift Reaction by Ambient-Pressure X-ray Photoelectron Spectroscopy Mudiyanselage, Kumudu; Senanayake, Sanjaya D.; Feria, Leticia Angewandte Chemie International Edition, Vol. 52, Issue 19 https://doi.org/10.1002/anie.201210077	journal	April 2013
Formation of a ZnO Overlayer in Industrial Cu/ZnO/Al ₂ O ₃ Catalysts Induced by Strong Metal-Support Interactions Lunkenbein, Thomas; Schumann, Julia; Behrens, Malte Angewandte Chemie International Edition, Vol. 54, Issue 15 https://doi.org/10.1002/anie.201411581	journal	February 2015
The Mechanism of CO and CO ₂ Hydrogenation to Methanol over Cu-Based Catalysts Studt, Felix; Behrens, Malte; Kunkes, Edward L. ChemCatChem, Vol. 7, Issue 7 https://doi.org/10.1002/cctc.201500123	journal	March 2015
Carbon Dioxide Recycling: Emerging Large-Scale Technologies with Industrial Potential Quadrelli, Elsje Alessandra; Centi, Gabriele; Duplan, Jean-Luc ChemSusChem, Vol. 4, Issue 9 https://doi.org/10.1002/cssc.201100473	journal	September 2011
A Surface Science Investigation of Methanol Synthesis over a Zn-Deposited Polycrystalline Cu Surface Nakamura, J.; Nakamura, I.; Uchijima, T. Journal of Catalysis, Vol. 160, Issue 1 https://doi.org/10.1006/jcat.1996.0124	journal	April 1996
Methanol Synthesis and Reverse Water–Gas Shift Kinetics over Cu(110) Model Catalysts: Structural Sensitivity Yoshihara, Jun; Campbell, Charles T. Journal of Catalysis, Vol. 161, Issue 2 https://doi.org/10.1006/jcat.1996.0240	journal	July 1996
Methanol synthesis on a Cu(100) catalyst Szanyi, J�nos; Goodman, D. Wayne Catalysis Letters, Vol. 10, Issue 5-6 https://doi.org/10.1007/BF00769173	journal	January 1991
Methanol synthesis on Cu(100) from a binary gas mixture of CO2 and H2 Rasmussen, P. B.; Holmblad, P. M.; Askgaard, T. Catalysis Letters, Vol. 26, Issue 3-4 https://doi.org/10.1007/BF00810611	journal	January 1994
Activity and Selectivity Trends in Synthesis Gas Conversion to Higher Alcohols Medford, Andrew J.; Lausche, Adam C.; Abild-Pedersen, Frank Topics in Catalysis, Vol. 57, Issue 1-4 https://doi.org/10.1007/s11244-013-0169-0	journal	October 2013
Microstructural and Defect Analysis of Metal Nanoparticles in Functional Catalysts by Diffraction and Electron Microscopy: The Cu/ZnO Catalyst for Methanol Synthesis Kandemir, Timur; Kasatkin, Igor; Girgsdies, Frank Topics in Catalysis, Vol. 57, Issue 1-4 https://doi.org/10.1007/s11244-013-0175-2	journal	October 2013
Conversion of methanol, formaldehyde and formic acid on the polar faces of zinc oxide Vohs, J. M.; Barteau, M. A. Surface Science, Vol. 176, Issue 1-2 https://doi.org/10.1016/0039-6028(86)90165-2	journal	October 1986
Cu/ZnO(0001̄) and ZnOx/Cu(111): Model catalysts for methanol synthesis Campbell, Charles T.; Daube, Karen A.; White, J. M. Surface Science, Vol. 182, Issue 3 https://doi.org/10.1016/0039-6028(87)90013-6	journal	April 1987
The electronic structure of stoichiometric and reduced CeO2 surfaces: an XPS, UPS and HREELS study Pfau, A.; Schierbaum, K. D. Surface Science, Vol. 321, Issue 1-2 https://doi.org/10.1016/0039-6028(94)90027-2	journal	December 1994
The synthesis of higher alcohols using modified Cu/ZnO/Al2O3 catalysts Slaa, J. C.; van Ommen, J. G.; Ross, J. R. H. Catalysis Today, Vol. 15, Issue 1 https://doi.org/10.1016/0920-5861(92)80125-7	journal	May 1992
