Mechanistic and kinetic relevance of hydrogen and water in CO2 hydrogenation on Cu-based catalysts

Lin, Ting C.; Nolen, Michelle A.; Farberow, Carrie A.; Kwon, Stephanie; Bhan, Aditya

doi:10.1016/j.jcat.2024.115936

Mechanistic and kinetic relevance of hydrogen and water in CO₂ hydrogenation on Cu-based catalysts

Journal Article · Thu Jan 02 00:00:00 EST 2025 · Journal of Catalysis

DOI:https://doi.org/10.1016/j.jcat.2024.115936· OSTI ID:2522823

Lin, Ting C. ^[1]; ^[2]; Farberow, Carrie A. ^[3]; Kwon, Stephanie ^[4]; ^[1]

University of Minnesota, Minneapolis, MN (United States)
Colorado School of Mines, Golden, CO (United States); National Renewable Energy Laboratory (NREL), Golden, CO (United States)
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Colorado School of Mines, Golden, CO (United States)

Here, we ally steady-state kinetics, kinetic isotope effects, and density functional theory (DFT) calculations to illustrate that Cu-based catalysts remain saturated by H-adatoms (H*) and molecular formic acid (HCOOH**) during CO₂ hydrogenation. High H* coverage under methanol synthesis conditions is evidenced by reverse water-gas shift (RWGS) rates that exhibit positive H₂ reaction orders only at P_H2 ≲ 0.5 bar, above which methanol synthesis and RWGS rates exhibit first and zeroth order dependence on P_H2, respectively. HCOOH** also accumulates on the surface with increasing P_CO2 as informed by the Langmuir-type dependence on P_CO2 (0.25-23 bar) for both methanol synthesis and RWGS. As both HCOOH** and H* have one H-atom per site occupied, the two species share the same P_H2 dependence and give rise to CO₂ reaction orders that are independent of P_H2. Surface coverages determined based on kinetic analyses are further corroborated with DFT-derived adsorption energies that show favorable HCOOH** adsorbate-adsorbate interactions as well as repulsive interactions for bidentate formate (HCOO**) on H*-saturated surfaces. Methanol selectivity remains invariant with P_CO2 and P_CO despite CO inhibiting reaction rates, thereby demonstrating methanol synthesis and RWGS occur on the same active site. In contrast, water preferentially inhibits methanol synthesis rates, increases methanol synthesis H₂ reaction order from 1.0 to 1.5, and alters the methanol synthesis H₂/D₂ kinetic isotope effect; the inhibitory effect of H₂O thus cannot be attributed to competitive adsorption alone and instead reflects a change in the rate-determining step for methanol synthesis. The disparate kinetics of methanol synthesis and RWGS evince a branching pathway where methanol is formed from formates and CO is formed from carboxylates. The presented work thus identifies the relevant surface species, underscores the distinct catalytic role of water in branching methanol synthesis and RWGS pathways, and, in doing so, details a mechanistic picture that yields predictable rates and reaction orders for both methanol synthesis and RWGS on Cu-based CO₂ hydrogenation catalysts.

View Accepted Manuscript (DOE)

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Bioenergy Technologies Office (BETO); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231; AC36-08GO28308; SC0025321

OSTI ID:: 2522823

Report Number(s):: NREL/JA--5100-92648; MainId:94429; UUID:fde91c30-9fb4-443c-9a92-8b7f853b15a3; MainAdminId:76162

Journal Information:: Journal of Catalysis, Journal Name: Journal of Catalysis Vol. 443; ISSN 0021-9517

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (75)

