Reactivity of a Zirconia–Copper Inverse Catalyst for CO2 Hydrogenation

Ma, Yilin; Wang, Jason; Goodman, Kenneth R.; Head, Ashley R.; Tong, Xiao; Stacchiola, Dario J.; White, Michael G.

doi:10.1021/acs.jpcc.0c06624

Title: Reactivity of a Zirconia–Copper Inverse Catalyst for CO₂ Hydrogenation

Journal Article · Mon Sep 14 00:00:00 EDT 2020 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.0c06624· OSTI ID:1670666

Ma, Yilin ^[1]; Wang, Jason ^[1]; Goodman, Kenneth R. ^[1];

^[2]; Tong, Xiao ^[2];

^[2];

^[3]

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

Copper–zirconia catalysts have been shown to be effective for methanol synthesis via CO₂ hydrogenation, yet the active phases and reaction mechanism remain uncertain. Here, an inverse model catalyst ZrO₂/CuO₂/Cu(111) was prepared by mass-selected ion deposition and tested for CO₂ hydrogenation under near-ambient pressure (AP) reaction conditions by using X-ray photoelectron spectroscopy (NAP-XPS) and infrared reflection–absorption spectroscopy (NAP-IRAS). The spatial resolution afforded by the small entrance cone of the AP-XPS spectrometer was used to resolve regions of the surface with and without Zr deposition. Carbon 1s core level spectra of the ZrO₂/Cu₂O/Cu(111) regions of the surface under 500 mTorr of CO₂ + H₂ (1:3 ratio) show evidence for reaction intermediates including carbonate (CO₃*), formate (HCOO*), and H_xCO* species, with methoxy having the highest surface concentration at 500–600 K. These intermediates are confirmed by IRAS vibrational spectra. In regions of the surface without Zr, the Cu₂O/Cu(111) is reduced to metallic Cu, and the surface intermediates are different and are present at much lower concentrations. The observed surface intermediates and their temperature dependence suggest a mechanism in which CO₂ is adsorbed on zirconia as carbonate (CO₃*) and then converted to HCOO* and H_xCO* hydrogenated intermediates that ultimately lead to methoxy (CH₃O*), the final surface-bound precursor for methanol. Overall, the results clearly demonstrate the promotional effects of small ZrO₂ particles for enhancing the reactivity of Cu surfaces for CO₂ hydrogenation.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Defense Threat Reduction Agency (DTRA)

Grant/Contract Number:: SC0012704; SC0012573; HDTRA11510005

OSTI ID:: 1670666

Report Number(s):: BNL-219917-2020-JAAM

Journal Information:: Journal of Physical Chemistry. C, Vol. 124, Issue 40; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (111)

