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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

S. Senanayake, P. Ramírez, I. Waluyo, S. Kundu, K. Mudiyanselage, Zongyuan Liu, Z. Liu, S. Axnanda, D. Stacchiola, J. Evans, J. Rodriguez
Published 2016 · Chemistry

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The role of the interface between a metal and oxide (CeOx–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 CeOx or ZnO on Cu(111), θoxi < 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) < CeOx/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 CeOx/Cu(111). The surface chemistry of the highly active CeOx–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 (CO2δ−) during the reaction. Our results show an active state of the catalyst rich in Ce3+ sites which stabilize a CO2δ− species that is an essential inter...
This paper references
10.1039/c001484b
Fundamental studies of methanol synthesis from CO(2) hydrogenation on Cu(111), Cu clusters, and Cu/ZnO(0001).
Y. Yang (2010)
CO2 Capture: Technologies to Reduce Greenhouse Gas Emissions
F. Lecomte (2010)
10.1007/s11244-013-0169-0
Activity and Selectivity Trends in Synthesis Gas Conversion to Higher Alcohols
Andrew J Medford (2013)
10.1002/anie.201411581
Formation of a ZnO overlayer in industrial Cu/ZnO/Al2 O3 catalysts induced by strong metal-support interactions.
T. Lunkenbein (2015)
10.1126/science.1253057
Highly active copper-ceria and copper-ceria-titania catalysts for methanol synthesis from CO2
J. Graciani (2014)
10.1007/BF00769173
Methanol synthesis on a Cu(100) catalyst
J. Szanyi (1991)
10.1038/526628a
How to make the most of carbon dioxide
X. Lim (2015)
10.1016/0039-6028(87)90013-6
Cu/ZnO(0001) and ZnOx/Cu(111): Model catalysts for methanol synthesis
C. Campbell (1987)
10.1002/cssc.201100473
Carbon dioxide recycling: emerging large-scale technologies with industrial potential.
E. A. Quadrelli (2011)
10.1016/0039-6028(94)90027-2
The electronic structure of stoichiometric and reduced CeO2 surfaces: an XPS, UPS and HREELS study
A. Pfau (1994)
10.1007/BF00810611
Methanol synthesis on Cu(100) from a binary gas mixture of CO2 and H2
P. B. Rasmussen (1994)
Feature : There ’ s Too Much Carbon Dioxide in the Air . Why Not Turn it Back into Fuel ?
R. F. Service (2015)
10.1021/cr3002017
Electron transfer at oxide surfaces. The MgO paradigm: from defects to ultrathin films.
G. Pacchioni (2013)
10.1021/ja8081268
Adsorbate-driven morphological changes of a gold surface at low temperatures.
J. Hrbek (2008)
10.1006/JCAT.1996.0124
A Surface Science Investigation of Methanol Synthesis over a Zn-Deposited Polycrystalline Cu Surface
J. Nakamura (1996)
10.1016/0039-6028(88)90576-6
Spectroscopic characterization of surface formates produced via reaction of HCOOH and HCOOCH3 on the (0001) surface of zinc oxide
J. Vohs (1988)
10.1002/cctc.201500123
The Mechanism of CO and CO2 Hydrogenation to Methanol over Cu‐Based Catalysts
Felix Studt (2015)
10.1002/anie.201210077
Importance of the metal-oxide interface in catalysis: in situ studies of the water-gas shift reaction by ambient-pressure X-ray photoelectron spectroscopy.
K. Mudiyanselage (2013)
10.1016/J.JCOU.2014.03.002
Formation of hydrocarbons via CO2 hydrogenation – A thermodynamic study
L. Torrente-Murciano (2014)
10.1007/s11244-013-0175-2
Microstructural and Defect Analysis of Metal Nanoparticles in Functional Catalysts by Diffraction and Electron Microscopy: The Cu/ZnO Catalyst for Methanol Synthesis
Timur Kandemir (2013)
Hydrogenation of CO 2 to Methanol : Importance of Metal-Oxide and Metal-Carbide Interfaces in the Activation of CO 2
J. Rodriguez (2015)
10.1016/0920-5861(92)80125-7
The synthesis of higher alcohols using modified Cu/ZnO/Al2O3 catalys
J. Slaa (1992)
10.1021/JP509947T
Unraveling the Nature of the Oxide−Metal Interaction in Ceria-Based Noble Metal Inverse Catalysts
J. Graciani (2014)
10.1063/1.1512336
A differentially pumped electrostatic lens system for photoemission studies in the millibar range
D. Ogletree (2002)
tives of CO 2 conversion into fuels and chemicals by catalytic , photocatalytic and electrocatalytic processes †
E. Kondratenko (2013)
10.1002/CHIN.199240131
The Synthesis of Higher Alcohols Using Modified Cu/ZnO/Al2O3 Catalysts.