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
Towards Oil Independence Through Renewable Methanol Chemistry Olah, George A. Angewandte Chemie International Edition, Vol. 52, Issue 1 https://doi.org/10.1002/anie.201204995	journal	December 2012
Methanol‐Assisted Autocatalysis in Catalytic Methanol Synthesis Thrane, Joachim; Kuld, Sebastian; Nielsen, Niels D. Angewandte Chemie International Edition, Vol. 59, Issue 41 https://doi.org/10.1002/anie.202006921	journal	August 2020
Cu‐Bound Formates are Main Reaction Intermediates during CO₂ Hydrogenation to Methanol over Cu/ZrO₂ Meunier, Frederic C.; Dansette, Isaac; Paredes‐Nunez, Anaelle Angewandte Chemie International Edition, Vol. 62, Issue 29 https://doi.org/10.1002/anie.202303939	journal	June 2023
Effect of the damping function in dispersion corrected density functional theory Grimme, Stefan; Ehrlich, Stephan; Goerigk, Lars Journal of Computational Chemistry, Vol. 32, Issue 7 https://doi.org/10.1002/jcc.21759	journal	March 2011
A Kinetic Model of Methanol Synthesis Askgaard, T. S.; Norskov, J. K.; Ovesen, C. V. Journal of Catalysis, Vol. 156, Issue 2 https://doi.org/10.1006/jcat.1995.1250	journal	October 1995
A Microkinetic Analysis of the Water–Gas Shift Reaction under Industrial Conditions Ovesen, C. V.; Clausen, B. S.; Hammershøi, B. S. Journal of Catalysis, Vol. 158, Issue 1 https://doi.org/10.1006/jcat.1996.0016	journal	January 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
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
In Situ Investigations of Structural Changes in Cu/ZnO Catalysts Grunwaldt, J. -D; Molenbroek, A. M.; Topsøe, N. -Y Journal of Catalysis, Vol. 194, Issue 2 https://doi.org/10.1006/jcat.2000.2930	journal	September 2000
Methods for Finding Saddle Points and Minimum Energy Paths Henkelman, Graeme; Jóhannesson, Gísli; Jónsson, Hannes Theoretical Methods in Condensed Phase Chemistry https://doi.org/10.1007/0-306-46949-9_10	book	January 2005
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
Thermal conductivity of some deuterated compounds in the gaseous phase Vargaftik, N. B.; Vanicheva, N. A. Journal of Engineering Physics, Vol. 27, Issue 2 https://doi.org/10.1007/BF00861605	journal	August 1974
Isotope Effects in Methanol Synthesis and the Reactivity of Copper Formates on a Cu/SiO2 Catalyst Yang, Y.; Mims, C. A.; Disselkamp, R. S. Catalysis Letters, Vol. 125, Issue 3-4 https://doi.org/10.1007/s10562-008-9592-4	journal	August 2008
Kinetics of low-pressure methanol synthesis Graaf, G. H.; Stamhuis, E. J.; Beenackers, A. A. C. M. Chemical Engineering Science, Vol. 43, Issue 12 https://doi.org/10.1016/0009-2509(88)85127-3	journal	January 1988
Catalytic synthesis of methanol from CO/H2IV. The effects of carbon dioxide Klier, K. Journal of Catalysis, Vol. 74, Issue 2 https://doi.org/10.1016/0021-9517(82)90040-9	journal	April 1982
Methanol synthesis from H2, CO, and C02 over Cu/ZnO catalysts Chanchlani, K. Journal of Catalysis, Vol. 136, Issue 1 https://doi.org/10.1016/0021-9517(92)90106-R	journal	July 1992
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
Mechanism of the flame ionization detector II. Isotope effects and heteroatom effects Holm, Torkil Journal of Chromatography A, Vol. 782, Issue 1 https://doi.org/10.1016/S0021-9673(97)00483-4	journal	October 1997