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
Formic acid as a hydrogen source – recent developments and future trends Grasemann, Martin; Laurenczy, Gábor Energy & Environmental Science, Vol. 5, Issue 8 https://doi.org/10.1039/c2ee21928j	journal	January 2012
Growth, Structure, and Stability of Au on Ordered ZrO ₂ (111) Thin Films Pan, Yonghe; Gao, Yan; Wang, Guodong The Journal of Physical Chemistry C, Vol. 115, Issue 21 https://doi.org/10.1021/jp201960t	journal	May 2011
Methanol Synthesis Waugh, K. C. Catalysis Today, Vol. 15, Issue 1 https://doi.org/10.1016/0920-5861(92)80122-4	journal	May 1992
Recent Advances in Catalysts for Methanol Synthesis via Hydrogenation of CO and CO ₂ Liu, Xin-Mei; Lu, G. Q.; Yan, Zi-Feng Industrial & Engineering Chemistry Research, Vol. 42, Issue 25 https://doi.org/10.1021/ie020979s	journal	December 2003
Beyond Oil and Gas: The Methanol Economy Olah, George A. Angewandte Chemie International Edition, Vol. 44, Issue 18 https://doi.org/10.1002/anie.200462121	journal	April 2005
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
Methanol synthesis over a Zn-deposited copper model catalyst Nakamura, J.; Nakamura, I.; Uchijima, T. Catalysis Letters, Vol. 31, Issue 4 https://doi.org/10.1007/BF00808596	journal	January 1995
Synthesis, characterization and activity pattern of Cu–ZnO/ZrO2 catalysts in the hydrogenation of carbon dioxide to methanol Arena, F.; Barbera, K.; Italiano, G. Journal of Catalysis, Vol. 249, Issue 2 https://doi.org/10.1016/j.jcat.2007.04.003	journal	July 2007
Methanol synthesis from CO2 hydrogenation over Cu/γ-Al2O3 catalysts modified by ZnO, ZrO2 and MgO Ren, Hong; Xu, Cheng-Hua; Zhao, Hao-Yang Journal of Industrial and Engineering Chemistry, Vol. 28 https://doi.org/10.1016/j.jiec.2015.03.001	journal	August 2015
Effective conversion of carbon dioxide and hydrogen to hydrocarbons Inui, Tomoyuki; Takeguchi, Tatsuya Catalysis Today, Vol. 10, Issue 1 https://doi.org/10.1016/0920-5861(91)80077-M	journal	August 1991
Efficient Conversion of Carbon Dioxide to Methanol Using Copper Catalyst by a New Low-temperature Hydrogenation Process Liu, Yong; Zhang, Yi; Wang, Tiejun Chemistry Letters, Vol. 36, Issue 9 https://doi.org/10.1246/cl.2007.1182	journal	September 2007
Catalytic reduction of CO ₂ by H ₂ for synthesis of CO, methanol and hydrocarbons: challenges and opportunities Porosoff, Marc D.; Yan, Binhang; Chen, Jingguang G. Energy & Environmental Science, Vol. 9, Issue 1 https://doi.org/10.1039/C5EE02657A	journal	January 2016
Structure and function of Cu-based composite catalysts for highly effective synthesis of methanol by hydrogenation of CO2 and CO Inui, Tomoyuki; Hara, Hideki; Takeguchi, Tatsuya Catalysis Today, Vol. 36, Issue 1 https://doi.org/10.1016/S0920-5861(96)00192-7	journal	April 1997
Effect of Mg and Mn oxide additions on structural and adsorptive properties of Cu/ZnO/ZrO2 catalysts for the methanol synthesis from CO2 Słoczyński, J.; Grabowski, R.; Kozłowska, A. Applied Catalysis A: General, Vol. 249, Issue 1 https://doi.org/10.1016/S0926-860X(03)00191-1	journal	August 2003
Glycine–nitrate combustion synthesis of CuO–ZnO–ZrO2 catalysts for methanol synthesis from CO2 hydrogenation Guo, Xiaoming; Mao, Dongsen; Lu, Guanzhong Journal of Catalysis, Vol. 271, Issue 2 https://doi.org/10.1016/j.jcat.2010.01.009	journal	May 2010
Effect of TiO2, ZrO2, and TiO2–ZrO2 on the performance of CuO–ZnO catalyst for CO2 hydrogenation to methanol Xiao, Jie; Mao, Dongsen; Guo, Xiaoming Applied Surface Science, Vol. 338 https://doi.org/10.1016/j.apsusc.2015.02.122	journal	May 2015
