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Zirconia-modified Copper Catalyst For CO2 Conversion To Methanol From DFT Study

Lingna Liu, Xuanyue Su, H. Zhang, Nengjian Gao, Fan Xue, Ya-jun Ma, Zhao Jiang, T. Fang
Published 2020 · Chemistry

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Abstract The hydrogenation of carbon dioxide (CO2) to methanol on (ZrO2)3/Cu(1 1 0) interface has been investigated by periodic density functional theory (DFT) calculations. With regard to the adsorption of all the species involved in methanol synthesis, the species prefer to adsorb on the interface between Cu(1 1 0) surface and (ZrO2)3 cluster and through C-Cu and O-Zr bonds. The adsorption energies of unsaturated species are increased on (ZrO2)3/Cu(1 1 0) interface compared to that on Cu(1 1 0) surface. Formate (HCOO), hydrocarboxy (COOH) and reverse water gas shift (RWGS) pathways in the reaction network of C O 2 + 3 H 2 → C H 3 OH + H 2 O were considered. In HCOO pathway, the binding CO2* primarily hydrogenates to bi-HCOO*, which hydrogenates subsequently to HCOOH*, H2COOH*, H2CO*, H3CO* and CH3OH*. The formation of H2CO* and OH* through H2COOH* decomposition has the highest reaction barrier of 1.39 eV, which is lower than the rate-limiting step of cis-COOH* dissociation with an activation barrier of 1.46 eV in RWGS pathway. COOH* is facile to go through HCOOH* intermediate comparing with the formation of t,t-COHOH* in COOH pathway, indicating that CH3OH is mainly produced via HCOOH channel in the reaction scheme on ZrO2/Cu(1 1 0) interface. The formation of byproducts such as HCOOH, H2CO and CO is significantly inhibited over (ZrO2)3/Cu(1 1 0) interface, showing a high selectivity for producing CH3OH. These results demonstrated that (ZrO2)3/Cu(1 1 0) is a potential candidate catalyst for methanol production via CO2 hydrogenation.
This paper references
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/ACSCATAL.8B03810
Catalytic Hydrogenation of Carbon Dioxide to Methanol: Synergistic Effect of Bifunctional Cu/Perovskite Catalysts
M. Huš (2019)
10.1038/nchem.728
The role of steps in surface catalysis and reaction oscillations.
Bas L. M. Hendriksen (2010)
10.1039/B912904A
The teraton challenge. A review of fixation and transformation of carbon dioxide
M. Mikkelsen (2010)
10.1021/jacs.6b05791
Optimizing Binding Energies of Key Intermediates for CO2 Hydrogenation to Methanol over Oxide-Supported Copper.
Shyam Kattel (2016)
10.1002/anie.201610166
CO2 -to-Methanol Hydrogenation on Zirconia-Supported Copper Nanoparticles: Reaction Intermediates and the Role of the Metal-Support Interface.
Kim Larmier (2017)
10.1016/S0039-6028(99)00900-0
Mechanism of the hydrogenation of CO2 to methanol on a Cu(100) surface: dipped adcluster model study
Zhen-ming Hu (1999)
10.1016/J.CATTOD.2006.02.029
Global challenges and strategies for control, conversion and utilization of CO2 for sustainable development involving energy, catalysis, adsorption and chemical processing
C. Song (2006)
10.1103/PHYSREVLETT.77.3865
Generalized Gradient Approximation Made Simple.
Perdew (1996)
10.1080/00268979300103121
Ab initio energy-adjusted pseudopotentials for elements of groups 13-17
A. Bergner (1993)
10.1111/J.1365-246X.1989.TB02055.X
Static alternating field demagnetizations of anhysteretic and rotational remanent magnetizations in rocks and synthesized samples
J. Edwards (1989)
10.1039/C001514H
Heterogeneous catalytic CO2 conversion to value-added hydrocarbons
R. Dorner (2010)
10.1021/CS500979C
Influence of ZrO2 Structure and Copper Electronic State on Activity of Cu/ZrO2 Catalysts in Methanol Synthesis from CO2
K. Samson (2014)
10.1039/c7cp03231e
Synthesis of methanol from CO2 hydrogenation promoted by dissociative adsorption of hydrogen on a Ga3Ni5(221) surface.