Evidence for a special formate species adsorbed on the Cu–Zn active site for methanol synthesis Nakamura, I.; Nakano, H.; Fujitani, T. Surface Science, Vol. 402-404 https://doi.org/10.1016/S0039-6028(97)00910-2	journal	May 1998
The activity and state of the copper surface in methanol synthesis catalysts Chinchen, G. C.; Waugh, K. C.; Whan, D. A. Applied Catalysis, Vol. 25, Issue 1-2 https://doi.org/10.1016/S0166-9834(00)81226-9	journal	August 1986
Mechanism of methanol synthesis from CO2/CO/H2 mixtures over copper/zinc oxide/alumina catalysts: use of14C-labelled reactants Chinchen, G. C.; Denny, P. J.; Parker, D. G. Applied Catalysis, Vol. 30, Issue 2 https://doi.org/10.1016/S0166-9834(00)84123-8	journal	April 1987
Kinetic study of the reverse water-gas shift reaction over CuO/ZnO/Al2O3 catalysts Ginés, M. J. L.; Marchi, A. J.; Apesteguía, C. R. Applied Catalysis A: General, Vol. 154, Issue 1-2 https://doi.org/10.1016/S0926-860X(96)00369-9	journal	June 1997
Kinetics of deactivation on Cu/ZnO/Al2O3 methanol synthesis catalysts Fichtl, Matthias B.; Schlereth, David; Jacobsen, Nikolas Applied Catalysis A: General, Vol. 502 https://doi.org/10.1016/j.apcata.2015.06.014	journal	August 2015
Catalysis of material surface defects: Multiscale modeling of methanol synthesis by CO2 reduction on copper Kopač, Drejc; Likozar, Blaž; Huš, Matej Applied Surface Science, Vol. 497 https://doi.org/10.1016/j.apsusc.2019.143783	journal	December 2019
By-product co-feeding reveals insights into the role of zinc on methanol synthesis catalysts Santiago, Marta; Barbera, Katia; Ferreira, Cristina Catalysis Communications, Vol. 21 https://doi.org/10.1016/j.catcom.2012.01.031	journal	May 2012
A DFT study of methanol synthesis from CO2 hydrogenation on Cu/ZnO catalyst Wang, Xingzi; Zhang, Hai; Qin, Huang Fuel, Vol. 346 https://doi.org/10.1016/j.fuel.2023.128381	journal	August 2023
Insight into methanol synthesis from CO2 hydrogenation on Cu(111): Complex reaction network and the effects of H2O Zhao, Ya-Fan; Yang, Yong; Mims, Charles Journal of Catalysis, Vol. 281, Issue 2 https://doi.org/10.1016/j.jcat.2011.04.012	journal	July 2011
CO hydrogenation to methanol on Cu–Ni catalysts: Theory and experiment Studt, Felix; Abild-Pedersen, Frank; Wu, Qiongxiao Journal of Catalysis, Vol. 293 https://doi.org/10.1016/j.jcat.2012.06.004	journal	September 2012
Mechanistic studies of methanol synthesis over Cu from CO/CO2/H2/H2O mixtures: The source of C in methanol and the role of water Yang, Y.; Mims, C. A.; Mei, D. H. Journal of Catalysis, Vol. 298 https://doi.org/10.1016/j.jcat.2012.10.028	journal	February 2013
Hydrogenation of CO2 to methanol and CO on Cu/ZnO/Al2O3: Is there a common intermediate or not? Kunkes, Edward L.; Studt, Felix; Abild-Pedersen, Frank Journal of Catalysis, Vol. 328 https://doi.org/10.1016/j.jcat.2014.12.016	journal	August 2015
Probing into the multifunctional role of copper species and reaction pathway on copper-cerium-zirconium catalysts for CO2 hydrogenation to methanol using high pressure in situ DRIFTS Wang, Weiwei; Qu, Zhenping; Song, Lixin Journal of Catalysis, Vol. 382 https://doi.org/10.1016/j.jcat.2019.12.022	journal	February 2020