Tuning of catalytic CO2 hydrogenation by changing composition of CuO–ZnO–ZrO2 catalysts Witoon, Thongthai; Kachaban, Nantana; Donphai, Waleeporn Energy Conversion and Management, Vol. 118 https://doi.org/10.1016/j.enconman.2016.03.075	journal	June 2016
Effect of Zr and pH in the preparation of Cu/ZnO catalysts for the methanol synthesis by CO2 hydrogenation Jeong, Heondo; Cho, Churl Hee; Kim, Tae Hwan Reaction Kinetics, Mechanisms and Catalysis, Vol. 106, Issue 2 https://doi.org/10.1007/s11144-012-0441-5	journal	April 2012
Influence of Zr on the performance of Cu/Zn/Al/Zr catalysts via hydrotalcite-like precursors for CO2 hydrogenation to methanol Gao, Peng; Li, Feng; Zhan, Haijuan Journal of Catalysis, Vol. 298 https://doi.org/10.1016/j.jcat.2012.10.030	journal	February 2013
Solid-state interactions, adsorption sites and functionality of Cu-ZnO/ZrO2 catalysts in the CO2 hydrogenation to CH3OH Arena, Francesco; Italiano, Giuseppe; Barbera, Katia Applied Catalysis A: General, Vol. 350, Issue 1 https://doi.org/10.1016/j.apcata.2008.07.028	journal	November 2008
Development of highly stable catalyst for methanol synthesis from carbon dioxide Li, Congming; Yuan, Xingdong; Fujimoto, Kaoru Applied Catalysis A: General, Vol. 469 https://doi.org/10.1016/j.apcata.2013.10.010	journal	January 2014
The effect of ageing time on co-precipitated Cu/ZnO/ZrO2 catalysts used in methanol synthesis from CO2 and H2 Raudaskoski, Riitta; Niemelä, Marita Veringa; Keiski, Riitta L. Topics in Catalysis, Vol. 45, Issue 1-4 https://doi.org/10.1007/s11244-007-0240-9	journal	August 2007
Bimetallic Pd–Cu catalysts for selective CO2 hydrogenation to methanol Jiang, Xiao; Koizumi, Naoto; Guo, Xinwen Applied Catalysis B: Environmental, Vol. 170-171 https://doi.org/10.1016/j.apcatb.2015.01.010	journal	July 2015
Study of CuZnMOx oxides (M=Al, Zr, Ce, CeZr) for the catalytic hydrogenation of CO2 into methanol Angelo, Laetitia; Kobl, Kilian; Tejada, Leidy Marcela Martinez Comptes Rendus Chimie, Vol. 18, Issue 3 https://doi.org/10.1016/j.crci.2015.01.001	journal	March 2015
Methanol synthesis from CO2 hydrogenation over Cu based catalyst supported on zirconia modified γ-Al2O3 Zhang, Yiping; Fei, Jinhua; Yu, Yingmin Energy Conversion and Management, Vol. 47, Issue 18-19 https://doi.org/10.1016/j.enconman.2006.01.010	journal	November 2006
On the mechanism of CO and CO2 hydrogenation reactions on zirconia-supported catalysts: a diffuse reflectance FTIR study Schild, C.; Wokaun, A.; Baiker, A. Journal of Molecular Catalysis, Vol. 63, Issue 2 https://doi.org/10.1016/0304-5102(90)85147-A	journal	December 1990
Surface species in CO2 methanation over amorphous palladium/zirconia catalysts Schild, C.; Wokaun, A.; Baiker, A. Journal of Molecular Catalysis, Vol. 69, Issue 3 https://doi.org/10.1016/0304-5102(91)80115-J	journal	November 1991
Influence of ZrO ₂ Structure and Copper Electronic State on Activity of Cu/ZrO ₂ Catalysts in Methanol Synthesis from CO ₂ Samson, K.; Śliwa, M.; Socha, R. P. ACS Catalysis, Vol. 4, Issue 10 https://doi.org/10.1021/cs500979c	journal	September 2014
Exploring the ternary interactions in Cu–ZnO–ZrO2 catalysts for efficient CO2 hydrogenation to methanol Wang, Yuhao; Kattel, Shyam; Gao, Wengui Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-09072-6	journal	March 2019
CO ₂ Hydrogenation to Methanol over ZrO ₂ -Containing Catalysts: Insights into ZrO ₂ Induced Synergy Li, Kongzhai; Chen, Jingguang G. ACS Catalysis, Vol. 9, Issue 9 https://doi.org/10.1021/acscatal.9b01943	journal	July 2019
Copper-zirconia catalysts for methanol synthesis from carbon dioxide: Effect of ZnO addition to Cu-ZrO2 catalysts Nitta, Yuriko; Suwata, Osamu; Ikeda, Yasuo Catalysis Letters, Vol. 26, Issue 3-4 https://doi.org/10.1007/BF00810608	journal	January 1994