Ultrathin metal films and particles on oxide surfaces: structural, electronic and chemisorptive properties Campbell, Charles T. Surface Science Reports, Vol. 27, Issue 1-3 https://doi.org/10.1016/S0167-5729(96)00011-8	journal	January 1997
Surface studies of supported model catalysts Henry, Claude R. Surface Science Reports, Vol. 31, Issue 7-8 https://doi.org/10.1016/S0167-5729(98)00002-8	journal	January 1998
Formation of hydrocarbons via CO2 hydrogenation – A thermodynamic study Torrente-Murciano, L.; Mattia, D.; Jones, M. D. Journal of CO2 Utilization, Vol. 6 https://doi.org/10.1016/j.jcou.2014.03.002	journal	June 2014
Direct CO2 hydrogenation to methane or methanol from post-combustion exhaust streams – A thermodynamic study Miguel, Carlos V.; Soria, Miguel A.; Mendes, Adélio Journal of Natural Gas Science and Engineering, Vol. 22 https://doi.org/10.1016/j.jngse.2014.11.010	journal	January 2015
Promoting Strong Metal Support Interaction: Doping ZnO for Enhanced Activity of Cu/ZnO:M (M = Al, Ga, Mg) Catalysts Schumann, Julia; Eichelbaum, Maik; Lunkenbein, Thomas ACS Catalysis, Vol. 5, Issue 6 https://doi.org/10.1021/acscatal.5b00188	journal	April 2015
Hydrogenation of CO ₂ to Methanol: Importance of Metal–Oxide and Metal–Carbide Interfaces in the Activation of CO ₂ Rodriguez, José A.; Liu, Ping; Stacchiola, Dario J. ACS Catalysis, Vol. 5, Issue 11 https://doi.org/10.1021/acscatal.5b01755	journal	October 2015
Electron Transfer at Oxide Surfaces. The MgO Paradigm: from Defects to Ultrathin Films Pacchioni, Gianfranco; Freund, Hajo Chemical Reviews, Vol. 113, Issue 6 https://doi.org/10.1021/cr3002017	journal	November 2012
Mechanism of Methanol Synthesis on Cu through CO ₂ and CO Hydrogenation Grabow, L. C.; Mavrikakis, M. ACS Catalysis, Vol. 1, Issue 4 https://doi.org/10.1021/cs200055d	journal	February 2011
Adsorbate-Driven Morphological Changes of a Gold Surface at Low Temperatures Hrbek, Jan; Hoffmann, Friedrich M.; Park, Joon B. Journal of the American Chemical Society, Vol. 130, Issue 51 https://doi.org/10.1021/ja8081268	journal	December 2008
Unraveling the Nature of the Oxide–Metal Interaction in Ceria-Based Noble Metal Inverse Catalysts Graciani, Jesús; Vidal, Alba B.; Rodriguez, José A. The Journal of Physical Chemistry C, Vol. 118, Issue 46 https://doi.org/10.1021/jp509947t	journal	November 2014
How to make the most of carbon dioxide Lim, XiaoZhi Nature, Vol. 526, Issue 7575 https://doi.org/10.1038/526628a	journal	October 2015
Fundamental studies of methanol synthesis from CO2 hydrogenation on Cu(111), Cu clusters, and Cu/ZnO(0001̄) Yang, Yixiong; Evans, Jaime; Rodriguez, Jose A. Physical Chemistry Chemical Physics, Vol. 12, Issue 33 https://doi.org/10.1039/c001484b	journal	January 2010
Density functional study of water-gas shift reaction on M3O3x/Cu(111) Vidal, Alba B.; Liu, Ping Physical Chemistry Chemical Physics, Vol. 14, Issue 48 https://doi.org/10.1039/c2cp42091k	journal	January 2012
Status and perspectives of CO2 conversion into fuels and chemicals by catalytic, photocatalytic and electrocatalytic processes Kondratenko, Evgenii V.; Mul, Guido; Baltrusaitis, Jonas Energy & Environmental Science, Vol. 6, Issue 11 https://doi.org/10.1039/c3ee41272e	journal	January 2013