Unimolecular and bimolecular formic acid decomposition routes on dispersed Cu nanoparticles Lin, Ting Chun; De La Torre, Unai; Hejazi, Ava Journal of Catalysis, Vol. 404 https://doi.org/10.1016/j.jcat.2021.08.049	journal	December 2021
Kinetically relevant variation triggered by hydrogen pressure: A mechanistic case study of CO2 hydrogenation to methanol over Cu/ZnO Wang, Xiuyi; Zhang, Hongbo Journal of Catalysis, Vol. 406 https://doi.org/10.1016/j.jcat.2021.12.034	journal	February 2022
Rates and reversibility of CO2 hydrogenation on Cu-based catalysts Lin, Ting C.; Bhan, Aditya Journal of Catalysis, Vol. 429 https://doi.org/10.1016/j.jcat.2023.115214	journal	January 2024
Recent progress in understanding the nature of active sites for methanol synthesis over Cu/ZnO catalysts Liu, Xinyu; Wang, Hengwei; Lu, Junling Journal of Catalysis, Vol. 436 https://doi.org/10.1016/j.jcat.2024.115561	journal	August 2024
Concepts Relevant for the Kinetic Analysis of Reversible Reaction Systems Razdan, Neil K.; Lin, Ting C.; Bhan, Aditya Chemical Reviews, Vol. 123, Issue 6 https://doi.org/10.1021/acs.chemrev.2c00510	journal	February 2023
Kinetics of Methanol Synthesis from Carbon Dioxide Hydrogenation over Copper–Zinc Oxide Catalysts Portha, Jean-François; Parkhomenko, Ksenia; Kobl, Kilian Industrial & Engineering Chemistry Research, Vol. 56, Issue 45 https://doi.org/10.1021/acs.iecr.7b01323	journal	June 2017
Essential Role of Water in the Autocatalysis Behavior of Methanol Synthesis from CO ₂ Hydrogenation on Cu: A Combined DFT and Microkinetic Modeling Study Xu, Dongyang; Wu, Panpan; Yang, Bo The Journal of Physical Chemistry C, Vol. 123, Issue 14 https://doi.org/10.1021/acs.jpcc.8b12460	journal	March 2019
CO₂ Hydrogenation to CH₃OH on Supported Cu Nanoparticles: Nature and Role of Ti in Bulk Oxides vs Isolated Surface Sites Noh, Gina; Docherty, Scott R.; Lam, Erwin The Journal of Physical Chemistry C, Vol. 123, Issue 51 https://doi.org/10.1021/acs.jpcc.9b09631	journal	December 2019
Surface Sites in Cu-Nanoparticles: Chemical Reactivity or Microscopy? Larmier, Kim; Tada, Shohei; Comas-Vives, Aleix The Journal of Physical Chemistry Letters, Vol. 7, Issue 16 https://doi.org/10.1021/acs.jpclett.6b01328	journal	August 2016
Disclosing the Reaction Mechanism of CO₂ Hydrogenation to Methanol over CuCeO_x/TiO₂: A Combined Kinetic, Spectroscopic, and Isotopic Study Vergara, Tomás; Gómez, Daviel; Lacerda de Oliveira Campos, Bruno ACS Catalysis, Vol. 13, Issue 22 https://doi.org/10.1021/acscatal.3c04243	journal	October 2023
Measuring Adsorbate Profiles in Heterogeneous Catalytic Reactors by Iso-Potential Operando DRIFTS Applied to CO₂ Methanation on Ni Sichert, Sebastian; Stahl, Sarah-Franziska; Korup, Oliver ACS Catalysis, Vol. 14, Issue 11 https://doi.org/10.1021/acscatal.4c00536	journal	May 2024
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
Significance of Surface Formate Coverage on the Reaction Kinetics of Methanol Synthesis from CO 2 Hydrogenation over Cu Wu, Panpan; Yang, Bo ACS Catalysis, Vol. 7, Issue 10 https://doi.org/10.1021/acscatal.7b01910	journal	September 2017
Mechanism Investigations on Water Gas Shift Reaction over Cu(111), Cu(100), and Cu(211) Surfaces Li, Zhiyuan; Li, Na; Wang, Nan ACS Omega, Vol. 7, Issue 4 https://doi.org/10.1021/acsomega.1c05991	journal	January 2022