Recent advances in catalytic hydrogenation of carbon dioxide Wang, Wei; Wang, Shengping; Ma, Xinbin Chemical Society Reviews, Vol. 40, Issue 7 https://doi.org/10.1039/c1cs15008a	journal	January 2011
Basic evidences for methanol-synthesis catalyst design Arena, F.; Italiano, G.; Barbera, K. Catalysis Today, Vol. 143, Issue 1-2 https://doi.org/10.1016/j.cattod.2008.11.022	journal	May 2009
Effects of oxide carriers on surface functionality and process performance of the Cu–ZnO system in the synthesis of methanol via CO2 hydrogenation Arena, Francesco; Mezzatesta, Giovanni; Zafarana, Giovanni Journal of Catalysis, Vol. 300 https://doi.org/10.1016/j.jcat.2012.12.019	journal	April 2013
Morphology-Dependent Interactions of ZnO with Cu Nanoparticles at the Materials’ Interface in Selective Hydrogenation of CO2 to CH3OH Liao, Fenglin; Huang, Yaqun; Ge, Junwei Angewandte Chemie International Edition, Vol. 50, Issue 9 https://doi.org/10.1002/anie.201007108	journal	January 2011
A highly selective and stable ZnO-ZrO ₂ solid solution catalyst for CO ₂ hydrogenation to methanol Wang, Jijie; Li, Guanna; Li, Zelong Science Advances, Vol. 3, Issue 10 https://doi.org/10.1126/sciadv.1701290	journal	October 2017
Methanol synthesis from CO2-rich syngas over a ZrO2 doped CuZnO catalyst Yang, Cheng; Ma, Zhongyi; Zhao, Ning Catalysis Today, Vol. 115, Issue 1-4 https://doi.org/10.1016/j.cattod.2006.02.077	journal	June 2006
The changing nature of the active site of Cu-Zn-Zr catalysts for the CO2 hydrogenation reaction to methanol Bonura, G.; Cordaro, M.; Cannilla, C. Applied Catalysis B: Environmental, Vol. 152-153 https://doi.org/10.1016/j.apcatb.2014.01.035	journal	June 2014
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
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
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
Methanol synthesis from CO2 hydrogenation over La–M–Cu–Zn–O (M = Y, Ce, Mg, Zr) catalysts derived from perovskite-type precursors Zhan, Haijuan; Li, Feng; Gao, Peng Journal of Power Sources, Vol. 251 https://doi.org/10.1016/j.jpowsour.2013.11.037	journal	April 2014
Effects of Zirconia Phase on the Synthesis of Methanol over Zirconia-Supported Copper Jung, Kyeong Taek; Bell, Alexis T. Catalysis Letters, Vol. 80, Issue 1/2, p. 63-68 https://doi.org/10.1023/A:1015326726898	journal	January 2002
In SituInfrared Study of Methanol Synthesis from CO2/H2on Titania and Zirconia Promoted Cu/SiO2 Schilke, Tobin C.; Fisher, Ian A.; Bell, Alexis T. Journal of Catalysis, Vol. 184, Issue 1 https://doi.org/10.1006/jcat.1999.2434	journal	May 1999
Development of copper/zinc oxide-based multicomponent catalysts for methanol synthesis from carbon dioxide and hydrogen Saito, M.; Fujitani, T.; Takeuchi, M. Applied Catalysis A: General, Vol. 138, Issue 2 https://doi.org/10.1016/0926-860X(95)00305-3	journal	May 1996
CO2 hydrogenation to methanol over Cu/ZnO/ZrO2 catalysts prepared by precipitation-reduction method Dong, Xiaosu; Li, Feng; Zhao, Ning Applied Catalysis B: Environmental, Vol. 191 https://doi.org/10.1016/j.apcatb.2016.03.014	journal	August 2016
Influences of particle size and crystallinity of highly loaded CuO/ZrO ₂ on CO ₂ hydrogenation to methanol Fujiwara, Kakeru; Tada, Shohei; Honma, Tetsuo AIChE Journal, Vol. 65, Issue 12 https://doi.org/10.1002/aic.16717	journal	July 2019
Cu Species Incorporated into Amorphous ZrO ₂ with High Activity and Selectivity in CO ₂ -to-Methanol Hydrogenation Tada, Shohei; Katagiri, Ayaka; Kiyota, Keiko The Journal of Physical Chemistry C, Vol. 122, Issue 10 https://doi.org/10.1021/acs.jpcc.7b11284	journal	February 2018