A differentially pumped electrostatic lens system for photoemission studies in the millibar range Ogletree, D. Frank; Bluhm, Hendrik; Lebedev, Gennadi Review of Scientific Instruments, Vol. 73, Issue 11 https://doi.org/10.1063/1.1512336	journal	November 2002
Modern Global Climate Change Karl, T. R. Science, Vol. 302, Issue 5651 https://doi.org/10.1126/science.1090228	journal	December 2003
Activity of CeOx and TiOx Nanoparticles Grown on Au(111) in the Water-Gas Shift Reaction Rodriguez, J. A.; Ma, S.; Liu, P. Science, Vol. 318, Issue 5857 https://doi.org/10.1126/science.1150038	journal	December 2007
Highly active copper-ceria and copper-ceria-titania catalysts for methanol synthesis from CO2 Graciani, J.; Mudiyanselage, K.; Xu, F. Science, Vol. 345, Issue 6196 https://doi.org/10.1126/science.1253057	journal	July 2014

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Ambient Pressure Photoelectron Spectroscopy: Opportunities in Catalysis from Solids to Liquids and Introducing Time Resolution Roy, Kanak; Artiglia, Luca; van Bokhoven, Jeroen A. ChemCatChem, Vol. 10, Issue 4 https://doi.org/10.1002/cctc.201701522	journal	January 2018
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The conversion of CO ₂ to methanol on orthorhombic β-Mo ₂ C and Cu/β-Mo ₂ C catalysts: mechanism for admetal induced change in the selectivity and activity Posada-Pérez, Sergio; Ramírez, Pedro J.; Gutiérrez, Ramón A. Catalysis Science & Technology, Vol. 6, Issue 18 https://doi.org/10.1039/c5cy02143j	journal	January 2016
Surface chemistry of group IB metals and related oxides Huang, Weixin; Sun, Guanghui; Cao, Tian Chemical Society Reviews, Vol. 46, Issue 7 https://doi.org/10.1039/c6cs00828c	journal	January 2017
Ceria-based model catalysts: fundamental studies on the importance of the metal–ceria interface in CO oxidation, the water–gas shift, CO ₂ hydrogenation, and methane and alcohol reforming Rodriguez, José A.; Grinter, David C.; Liu, Zongyuan Chemical Society Reviews, Vol. 46, Issue 7 https://doi.org/10.1039/c6cs00863a	journal	January 2017
Thermal reduction of ceria nanostructures on rhodium(111) and re-oxidation by CO ₂ Schaefer, Andreas; Hagman, Benjamin; Höcker, Jan Physical Chemistry Chemical Physics, Vol. 20, Issue 29 https://doi.org/10.1039/c8cp01505h	journal	January 2018
New horizon in C1 chemistry: breaking the selectivity limitation in transformation of syngas and hydrogenation of CO ₂ into hydrocarbon chemicals and fuels Zhou, Wei; Cheng, Kang; Kang, Jincan Chemical Society Reviews, Vol. 48, Issue 12 https://doi.org/10.1039/c8cs00502h	journal	January 2019
Recent progress in improving the stability of copper-based catalysts for hydrogenation of carbon–oxygen bonds Ye, Run-Ping; Lin, Ling; Li, Qiaohong Catalysis Science & Technology, Vol. 8, Issue 14 https://doi.org/10.1039/c8cy00608c	journal	January 2018
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Active sites for CO ₂ hydrogenation to methanol on Cu/ZnO catalysts Kattel, Shyam; Ramírez, Pedro J.; Chen, Jingguang G. Science, Vol. 355, Issue 6331 https://doi.org/10.1126/science.aal3573	journal	March 2017
Response to Comment on “Active sites for CO ₂ hydrogenation to methanol on Cu/ZnO catalysts” Kattel, Shyam; Ramírez, Pedro J.; Chen, Jingguang G. Science, Vol. 357, Issue 6354 https://doi.org/10.1126/science.aan8210	journal	August 2017
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