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On The Issue Of The Active Site And The Role Of ZnO In Cu/ZnO Methanol Synthesis Catalysts

J. Nakamura, Y. Choi, T. Fujitani
Published 2003 · Chemistry

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The problem concerning the active site and the role of ZnO in Cu/ZnO-based methanol synthesis catalysts can be consistently explained based on the literature results by distinguishing CO2 and CO hydrogenations. Although only metallic copper has some activities for methanol synthesis by the hydrogenation of CO2, Cu-Zn alloying in Cu particles is responsible for the major promotional role of ZnO in industrial Cu/ZnO-based catalysts. The morphology effect reported in the literature will probably appear for the system of highly dispersed Cu particles supported on ZnO. As for the hydrogenation of CO, Cu+ species or Cu-O-Zn sites are the active sites for methanol synthesis. The spillover effect of the Cu-ZnO system is not significant compared to the effect of ZnO on the creation of the Cu-O-Zn site.
This paper references
10.1006/JCAT.1995.1250
A Kinetic Model of Methanol Synthesis
T. Askgaard (1995)
10.1006/JCAT.1998.2301
Methanol Synthesis from CO2, CO, and H2over Cu(100) and Ni/Cu(100)
J. Nerlov (1999)
10.1006/JCAT.1997.1629
Kinetic Implications of Dynamical Changes in Catalyst Morphology during Methanol Synthesis over Cu/ZnO Catalysts
C. V. Ovesen (1997)
10.1039/F19898503569
Synergy between copper and zinc oxide during methanol synthesis. Transfer of activating species
R. Burch (1989)
10.1007/BF00816308
The chemisorption of methanol on Cu films on ZnO(000¯1)-O
R. Zhang (1994)
10.1038/334577A0
Junction effect interactions in methanol synthesis catalysts
J. C. Frost (1988)
10.1016/S0926-860X(00)00712-2
The role of ZnO in Cu/ZnO methanol synthesis catalysts — morphology effect or active site model?
Y. Choi (2001)
10.1016/0021-9517(74)90030-X
Brass formation in a copper/zinc oxide CO shift catalyst
T. Vanherwijnen (1974)
10.1039/FT9928801033
Evidence for the adsorption of molecules at special sites located at copper/zinc oxide interfaces: part 1.—A Fourier-transform infrared study of formic acid and formaldehyde adsorption on reduced and oxidised Cu/ZnO/SiO2 catalysts
G. Millar (1992)
10.1016/0021-9517(86)90354-4
Electronic effect of supports on copper catalysts
H. Chen (1986)
10.1016/0021-9517(89)90115-2
Differences in the promotional effect of the group IA elements on unsupported copper catalysts for carbon monoxide hydrogenation
G. Sheffer (1989)
10.1016/0039-6028(94)91157-6
The chemisorption and reactions of formic acid on Cu films on ZnO (0001)-O
A. Ludviksson (1994)
10.1016/S0039-6028(87)81127-5
α-Brass formation in copper/zinc oxide catalysts: I. Bulk equilibrium concentrations of zinc under methanol synthesis and water-gas shift reaction conditions
M. S. Spencer (1987)
10.1016/0039-6028(94)90101-5
Synthesis of methanol from a mixture of H2 and CO2 on Cu(100)
P. B. Rasmussen (1994)
10.1016/S0039-6028(97)00899-6
The synthesis of methanol and the reverse water-gas shift reaction over Zn-deposited Cu(100) and Cu(110) surfaces: comparison with Zn/Cu(111)
I. Nakamura (1998)
10.1016/0021-9517(89)90018-3
NMR studies of 65Cu and 133Cs in alkali-metal-promoted copper catalysts☆
Po-Jen Chu (1989)
10.1039/FT9928801477
Infrared study of CO, CO2, H2 and H2O interactions on potassium-promoted reduced and oxidised silica-supported copper catalysts
G. Millar (1992)
10.1006/JCAT.1993.1148
The Chemisorption of CO on Cu Films on ZnO(0001)-O
A. Ludviksson (1993)