Frontiers, Opportunities, and Challenges in Biochemical and Chemical Catalysis of CO ₂ Fixation Appel, Aaron M.; Bercaw, John E.; Bocarsly, Andrew B. Chemical Reviews, Vol. 113, Issue 8 https://doi.org/10.1021/cr300463y	journal	June 2013
Reaction Network of Methanol Synthesis over Cu/ZnO Nanocatalysts Martínez-Suárez, Luis; Siemer, Niklas; Frenzel, Johannes ACS Catalysis, Vol. 5, Issue 7 https://doi.org/10.1021/acscatal.5b00442	journal	June 2015
CO2 fixation into methanol at Cu/ZrO2 interface from first principles kinetic Monte Carlo Tang, Qian-Lin; Hong, Qi-Jun; Liu, Zhi-Pan Journal of Catalysis, Vol. 263, Issue 1 https://doi.org/10.1016/j.jcat.2009.01.017	journal	April 2009
Optimizing Binding Energies of Key Intermediates for CO ₂ Hydrogenation to Methanol over Oxide-Supported Copper Kattel, Shyam; Yan, Binhang; Yang, Yixiong Journal of the American Chemical Society, Vol. 138, Issue 38 https://doi.org/10.1021/jacs.6b05791	journal	September 2016
In Situ Infrared Study of Methanol Synthesis from H2/CO over Cu/SiO2and Cu/ZrO2/SiO2 Fisher, Ian A.; Bell, Alexis T. Journal of Catalysis, Vol. 178, Issue 1 https://doi.org/10.1006/jcat.1998.2134	journal	August 1998
Theoretical Study of Methanol Synthesis from CO ₂ Hydrogenation on Metal-Doped Cu(111) Surfaces Yang, Yixiong; White, Michael G.; Liu, Ping The Journal of Physical Chemistry C, Vol. 116, Issue 1 https://doi.org/10.1021/jp208448c	journal	December 2011
Mechanism of CO2 hydrogenation over Cu/ZrO2(2̅12) interface from first-principles kinetics Monte Carlo simulations Hong, Qi-Jun; Liu, Zhi-Pan Surface Science, Vol. 604, Issue 21-22 https://doi.org/10.1016/j.susc.2010.07.018	journal	October 2010
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
CO ₂ -to-Methanol Hydrogenation on Zirconia-Supported Copper Nanoparticles: Reaction Intermediates and the Role of the Metal-Support Interface Larmier, Kim; Liao, Wei-Chih; Tada, Shohei Angewandte Chemie International Edition, Vol. 56, Issue 9 https://doi.org/10.1002/anie.201610166	journal	January 2017
Tuning Selectivity of CO ₂ Hydrogenation Reactions at the Metal/Oxide Interface Kattel, Shyam; Liu, Ping; Chen, Jingguang G. Journal of the American Chemical Society, Vol. 139, Issue 29 https://doi.org/10.1021/jacs.7b05362	journal	July 2017
Surface active structure of ultra-fine Cu/ZrO2 catalysts used for the CO2+H2 to methanol reaction Liu, Jinyao; Shi, Jiangliu; He, Dehua Applied Catalysis A: General, Vol. 218, Issue 1-2 https://doi.org/10.1016/S0926-860X(01)00625-1	journal	September 2001
Gas-Phase Reactivity of the Ti ₈ C ₁₂ ⁺ Met-car with Triatomic Sulfur-Containing Molecules: CS ₂ , SCO, and SO ₂ Lightstone, James M.; Patterson, Melissa J.; Liu, Ping The Journal of Physical Chemistry A, Vol. 110, Issue 10 https://doi.org/10.1021/jp057277b	journal	March 2006
Catalysis Applications of Size-Selected Cluster Deposition Vajda, Stefan; White, Michael G. ACS Catalysis, Vol. 5, Issue 12 https://doi.org/10.1021/acscatal.5b01816	journal	November 2015
Oxidation of Cu(111): two new oxygen induced reconstructions Jensen, F.; Besenbacher, F.; Lægsgaard, E. Surface Science, Vol. 259, Issue 3 https://doi.org/10.1016/0039-6028(91)90550-C	journal	December 1991
Two new oxygen induced reconstructions on Cu(111) Jensen, F.; Besenbacher, F.; Stensgaard, I. Surface Science, Vol. 269-270 https://doi.org/10.1016/0039-6028(92)91282-G	journal	May 1992
Scanning tunneling microscopy studies of oxygen adsorption on Cu(111) Matsumoto, T.; Bennett, R. A.; Stone, P. Surface Science, Vol. 471, Issue 1-3 https://doi.org/10.1016/S0039-6028(00)00918-3	journal	January 2001