Spatially Resolved Reaction Profiles of CO₂ Hydrogenation to Methanol Using In-Based Catalysts in a Compact Profile Reactor Kampe, Philipp; Herrmann, Nick; Ruhmlieb, Charlotte ACS Sustainable Chemistry & Engineering, Vol. 12, Issue 25 https://doi.org/10.1021/acssuschemeng.4c03279	journal	June 2024
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
On the Mechanism of Low-Temperature Water Gas Shift Reaction on Copper Gokhale, Amit A.; Dumesic, James A.; Mavrikakis, Manos Journal of the American Chemical Society, Vol. 130, Issue 4 https://doi.org/10.1021/ja0768237	journal	January 2008
Deciphering Metal–Oxide and Metal–Metal Interplay via Surface Organometallic Chemistry: A Case Study with CO₂ Hydrogenation to Methanol Docherty, Scott R.; Copéret, Christophe Journal of the American Chemical Society, Vol. 143, Issue 18 https://doi.org/10.1021/jacs.1c02555	journal	May 2021
Hydrogenation of Formate Species Using Atomic Hydrogen on a Cu(111) Model Catalyst Takeyasu, Kotaro; Sawaki, Yasutaka; Imabayashi, Takumi Journal of the American Chemical Society, Vol. 144, Issue 27 https://doi.org/10.1021/jacs.2c02797	journal	June 2022
Methanol Synthesis from CO₂/CO Mixture on Cu–Zn Catalysts from Microkinetics-Guided Machine Learning Pathway Search Shi, Yun-Fei; Kang, Pei-Lin; Shang, Cheng Journal of the American Chemical Society, Vol. 144, Issue 29 https://doi.org/10.1021/jacs.2c06044	journal	July 2022
Shape-Dependent CO₂ Hydrogenation to Methanol over Cu₂O Nanocubes Supported on ZnO Kordus, David; Jelic, Jelena; Lopez Luna, Mauricio Journal of the American Chemical Society, Vol. 145, Issue 5 https://doi.org/10.1021/jacs.2c11540	journal	January 2023
Gas-Dependent Active Sites on Cu/ZnO Clusters for CH₃OH Synthesis Tu, Weifeng; Ren, Pengchao; Li, Yuanjie Journal of the American Chemical Society, Vol. 145, Issue 16 https://doi.org/10.1021/jacs.2c13784	journal	March 2023
Water and Cu⁺ Synergy in Selective CO₂ Hydrogenation to Methanol over Cu-MgO-Al₂O₃ Catalysts Fernández-Villanueva, Estefanía; Lustemberg, Pablo G.; Zhao, Minjie Journal of the American Chemical Society, Vol. 146, Issue 3 https://doi.org/10.1021/jacs.3c10685	journal	January 2024
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
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
Isolated Zr Surface Sites on Silica Promote Hydrogenation of CO ₂ to CH ₃ OH in Supported Cu Catalysts Lam, Erwin; Larmier, Kim; Wolf, Patrick Journal of the American Chemical Society, Vol. 140, Issue 33 https://doi.org/10.1021/jacs.8b05595	journal	July 2018
(Non)formation of Methanol by Direct Hydrogenation of Formate on Copper Catalysts Yang, Yong; Mims, C. A.; Disselkamp, R. S. The Journal of Physical Chemistry C, Vol. 114, Issue 40 https://doi.org/10.1021/jp104068k	journal	July 2010
Influence of Dipole–Dipole Interactions on Coverage-Dependent Adsorption: CO and NO on Pt(111) Deshlahra, Prashant; Conway, Jonathan; Wolf, Eduardo E. Langmuir, Vol. 28, Issue 22 https://doi.org/10.1021/la300975s	journal	May 2012
Identifying the nature of the active sites in methanol synthesis over Cu/ZnO/Al2O3 catalysts Laudenschleger, Daniel; Ruland, Holger; Muhler, Martin Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-17631-5	journal	August 2020