10.1007/BF00808597
Spectroscopic evidence for adsorption sites located at Cu/ZnO interfaces
Julian E. Bailie (1995)
10.1016/S0039-6028(87)81129-9
α-brass formation in copper/zinc oxide catalysts: III. Surface segregation of zinc in α-brass
M. Spencer (1987)
10.1016/0021-9517(89)90334-5
Mechanism of methanol synthesis from carbon monoxide and hydrogen on copper catalysts
M. E. Fakley (1989)
10.1023/A:1018962016811
Adsorption and reaction induced morphological changes of the copper surface of a methanol synthesis catalyst
R. A. Hadden (1997)
10.1006/JCAT.1996.0124
A Surface Science Investigation of Methanol Synthesis over a Zn-Deposited Polycrystalline Cu Surface
J. Nakamura (1996)
10.1023/A:1019017931794
The role of surface oxygen on copper metal in catalysts for the synthesis of methanol
M. S. Spencer (1999)
10.1023/A:1019077223500
Reply to the comment on “The effect of ZnO in methanol synthesis catalysts on Cu dispersion and the specific activity” [by K.C. Waugh]
T. Fujitani (1999)
10.1006/JCAT.2000.2930
In Situ Investigations of Structural Changes in Cu/ZnO Catalysts
J. Grunwaldt (2000)
10.1016/S1381-1169(99)00314-3
Synthesis and decomposition of formate on a Cu(111) surface — kinetic analysis
H. Nishimura (2000)
10.1007/BF00769173
Methanol synthesis on a Cu(100) catalyst
J. Szanyi (1991)
10.1006/JCAT.1995.1306
Mechanisms of Methanol Synthesis from Carbon Dioxide and from Carbon Monoxide at Atmospheric Pressure over Cu/ZnO
S. Fujita (1995)
10.1006/JCAT.1996.0240
Methanol Synthesis and Reverse Water–Gas Shift Kinetics over Cu(110) Model Catalysts: Structural Sensitivity
J. Yoshihara (1996)
10.1021/JP9920242
Scanning Tunneling Microscopy Study of Formate Species Synthesized from CO2 Hydrogenation and Prepared by Adsorption of Formic Acid over Cu(111)
T. Fujitani (2000)
10.1016/S0166-9834(00)81226-9
The activity and state of the copper surface in methanol synthesis catalysts
G. Chinchen (1986)
10.1116/1.579970
A model catalyst for methanol synthesis: Zn‐deposited and Zn‐free Cu surfaces
I. Nakamura (1996)
10.1016/0926-860X(92)80041-A
Methanol synthesis by means of diffuse reflectance infrared Fourier transform and temperature-programmed reaction spectroscopy
S. Neophytides (1992)
10.1016/0021-9517(79)90001-0
Catalytic synthesis of methanol from COH2: II. Electron microscopy (TEM, STEM, microdiffraction, and energy dispersive analysis) of the CuZnO and Cu/ZnO/Cr2O3 catalysts
S. Mehta (1979)
10.1023/A:1019098414820
Role of ZnO in methanol synthesis on copper catalysts
M. Spencer (1998)
10.1023/A:1019025816831
Comments on “The effect of ZnO in methanol synthesis catalysts on Cu dispersion and the specific activity” [by T. Fujitani and J. Nakamura]
K. C. Waugh (1999)
10.1016/S0166-9834(00)80103-7
Synthesis of Methanol
G. Chinchen (1988)
10.1021/JP990375A
Cu/ZnO and Cu/ZnO/SiO2 catalysts studied by low-energy ion scattering
M. Viitanen (1999)
10.1006/JCAT.1998.1964
Methanol Synthesis from CO/CO2/H2over Cu/ZnO/Al2O3at Differential and Finite Conversions
M. Sahibzada (1998)
10.1039/FT9928802085
A combined temperature-programmed reaction spectroscopy and Fourier-transform infrared spectroscopy study of CO2–H2 and CO–CO2–H2 interactions with model ZnO/SiO2, Cu/SiO2 and Cu/ZnO/SiO2 methanol-synthesis catalysts
G. Millar (1992)
10.1016/0021-9517(89)90042-0
Potassium's promotional effect of unsupported copper catalysts for methanol synthesis
G. Sheffer (1989)
10.1007/BF00810611
Methanol synthesis on Cu(100) from a binary gas mixture of CO2 and H2
P. B. Rasmussen (1994)
10.1016/S0039-6028(87)81128-7