Autocatalytic Reduction of a Cu ₂ O/Cu(111) Surface by CO: STM, XPS, and DFT Studies Yang, Fan; Choi, YongMan; Liu, Ping The Journal of Physical Chemistry C, Vol. 114, Issue 40 https://doi.org/10.1021/jp1029079	journal	July 2010
Mechanistic Study of CO Titration on Cu _x O/Cu(1 1 1) ( x ≤2) Surfaces An, Wei; Baber, Ashleigh E.; Xu, Fang ChemCatChem, Vol. 6, Issue 8 https://doi.org/10.1002/cctc.201402177	journal	June 2014
Growth of an Ultrathin Zirconia Film on Pt ₃ Zr Examined by High-Resolution X-ray Photoelectron Spectroscopy, Temperature-Programmed Desorption, Scanning Tunneling Microscopy, and Density Functional Theory Li, Hao; Choi, Joong-Il Jake; Mayr-Schmölzer, Wernfried The Journal of Physical Chemistry C https://doi.org/10.1021/jp5100846	journal	January 2015
Oxygen adsorption and stability of surface oxides on $Cu (111)$ : A first-principles investigation Soon, Aloysius; Todorova, Mira; Delley, Bernard Physical Review B, Vol. 73, Issue 16 https://doi.org/10.1103/PhysRevB.73.165424	journal	April 2006
CO ₂ Adsorption on Cu ₂ O(111): A DFT+U and DFT-D Study Bendavid, Leah Isseroff; Carter, Emily A. The Journal of Physical Chemistry C, Vol. 117, Issue 49 https://doi.org/10.1021/jp407468t	journal	November 2013
Investigation of CO and CO ₂ Adsorption on Tetragonal and Monoclinic Zirconia Pokrovski, Konstantin; Jung, Kyeong Taek; Bell, Alexis T. Langmuir, Vol. 17, Issue 14 https://doi.org/10.1021/la001723z	journal	July 2001
Surface Chemistry of Cu in the Presence of CO ₂ and H ₂ O Deng, Xingyi; Verdaguer, Albert; Herranz, Tirma Langmuir, Vol. 24, Issue 17 https://doi.org/10.1021/la8011052	journal	September 2008
In-situ FT-IR study on CO2 hydrogenation over Cu catalysts supported on SiO2, Al2O3, and TiO2 Bando, Kyoko Kitamura; Sayama, Kazuhiro; Kusama, Hitoshi Applied Catalysis A: General, Vol. 165, Issue 1-2 https://doi.org/10.1016/S0926-860X(97)00221-4	journal	December 1997
Probing Surface Structures of CeO ₂ , TiO ₂ , and Cu ₂ O Nanocrystals with CO and CO ₂ Chemisorption Chen, Shilong; Cao, Tian; Gao, Yuxian The Journal of Physical Chemistry C, Vol. 120, Issue 38 https://doi.org/10.1021/acs.jpcc.6b06158	journal	September 2016
The effects of zirconia morphology on methanol synthesis from CO and H2 over Cu/ZrO2 catalystsPart II. Transient-response infrared studies Rhodes, M.; Pokrovski, K.; Bell, A. Journal of Catalysis, Vol. 233, Issue 1 https://doi.org/10.1016/j.jcat.2005.04.027	journal	July 2005
Intermediate species on zirconia supported methanol aerogel catalysts Bianchi, Daniel; Chafik, Tarik; Khalfallah, Mohamed Applied Catalysis A: General, Vol. 105, Issue 2 https://doi.org/10.1016/0926-860X(93)80250-T	journal	November 1993
Structure–activity relationships of Cu–ZrO ₂ catalysts for CO ₂ hydrogenation to methanol: interaction effects and reaction mechanism Wang, Yu Hao; Gao, Wen Gui; Wang, Hua RSC Advances, Vol. 7, Issue 14 https://doi.org/10.1039/C6RA28305E	journal	January 2017
Infrared study of syngas adsorption on zirconia Guglielminotti, Eugenio Langmuir, Vol. 6, Issue 9 https://doi.org/10.1021/la00099a005	journal	September 1990
In-SituInfrared Study of Methanol Synthesis from H2/CO2over Cu/SiO2and Cu/ZrO2/SiO2 Fisher, Ian A.; Bell, Alexis T. Journal of Catalysis, Vol. 172, Issue 1 https://doi.org/10.1006/jcat.1997.1870	journal	November 1997
CO2 activation on ultrathin ZrO2 film by H2O co-adsorption: In situ NAP-XPS and IRAS studies Li, Hao; Rameshan, Christoph; Bukhtiyarov, Andrey V. Surface Science, Vol. 679 https://doi.org/10.1016/j.susc.2018.08.028	journal	January 2019
Intermediate species on zirconia supported methanol aerogel catalysts V. Adsorption of methanol Bianchi, D.; Chafik, T.; Khalfallah, M. Applied Catalysis A: General, Vol. 123, Issue 1 https://doi.org/10.1016/0926-860X(94)00242-8	journal	March 1995
