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Promotion Of Methanol Synthesis And The Water-gas Shift Reactions By Adsorbed Oxygen On Supported Copper Catalysts

G. Chinchen, M. Spencer, K. C. Waugh, D. Whan
Published 1987 · Chemistry

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The surfaces of the copper metal crystallites of working Cu/ZuO/Al2O3 and other copper catalysts are partially oxidised in reaction mixtures for methanol synthesis and the water-gas shift reaction. Work with unsupported polycrystalline copper has confirmed earlier results that copper metal is the active phase in supported copper catalysts. The coverage of adsorbed oxygen, O(a), up to half-monolayer, was determined by reaction with N2O and it was found to be controlled by the overall reaction CO2(g)= CO(g)+ O(a). The free energy of formation of O(a) was calculated to be –240 kJ mol–1 at 513 K. The induction period found in methanol synthesis from CO–CO2–H2 mixtures is consistent with the calculated rate of formation of O(a). The role of O(a) in the methanol synthesis and water-gas shift reactions is both as promoter and reaction intermediate. The dissociative chemisorption of hydrogen on copper is promoted by O(a) but this is not necessary for the reactions. Experiments with unsupported polycrystalline copper have shown that O(a) both increases the extent of physisorption of CO2 and creates new chemisorbed states of CO2, with desorption energies of 109, 113 and 125 kJ mol–1. O(a) is also essential for the dissociative chemisorption of water on copper. A regenerative mechanism for the water-gas shift reaction on copper [involving the formation and reaction of O(a)] has been established by observation of the separate stages. The adsorbed formate intermediate, pivotal in methanol synthesis from carbon dioxide, is irrelevant to the water-gas shift reaction.



This paper is referenced by
10.1002/9781119951438.EIBC0209
Solids: Computer Modeling
R. Catlow (2006)
10.2172/973340
LDRD final report on "fundamentals of synthetic conversion of CO2 to simple hydrocarbon fuels" (LDRD 113486).
Christos T. Maravelias (2009)
10.1002/CJOC.200690033
Role of nanosized zirconia on the properties of Cu/Ga2O3/ZrO2 catalysts for methanol synthesis
X. Liu (2006)
10.1007/S41365-016-0170-Y
Local structural evolutions of CuO/ZnO/Al2O3 catalyst for methanol synthesis under operando conditions studied by in situ quick X-ray absorption spectroscopy
Xueping Sun (2016)
10.1016/S0166-1280(03)00209-4
Investigation of the kinetic properties for the forward and reverse WGS reaction by energetic analysis
Guichang Wang (2003)
10.1007/BF00769173
Methanol synthesis on a Cu(100) catalyst
J. Szanyi (1991)
10.1016/J.PROGSURF.2014.03.002
Surface chemistry of CO2 – Adsorption of carbon dioxide on clean surfaces at ultrahigh vacuum
U. Burghaus (2014)
10.1039/B200615B
Conversion of methane into higher hydrocarbons in the presence of ethylene over H-ZSM-5 loaded with silver cations
T. Baba (2002)
10.1016/S1872-2067(18)30010-X
Synthesis and Reforming of Dimethoxymethane
Fu Yu-chuan (2009)
10.1016/0169-4332(94)90277-1
Influence of atomic Cu-layer epitaxy on Co2 and CO phtoinduced desorption from ZnO(0001)
P. Møller (1994)
10.1016/S0039-6028(98)00105-8
Adsorption and reaction of carbon dioxide on pure and alkali-metal promoted cold-deposited copper films
M. Pohl (1998)
10.1016/0920-5861(94)00135-O
Water-gas shift reaction: finding the mechanistic boundary
C. Rhodes (1995)
10.1016/J.CATTOD.2006.10.003
On the complexity of the water-gas shift reaction mechanism over a Pt/CeO2 catalyst: Effect of the temperature on the reactivity of formate surface species studied by operando DRIFT during isotopic transient at chemical steady-state
F. Meunier (2007)
10.1007/978-1-4471-5119-7_9
Advances in Catalysts and Processes for Methanol Synthesis from CO2
G. Centi (2013)
10.1016/S0926-860X(03)00048-6
CO removal from reformed fuels over Cu and precious metal catalysts
Toshimasa Utaka (2003)
10.1016/0021-9517(91)90141-P
The effects of carbon dioxide, methanol, and alkali promoter concentration on the higher alcohol synthesis over a Cu/ZnO/Cr2O3 catalyst
E. M. Calverley (1991)
10.1007/BF02699049
Effects of space velocity on methanol synthesis from Co2/Co/H2 over Cu/ZnO/Al2O3 catalyst
J. Lee (2000)
10.1016/J.NIMA.2008.12.155
Photoelectron spectroscopy under ambient pressure and temperature conditions
D. Ogletree (2009)
10.1002/cphc.201200517
Activation of carbon dioxide over zinc oxide by localised electrons.
G. Dutta (2012)
10.1016/J.SUSC.2012.04.007
Atomistic simulations of the adsorption and migration barriers of Cu adatoms on ZnO surfaces using COMB potentials
Yuting Cheng (2012)
10.1016/J.SUSC.2009.04.011
A theoretical study of the water gas shift reaction mechanism on Cu(111) model system
Qian-Lin Tang (2009)
10.1098/rsta.2004.1529
Computational approaches to the determination of active site structures and reaction mechanisms in heterogeneous catalysts
C. R. Catlow (2005)
10.1002/ANGE.19931050308
Heterogene Katalyse ‐ immer noch Kunst oder schon Wissenschaft?
R. Schlögl (1993)
10.1016/0039-6028(92)91441-D
Roughness induced reactions of N2 and CO2 on noble and alkali metals
W. Akemann (1992)
10.1016/S0167-2991(08)60686-2
Effect of Cobalt on the Surface Properties of Zn-Cr and Cu-Zn-Cr Methanol Synthesis Catalysts
G. Busca (1989)
10.1063/1.3506897
Water-gas shift reaction on oxide∕Cu(111): Rational catalyst screening from density functional theory.
P. Liu (2010)
10.1007/BF00765350
The adsorption and decomposition of carbon dioxide on polycrystalline copper
R. A. Hadden (1988)
10.1007/BF02137613
Water-gas shift reaction over chromia-promoted magnetite. Use of temperature-programmed desorption and chemical trapping in the study of the reaction mechanism
C. Diagne (1990)
10.1007/978-3-642-78632-7_15
Structural and Electronic Properties of Ultrathin Cu-Layers on some Crystalline Metal-Oxides
P. Møller (1993)
10.3390/ma13245601
Catalysts for Hydrogen Generation via Oxy–Steam Reforming of Methanol Process
Magdalena Mosińska (2020)
Catalytic Hydrogenation of CO 2 to Methanol : Study of Synergistic Effect on Adsorption Properties of CO 2 and H 2 in CuO / ZnO / ZrO 2 System
C. Huang (2015)
10.1016/S0926-860X(02)00516-1
The active role of CO2 at low temperature in oxidation processes: the case of the oxidative dehydrogenation of propane on NiMoO4 catalysts
Frédéric Dury (2003)
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