α-Brass formation in copper/zinc oxide catalysts: II. Diffusion of zinc in copper and α-brass under reaction conditions
M. Spencer (1987)
10.1021/J100272A019
The structure of the copper/zinc oxide catalyst by an in-situ EXAFS study
K. Tohji (1985)
10.1016/S0039-6028(97)00192-1
The kinetics and mechanism of methanol synthesis by hydrogenation of CO2 over a Zn-deposited Cu(111) surface
T. Fujitani (1997)
10.1007/BF00806562
The synergy between Cu and ZnO in methanol synthesis catalysts
Y. Kanai (1996)
10.1023/A:1019069708459
Creation of the active site for methanol synthesis on a Cu/SiO2 catalyst
T. Fujitani (1997)
10.1023/A:1019000927366
The effect of ZnO in methanol synthesis catalysts on Cu dispersion and the specific activity
T. Fujitani (1998)
10.1016/S0039-6028(97)00910-2
Evidence for a special formate species adsorbed on the Cu–Zn active site for methanol synthesis
I. Nakamura (1998)
10.1007/BF00808595
Methanol synthesis and reverse water-gas shift kinetics over clean polycrystalline copper
J. Yoshihara (1995)
10.1006/JCAT.2000.2810
Synthesis and Decomposition of Formate on a Cu/SiO2 Catalyst: Comparison to Cu(111)
T. Yatsu (2000)
10.1016/0021-9517(88)90047-4
Methanol synthesis activity of Cu/ZnO catalysts
W. Pan (1988)
10.1007/BF00806979
Evidence for the migration of ZnOx in a Cu/ZnO methanol synthesis catalyst
Y. Kanai (1994)
10.1039/F19878302193
Promotion of methanol synthesis and the water-gas shift reactions by adsorbed oxygen on supported copper catalysts
G. Chinchen (1987)
10.1016/S0039-6028(98)00201-5
Chemisorption of formic acid and CO on Cu particles on the Zn-terminated ZnO(0001) surface
J. Yoshihara (1998)
10.1006/JCAT.1998.2167
Basic Metal Oxides as Cocatalysts for Cu/SiO2Catalysts in the Conversion of Synthesis Gas to Methanol
A. Gotti (1998)
10.1016/S0169-4332(97)00372-3
Methanol synthesis by hydrogenation of CO2 over a Zn-deposited Cu(111): formate intermediate
T. Fujitani (1997)
10.1023/A:1019033517855
Promotion through gas phase induced surface segregation: methanol synthesis from CO, CO2 and H2 over Ni/Cu(100)
J. Nerlov (1998)
10.1039/FT9908602683
The role of copper and zinc oxide in methanol synthesis catalysts
R. Burch (1990)
10.1016/0021-9517(79)90132-5
Catalytic synthesis of methanol from COH2: I. Phase composition, electronic properties, and activities of the Cu/ZnO/M2O3 catalysts
R. Herman (1979)



This paper is referenced by
10.1201/b17552-7
Syngas to methanol and ethanol
M. Muhler (2015)
Nanoscale Modification of Copper for Novel Methanol and Water-Gas Shift Catalysts
N. Schumacher (2008)
10.1002/AIC.15010
PtZn‐ETS‐2: A novel catalyst for ethane dehydrogenation
Z. Yu (2015)
10.1039/d0ta00509f
Cu/M:ZnO (M = Mg, Al, Cu) colloidal nanocatalysts for the solution hydrogenation of carbon dioxide to methanol
A. Leung (2020)
Electrochemical reduction of CO2 to methanol
Minh Tuyen Hoang Le (2011)
10.1021/ACSCATAL.5B00877
Zinc-Rich Copper Catalysts Promoted by Gold for Methanol Synthesis
O. Martin (2015)
10.1002/cctc.201700213
DFT Study of Nickel‐Catalyzed Low‐Temperature Methanol Synthesis
D. McGuinness (2017)
10.1039/c9cy01242g
Intermetallic PdIn catalyst for CO2 hydrogenation to methanol: mechanistic studies with a combined DFT and microkinetic modeling method
Panpan Wu (2019)
10.1002/jcc.21043
Adsorption of single Cu atoms at differently stabilized polar ZnO surfaces: An ab initio study
Ilka Hegemann (2008)
10.2478/CPE-2013-0039
COPPER/ZINC CATALYSTS IN HYDROGENATION OF CARBON OXIDES
M. Kulawska (2013)
10.1002/cssc.200900183
The role of chemistry in the energy challenge.