J. Slaa (1992)
10.1016/S0167-5729(96)00011-8
Ultrathin metal films and particles on oxide surfaces: structural, electronic and chemisorptive properties
C. Campbell (1997)
10.1006/JCAT.1996.0240
Methanol Synthesis and Reverse Water–Gas Shift Kinetics over Cu(110) Model Catalysts: Structural Sensitivity
J. Yoshihara (1996)
10.1002/9783527629916
Carbon dioxide as chemical feedstock
M. Aresta (2010)
10.1126/SCIENCE.1090228
Modern Global Climate Change
T. Karl (2003)
10.1021/CS200055D
Mechanism of Methanol Synthesis on Cu through CO2 and CO Hydrogenation
L. Grabow (2011)
10.1016/J.JNGSE.2014.11.010
Direct CO2 hydrogenation to methane or methanol from post-combustion exhaust streams – A thermodynamic study
C. Miguel (2015)
10.1021/ACSCATAL.5B01755
Hydrogenation of CO2 to Methanol: Importance of Metal–Oxide and Metal–Carbide Interfaces in the Activation of CO2
J. Rodriguez (2015)
Carbon Dioxide as Chemical Feedstock; Aresta, M., Ed.; WileyVCH
R. F. Service (2010)
10.1039/c2cp42091k
Density functional study of water-gas shift reaction on M3O(3x)/Cu(111).
A. B. Vidal (2012)
10.1126/science.1150038
Activity of CeOx and TiOx Nanoparticles Grown on Au(111) in the Water-Gas Shift Reaction
J. Rodriguez (2007)
10.1016/S0167-5729(98)00002-8
Surface studies of supported model catalysts
C. Henry (1998)
10.1021/ACSCATAL.5B00188
Promoting Strong Metal Support Interaction: Doping ZnO for Enhanced Activity of Cu/ZnO:M (M = Al, Ga, Mg) Catalysts
Julia Schumann (2015)



This paper is referenced by
10.1002/CNMA.201900195
H2 Adsorption on Wurtzite ZnO and on ZnO/M(111) (M=Cu, Ag and Au) Bilayer Films
H. Thang (2019)
10.1016/J.MCAT.2019.110499
CO2 hydrogenation over acid-activated Attapulgite/Ce0.75Zr0.25O2 nanocomposite supported Cu-ZnO based catalysts
Haijun Guo (2019)
10.1039/c8cp01505h
Thermal reduction of ceria nanostructures on rhodium(111) and re-oxidation by CO2.
A. Schäfer (2018)
10.1016/J.CATTOD.2018.04.021
A review of research progress on heterogeneous catalysts for methanol synthesis from carbon dioxide hydrogenation
Shanshan Dang (2019)
10.1039/c9cp05831a
In situ environmental TEM observation of two-stage shrinking of Cu2O islands on Cu(100) during methanol reduction.
H. Chi (2020)
10.1126/science.aan8210
Response to Comment on “Active sites for CO2 hydrogenation to methanol on Cu/ZnO catalysts”
Shyam Kattel (2017)
10.1007/s00894-017-3567-6
CO oxidation on inverse Ce6O12/Cu(111) catalyst: role of copper–ceria interactions
B. Yang (2017)
10.1016/J.JCAT.2018.01.035
Ab initio study of CO 2 hydrogenation mechanisms on inverse ZnO/Cu catalysts
Thomas Reichenbach (2018)
10.1016/J.JCOU.2017.12.005
DFT insight into the support effect on the adsorption and activation of key species over Co catalysts for CO2 methanation
X. Nie (2018)
10.1016/j.apsusc.2020.146900
Zirconia-modified copper catalyst for CO2 conversion to methanol from DFT study
Lingna Liu (2020)
10.1016/J.JECHEM.2019.03.001
CO2 hydrogenation to methanol over Cu/CeO2 and Cu/ZrO2 catalysts: Tuning methanol selectivity via metal-support interaction
W. Wang (2020)
10.1016/J.SUSC.2016.10.001
Adsorption and dissociation of molecular hydrogen on orthorhombic β- Mo2C and cubic δ-MoC (001) surfaces
Sergio Posada-Pérez (2017)
10.1039/c6cs00863a
Ceria-based model catalysts: fundamental studies on the importance of the metal-ceria interface in CO oxidation, the water-gas shift, CO2 hydrogenation, and methane and alcohol reforming.