Qingli Tang (2017)
10.1007/BF00808595
Methanol synthesis and reverse water-gas shift kinetics over clean polycrystalline copper
J. Yoshihara (1995)
10.1021/jacs.7b00102
Enhancing CO2 Electroreduction with the Metal-Oxide Interface.
Dunfeng Gao (2017)
10.1021/JP208448C
Theoretical Study of Methanol Synthesis from CO2 Hydrogenation on Metal-Doped Cu(111) Surfaces
Y. Yang (2012)
10.1126/science.1219831
The Active Site of Methanol Synthesis over Cu/ZnO/Al2O3 Industrial Catalysts
M. Behrens (2012)
10.1039/c001484b
Fundamental studies of methanol synthesis from CO(2) hydrogenation on Cu(111), Cu clusters, and Cu/ZnO(0001).
Y. Yang (2010)
10.1016/J.JCAT.2011.04.012
Insight into methanol synthesis from CO2 hydrogenation on Cu(111): Complex reaction network and the effects of H2O
Yafan Zhao (2011)
10.1016/J.JCAT.2013.01.022
Trends in the catalytic reduction of CO2 by hydrogen over supported monometallic and bimetallic catalysts
Marc D. Porosoff (2013)
10.1016/J.CATTOD.2009.07.075
Opportunities and prospects in the chemical recycling of carbon dioxide to fuels
G. Centi (2009)
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)
10.1016/J.JCAT.2018.01.035
Ab initio study of CO 2 hydrogenation mechanisms on inverse ZnO/Cu catalysts
Thomas Reichenbach (2018)
10.1002/ANIE.200702600
Role of lattice strain and defects in copper particles on the activity of Cu/ZnO/Al(2)O(3) catalysts for methanol synthesis.
I. Kasatkin (2007)
10.1002/CHIN.198823148
The Mechanism of Methanol Synthesis on Copper/Zinc Oxide/Alumina Catalysts
Michael Bowker (1988)
10.1021/ACSCATAL.5B00442
Reaction Network of Methanol Synthesis over Cu/ZnO Nanocatalysts
Luis Martínez-Suárez (2015)
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)
10.1016/J.APSUSC.2016.06.074
Insight into the influence of liquid paraffin for methanol synthesis on Cu(110) surface using continuum and atomistic models
W. Jiao (2016)
10.1126/science.aal3573
Active sites for CO2 hydrogenation to methanol on Cu/ZnO catalysts
Shyam Kattel (2017)
10.1006/JCAT.1995.1250
A Kinetic Model of Methanol Synthesis
T. Askgaard (1995)
10.1016/J.APCATB.2015.01.010
Bimetallic Pd–Cu catalysts for selective CO2 hydrogenation to methanol
Xiao Jiang (2015)
10.1016/J.MCAT.2019.01.009
Mechanistic study of methanol synthesis from CO2 hydrogenation on Rh-doped Cu(111) surfaces
Lingna Liu (2019)
10.1002/anie.201601661
CO2 Hydrogenation over Oxide-Supported PtCo Catalysts: The Role of the Oxide Support in Determining the Product Selectivity.
Shyam Kattel (2016)
10.1006/JCAT.1995.1173
An Infrared Study of Methanol Synthesis from CO2 on Clean and Potassium-Promoted Cu/SiO2
D. Clarke (1995)
10.1063/1.1316015
From molecules to solids with the DMol3 approach
B. Delley (2000)
10.1038/nchem.1873
Discovery of a Ni-Ga catalyst for carbon dioxide reduction to methanol.