R. Schlögl (2010)
10.1021/JP201839S
Dynamic Cu/Zn Interaction in SiO2 Supported Methanol Synthesis Catalysts Unraveled by in Situ XAFS
D. Grandjean (2011)
Final Research Project in MSc Chemical Engineering Kinetics of High Pressure Methanol Synthesis Part of Supermethanol , GtM Project
J. V. Bennekom (2014)
10.1002/anie.201600943
Indium Oxide as a Superior Catalyst for Methanol Synthesis by CO2 Hydrogenation.
O. Martin (2016)
10.1063/1.5132979
The roles of step-site and zinc in surface chemistry of formic acid on clean and Zn-modified Cu(111) and Cu(997) surfaces studied by HR-XPS, TPD, and IRAS.
Yuichiro Shiozawa (2020)
10.1039/c0cc04933f
Knowledge-based development of a nitrate-free synthesis route for Cu/ZnO methanol synthesis catalysts via formate precursors.
M. Behrens (2011)
10.1002/9783527610044.HETCAT0042
Scanning Probe Techniques
F. Besenbacher (2008)
10.1007/s11244-020-01283-2
The Challenge of CO Hydrogenation to Methanol: Fundamental Limitations Imposed by Linear Scaling Relations
Ahmed O. Elnabawy (2020)
10.1007/s11244-016-0551-9
Sustainable Energy Systems: The Strategic Role of Chemical Energy Conversion
R. Schlögl (2016)
10.1016/B978-0-444-64235-6.50017-6
Kinetic Modeling of Methanol Synthesis - Impact of Catalyst Deactivation
C. Seidel (2018)
10.1016/J.SUSC.2008.09.063
The surface chemistry of ZnO nanoparticles applied as heterogeneous catalysts in methanol synthesis
J. Strunk (2009)
10.1016/S0167-2991(04)80212-X
Heterogeneous Catalytic Reactions with CO2: Status and Perspectives
G. Centi (2004)
10.1002/anie.201106591
Hydrogen Production by Methanol Steam Reforming on Copper Boosted by Zinc–Assisted Water Activation**
Christoph Rameshan (2012)
10.1021/JP3051438
Exploring the activated state of Cu/ZnO(0001)-Zn, a model catalyst for methanol synthesis
E. Batyrev (2012)
10.1063/1.4941060
Observation of Fano line shapes in infrared vibrational spectra of CO2 adsorbed on Cu(997) and Cu(111).
T. Koitaya (2016)
10.1016/J.RSER.2013.11.045
Conversion of carbon dioxide into methanol – a potential liquid fuel: Fundamental challenges and opportunities (a review)
I. Ganesh (2014)
10.1038/s41467-020-16342-1
The unique interplay between copper and zinc during catalytic carbon dioxide hydrogenation to methanol
Maxim Zabilskiy (2020)
10.1039/B709384E
Kinetic explosion and bistability in adsorption and reaction of acetic acid on Pd(110).
M. Bowker (2007)
10.1039/c0cc00751j
Synthesis of dimethylformamide from CO2, H2 and dimethylamine over Cu/ZnO.
J. Liu (2010)
10.1016/J.JCAT.2013.10.015
Thermochemistry and micro-kinetic analysis of methanol synthesis on ZnO (0001)
Andrew J Medford (2014)
10.1007/s11244-012-9863-6
Synergy of Components in CuZnO and CuZnO/Al2O3 on Methanol Synthesis: Analysis at the Site Level by SSITKA
Yu-Tung Tsai (2012)
10.1039/c4cp05518g
Effect of the components' interface on the synthesis of methanol over Cu/ZnO from CO2/H2: a microkinetic analysis based on DFT + U calculations.
Qian-Lin Tang (2015)
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