Surface energies of elemental crystals Tran, Richard; Xu, Zihan; Radhakrishnan, Balachandran Scientific Data, Vol. 3, Issue 1 https://doi.org/10.1038/sdata.2016.80	journal	September 2016
Kinetics and mechanism of the water-gas shift reaction catalysed by the clean and Cs-promoted Cu(110) surface: a comparison with Cu(111) Nakamura, Junji; Campbell, Joseph M.; Campbell, Charles T. Journal of the Chemical Society, Faraday Transactions, Vol. 86, Issue 15 https://doi.org/10.1039/ft9908602725	journal	January 1990
Is the observed hydrogenation of formate the rate-limiting step in methanol synthesis? Taylor, Patrick A.; Rasmussen, Peter B.; Chorkendorff, Ib Journal of the Chemical Society, Faraday Transactions, Vol. 91, Issue 8 https://doi.org/10.1039/ft9959101267	journal	January 1995
Optimization methods for finding minimum energy paths Sheppard, Daniel; Terrell, Rye; Henkelman, Graeme The Journal of Chemical Physics, Vol. 128, Issue 13 https://doi.org/10.1063/1.2841941	journal	April 2008
A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives Henkelman, Graeme; Jónsson, Hannes The Journal of Chemical Physics, Vol. 111, Issue 15 https://doi.org/10.1063/1.480097	journal	October 1999
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
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
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
Inelastic transport theory from first principles: Methodology and application to nanoscale devices Frederiksen, Thomas; Paulsson, Magnus; Brandbyge, Mads Physical Review B, Vol. 75, Issue 20 https://doi.org/10.1103/PhysRevB.75.205413	journal	May 2007
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data Momma, Koichi; Izumi, Fujio Journal of Applied Crystallography, Vol. 44, Issue 6 https://doi.org/10.1107/S0021889811038970	journal	October 2011
Doubling the life of Cu/ZnO methanol synthesis catalysts via use of Si as a structural promoter to inhibit sintering Barrow, Nathan; Bradley, Jonathan; Corrie, Benjamin Science Advances, Vol. 10, Issue 3 https://doi.org/10.1126/sciadv.adk2081	journal	January 2024
The Active Site of Methanol Synthesis over Cu/ZnO/Al₂O₃ Industrial Catalysts Behrens, M.; Studt, F.; Kasatkin, I. Science, Vol. 336, Issue 6083, p. 893-897 https://doi.org/10.1126/science.1219831	journal	April 2012
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

Similar Records

Methanol Synthesis from CO2 Hydrogenation over a Pd4/In2O3 Model Catalyst: A Combined DFT and Kinetic Study

Journal Article · Fri Aug 01 00:00:00 EDT 2014 · Journal of Catalysis, 317:44-53 · OSTI ID:1155126

Rates and reversibility of CO₂ hydrogenation on Cu-based catalysts

Journal Article · Sun Nov 19 19:00:00 EST 2023 · Journal of Catalysis · OSTI ID:2479056

Fundamental Studies of Methanol Synthesis from CO2 Hydrogenation on Cu(111), Cu Clusters, and Cu/ZnO(000ī)

Journal Article · Mon Jun 21 00:00:00 EDT 2010 · Physical Chemistry Chemical Physics · OSTI ID:1004644

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Active site
Adsorption energy
CO2
Coverage
Mechanism
Methanol
Rate-determining step

Mechanistic and kinetic relevance of hydrogen and water in CO2 hydrogenation on Cu-based catalysts

Citation Formats

References (75)

Similar Records

Related Subjects

Mechanistic and kinetic relevance of hydrogen and water in CO₂ hydrogenation on Cu-based catalysts