F. Studt (2014)
10.1103/PHYSREVB.45.13244
Accurate and simple analytic representation of the electron-gas correlation energy.
Perdew (1992)
10.1021/ACSCATAL.8B01396
Design of Interfacial Sites between Cu and Amorphous ZrO2 Dedicated to CO2-to-Methanol Hydrogenation
Shohei Tada (2018)
10.1007/S10562-008-9592-4
Isotope Effects in Methanol Synthesis and the Reactivity of Copper Formates on a Cu/SiO2 Catalyst
Yong Yang (2008)
10.1021/ACS.JPCC.7B06166
Mechanistic Study of Pd–Cu Bimetallic Catalysts for Methanol Synthesis from CO2 Hydrogenation
Lingna Liu (2017)
10.1063/1.458452
An all‐electron numerical method for solving the local density functional for polyatomic molecules
B. Delley (1990)
10.1021/JP971077L
Adsorption and Reaction of Aldehydes on Pd Surfaces
R. Shekhar (1997)
10.1016/J.APSUSC.2018.11.038
Comprehensive theoretical analysis of the influence of surface alloying by zinc on the catalytic performance of Cu(1 1 0) for the production of methanol from CO2 selective hydrogenation: Part 1 – Thermochemical aspects
X. Fan (2019)
10.1149/1.3645178
Beyond oil and gas: the methanol economy.
G. Olah (2005)
10.1016/J.JCAT.2009.01.017
CO2 fixation into methanol at Cu/ZrO2 interface from first principles kinetic Monte Carlo
Qian-Lin Tang (2009)
10.1006/JCAT.1999.2682
CO2 Hydrogenation to Methanol on a YBa2Cu3O7 Catalyst
L. Gao (2000)
10.1016/0926-860X(96)00015-4
Vibrational spectroscopic study of IB metal/zirconia catalysts for the synthesis of methanol
J. Weigel (1996)
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.JCAT.2014.06.002
Methanol synthesis from CO2 hydrogenation over a Pd4/In2O3 model catalyst: A combined DFT and kinetic study
Jing-yun Ye (2014)
10.1002/(SICI)1097-461X(2000)77:1<341::AID-QUA33>3.0.CO;2-T
Mechanism of Methanol Synthesis on Cu(100) and Zn/Cu(100) Surfaces: Comparative Dipped Adcluster Model Study
H. Nakatsuji (2000)
10.1021/JP107678D
First-Principles Study on the Origin of the Different Selectivities for Methanol Steam Reforming on Cu(111) and Pd(111)
Xiang-Kui Gu (2010)
10.1016/j.apsusc.2019.143783
Catalysis of material surface defects: Multiscale modeling of methanol synthesis by CO2 reduction on copper
D. Kopač (2019)
10.1016/J.APCATB.2017.01.077
Mechanism, kinetics and thermodynamics of carbon dioxide hydrogenation to methanol on Cu/ZnAl2O4 spinel-type heterogeneous catalysts
M. Huš (2017)
10.1016/0009-2614(77)80574-5
The synchronous-transit method for determining reaction pathways and locating molecular transition states
T. Halgren (1977)
10.1021/CS200055D
Mechanism of Methanol Synthesis on Cu through CO2 and CO Hydrogenation
L. Grabow (2011)
10.1021/ACS.JPCC.5B12012
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 (2016)
10.1039/c7cp03859c
DFT study of CO2 conversion on InZr3(110) surface.
M. Zhang (2017)
10.1021/acs.jpclett.6b00499
Inverse Oxide/Metal Catalysts in Fundamental Studies and Practical Applications: A Perspective of Recent Developments.
J. Rodriguez (2016)
10.1021/ACS.JPCC.8B00085
First-Principles and Microkinetic Simulation Studies of the Structure Sensitivity of Cu Catalyst for Methanol Steam Reforming
Shasha Wang (2018)



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