J. Rodriguez (2017)
10.1039/c6cs00828c
Surface chemistry of group IB metals and related oxides.
W. Huang (2017)
10.1016/J.APCATB.2016.05.037
The role of Copper–Ceria interactions in catalysis science: Recent theoretical and experimental advances
M. Konsolakis (2016)
10.1007/s10971-018-4680-4
CO2 hydrogenation to methanol over CuO–ZnO–TiO2–ZrO2: a comparison of catalysts prepared by sol–gel, solid-state reaction and solution-combustion
D. Chen (2018)
10.1039/C5CY02143J
The conversion of CO2 to methanol on orthorhombic β-Mo2C and Cu/β-Mo2C catalysts: mechanism for admetal induced change in the selectivity and activity
Sergio Posada-Pérez (2016)
10.1039/C9RA00658C
Cylindrical shaped ZnO combined Cu catalysts for the hydrogenation of CO2 to methanol
Hong Lei (2019)
10.3389/fenrg.2020.545431
Improving the Cu/ZnO-Based Catalysts for Carbon Dioxide Hydrogenation to Methanol, and the Use of Methanol As a Renewable Energy Storage Media
U. Etim (2020)
10.1016/J.SURFREP.2018.02.001
Regulating the surface of nanoceria and its applications in heterogeneous catalysis
Yuan-yuan Ma (2018)
10.1016/j.jcou.2019.11.029
Active site structure study of Cu/Plate ZnO model catalysts for CO2 hydrogenation to methanol under the real reaction conditions
Yuhai Sun (2020)
10.1021/ACS.JPCC.7B02661
Basic Mechanisms of Al Interaction with the ZnO Surface
Yuzhi Gao (2017)
10.1016/S1872-2067(17)62838-9
Comparative studies of leached Pt-Fe and Pt-Co catalysts for CO oxidation reactions
H. Xu (2017)
10.1021/jacs.7b05362
Tuning Selectivity of CO2 Hydrogenation Reactions at the Metal/Oxide Interface.
Shyam Kattel (2017)
10.1002/cctc.202000777
Cu−Zn Alloy Formation as Unfavored State for Efficient Methanol Catalysts
E. Frei (2020)
10.1063/1.5043490
Exotic electronic structures of SmxCe3-xOy (x = 0-3; y = 2-4) clusters and the effect of high neutral density of low-lying states on photodetachment transition intensities.
Josey E. Topolski (2018)
10.1039/c8cs00502h
New horizon in C1 chemistry: breaking the selectivity limitation in transformation of syngas and hydrogenation of CO2 into hydrocarbon chemicals and fuels.
W. Zhou (2019)
10.1016/j.apcatb.2020.119148
Electrochemical promotion of Ru nanoparticles deposited on a proton conductor electrolyte during CO2 hydrogenation
Dimitrios Zagoraios (2020)
10.1016/J.APCATB.2017.01.076
Hydrogenation of CO2 to methanol over CuCeTiOx catalysts
Kuan Chang (2017)
10.1016/j.jcat.2019.11.017
Investigating the dynamic structural changes on Cu/CeO2 catalysts observed during CO2 hydrogenation
Pramod Sripada (2020)
10.1016/j.jece.2020.103726
Metal oxides and metal organic frameworks for the photocatalytic degradation: A review
Sanjeev Gautam (2020)
10.3390/CATAL9010022
Reducible Inverse CeOx-Based Catalyst as a Potential Candidate for Electroreduction
Yongli Shen (2018)
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