Confinement of Ultrasmall Cu/ZnO _x Nanoparticles in Metal–Organic Frameworks for Selective Methanol Synthesis from Catalytic Hydrogenation of CO ₂ An, Bing; Zhang, Jingzheng; Cheng, Kang Journal of the American Chemical Society, Vol. 139, Issue 10 https://doi.org/10.1021/jacs.7b00058	journal	March 2017
An Infrared Study of Methanol Synthesis from CO2 on Clean and Potassium-Promoted Cu/SiO2 Clarke, D. B.; Bell, A. T. Journal of Catalysis, Vol. 154, Issue 2 https://doi.org/10.1006/jcat.1995.1173	journal	July 1995
Wet Chemical Growth and Thermocatalytic Activity of Cu-Based Nanoparticles Supported on TiO ₂ Nanoparticles/HOPG: In Situ Ambient Pressure XPS Study of the CO ₂ Hydrogenation Reaction Ferrah, Djawhar; Haines, Amanda R.; Galhenage, Randima P. ACS Catalysis, Vol. 9, Issue 8 https://doi.org/10.1021/acscatal.9b01419	journal	June 2019
CO ₂ Activation and Reaction on Zn-Deposited Cu Surfaces Studied by Ambient-Pressure X-ray Photoelectron Spectroscopy Koitaya, Takanori; Yamamoto, Susumu; Shiozawa, Yuichiro ACS Catalysis, Vol. 9, Issue 5 https://doi.org/10.1021/acscatal.9b00041	journal	April 2019
Carbonate formation on Al2O3 thin film model catalyst supports Weilach, Christian; Spiel, Christian; Föttinger, Karin Surface Science, Vol. 605, Issue 15-16 https://doi.org/10.1016/j.susc.2011.05.025	journal	August 2011
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
Hydrogenation of CO ₂ to Methanol on CeO _x /Cu(111) and ZnO/Cu(111) Catalysts: Role of the Metal–Oxide Interface and Importance of Ce ³⁺ Sites Senanayake, Sanjaya D.; Ramírez, Pedro J.; Waluyo, Iradwikanari The Journal of Physical Chemistry C, Vol. 120, Issue 3 https://doi.org/10.1021/acs.jpcc.5b12012	journal	January 2016
Hydrogenation of CO ₂ on ZnO/Cu(100) and ZnO/Cu(111) Catalysts: Role of Copper Structure and Metal–Oxide Interface in Methanol Synthesis Palomino, Robert M.; Ramírez, Pedro J.; Liu, Zongyuan The Journal of Physical Chemistry B, Vol. 122, Issue 2 https://doi.org/10.1021/acs.jpcb.7b06901	journal	August 2017
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
Catalytic Intermediates of CO ₂ Hydrogenation on Cu(111) Probed by In Operando Near-Ambient Pressure Technique Ren, Yinjuan; Yuan, Kaidi; Zhou, Xiong Chemistry - A European Journal, Vol. 24, Issue 60 https://doi.org/10.1002/chem.201802931	journal	October 2018
Intermediates Arising from the Water–Gas Shift Reaction over Cu Surfaces: From UHV to Near Atmospheric Pressures Mudiyanselage, K.; Senanayake, S. D.; Ramirez, P. J. Topics in Catalysis, Vol. 58, Issue 4-6 https://doi.org/10.1007/s11244-015-0368-y	journal	March 2015
Surface Chemistry of Carbon Dioxide on Copper Model Catalysts Studied by Ambient-Pressure X-ray Photoelectron Spectroscopy Koitaya, Takanori; Yamamoto, Susumu; Matsuda, Iwao e-Journal of Surface Science and Nanotechnology, Vol. 17, Issue 0 https://doi.org/10.1380/ejssnt.2019.169	journal	January 2019
Hydroxylation of ZnO/Cu(1 1 1) inverse catalysts under ambient water vapor and the water–gas shift reaction Orozco, Ivan; Huang, Erwei; Gutiérrez, Ramón A. Journal of Physics D: Applied Physics, Vol. 52, Issue 45 https://doi.org/10.1088/1361-6463/ab37da	journal	August 2019
Experimental and theoretical investigation of the electronic structure of Cu ₂ O and CuO thin films on Cu(110) using x-ray photoelectron and absorption spectroscopy Jiang, Peng; Prendergast, David; Borondics, Ferenc The Journal of Chemical Physics, Vol. 138, Issue 2 https://doi.org/10.1063/1.4773583	journal	January 2013
Sensitivity factors for XPS analysis of surface atoms Wagner, C. D. Journal of Electron Spectroscopy and Related Phenomena, Vol. 32, Issue 2 https://doi.org/10.1016/0368-2048(83)85087-7	journal	January 1983
Enhancement of the oxygen reduction on nitride stabilized pt-M (M=Fe, Co, and Ni) core–shell nanoparticle electrocatalysts Kuttiyiel, Kurian A.; Choi, YongMan; Hwang, Sun-Mi Nano Energy, Vol. 13 https://doi.org/10.1016/j.nanoen.2015.03.007	journal	April 2015
The role of copper oxidation state in Cu/ZnO/Al2O3 catalysts in CO2 hydrogenation and methanol productivity Dasireddy, Venkata D. B. C.; Likozar, Blaž Renewable Energy, Vol. 140 https://doi.org/10.1016/j.renene.2019.03.073	journal	September 2019
Accelerated Cu ₂ O Reduction by Single Pt Atoms at the Metal-Oxide Interface Schilling, Alex C.; Groden, Kyle; Simonovis, Juan Pablo ACS Catalysis, Vol. 10, Issue 7 https://doi.org/10.1021/acscatal.9b05270	journal	March 2020
In Situ Imaging of Cu ₂ O under Reducing Conditions: Formation of Metallic Fronts by Mass Transfer Baber, Ashleigh E.; Xu, Fang; Dvorak, Filip Journal of the American Chemical Society, Vol. 135, Issue 45 https://doi.org/10.1021/ja408506y	journal	October 2013
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
The adsorption of atomic hydrogen on Cu(111) investigated by reflection-absorption infrared spectroscopy, electron energy loss spectroscopy and low energy electron diffraction Mccash, Elaine M.; Parker, Stewart F.; Pritchard, John Surface Science, Vol. 215, Issue 3 https://doi.org/10.1016/0039-6028(89)90266-5	journal	May 1989
Hydrogen Adsorption on Monoclinic (1̅11) and (1̅01) ZrO ₂ Surfaces: A Periodic ab Initio Study Syzgantseva, Olga; Calatayud, Monica; Minot, Christian The Journal of Physical Chemistry C, Vol. 114, Issue 27 https://doi.org/10.1021/jp103463s	journal	June 2010
Theoretical study of H2 dissociation on a ZrO2 cluster Syzgantseva, Olga; Calatayud, Monica; Minot, Christian Chemical Physics Letters, Vol. 503, Issue 1-3 https://doi.org/10.1016/j.cplett.2010.11.005	journal	February 2011
Surface Species in CO and CO ₂ Hydrogenation over Copper/Zirconia: On the Methanol Synthesis Mechanism Weigel, J.; Koeppel, R. A.; Baiker, A. Langmuir, Vol. 12, Issue 22 https://doi.org/10.1021/la9506990	journal	January 1996
Active Oxygen Vacancy Site for Methanol Synthesis from CO ₂ Hydrogenation on In ₂ O ₃ (110): A DFT Study Ye, Jingyun; Liu, Changjun; Mei, Donghai ACS Catalysis, Vol. 3, Issue 6 https://doi.org/10.1021/cs400132a	journal	April 2013
A Mechanistic Study of Methanol Decomposition over Cu/SiO2, ZrO2/SiO2, and Cu/ZrO2/SiO2 Fisher, Ian A.; Bell, Alexis T. Journal of Catalysis, Vol. 184, Issue 2 https://doi.org/10.1006/jcat.1999.2420	journal	June 1999
Implication of the role of oxygen anions and oxygen vacancies for methanol decomposition over zirconia supported copper catalysts Wu, Gui-Sheng; Wang, Lu-Cun; Liu, Yong-Mei Applied Surface Science, Vol. 253, Issue 2 https://doi.org/10.1016/j.apsusc.2006.01.056	journal	November 2006
Role of the Cu-ZrO ₂ Interfacial Sites for Conversion of Ethanol to Ethyl Acetate and Synthesis of Methanol from CO ₂ and H ₂ Ro, Insoo; Liu, Yifei; Ball, Madelyn R. ACS Catalysis, Vol. 6, Issue 10 https://doi.org/10.1021/acscatal.6b01805	journal	September 2016
CO 2 hydrogenation to methanol over Cu/ZrO 2 catalysts: Effects of zirconia phases Witoon, Thongthai; Chalorngtham, Jiraporn; Dumrongbunditkul, Porntipar Chemical Engineering Journal, Vol. 293 https://doi.org/10.1016/j.cej.2016.02.069	journal	June 2016
Design of Interfacial Sites between Cu and Amorphous ZrO ₂ Dedicated to CO ₂ -to-Methanol Hydrogenation Tada, Shohei; Kayamori, Shingo; Honma, Tetsuo ACS Catalysis, Vol. 8, Issue 9 https://doi.org/10.1021/acscatal.8b01396	journal	July 2018

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