Online citations, reference lists, and bibliographies.
← Back to Search

Reaction Mechanisms Of Methanol Synthesis From CO/CO2 Hydrogenation On Cu2O(111): Comparison With Cu(111)

Y. Liu, Jiangtao Liu, Shi-zhong Liu, J. Li, Z. Gao, Zhi-jun Zuo, W. Huang
Published 2017 · Chemistry

Cite This
Download PDF
Analyze on Scholarcy
Share
Abstract A systematic theoretical study was performed to investigate methanol synthesis from CO/CO 2 hydrogenation and the water-gas-shift (WGS) reaction on Cu(111) and Cu 2 O(111) surfaces using density functional theory (DFT) and kinetic Monte Carlo (KMC) simulations. Specifically, DFT was used to investigate methanol synthesis from CO/CO 2 hydrogenation on these surfaces at P = 80 atm, T = 553 K and (CO+ CO 2 )/H 2  = 20/80. The results show that methanol can be synthesized from CO or CO 2 hydrogenation and is dependent on the catalyst’s preparation as well as the active site type. Further, CO is the main carbon source when the surface is predominantly covered by Cu + species. However, CO 2 is the primary carbon source when metallic Cu covers the surface. Under the reaction conditions investigated, H 2 and CO easily reduce Cu 2 O to metallic Cu, and the Cu + species are stabilized by the presence of H 2 O, CO 2 , carrier (such as MgO) or alkali metals. For this reason, the scale of methanol produced from CO or CO 2 hydrogenation depends on the ratio of Cu + /Cu 0 .
This paper references
10.1021/JZ101150W
Structure Sensitivity for Forward and Reverse Water-Gas Shift Reactions on Copper Surfaces: A DFT Study
Guichang Wang (2010)
10.1021/ja408506y
In situ imaging of Cu2O under reducing conditions: formation of metallic fronts by mass transfer.
A. Baber (2013)
10.1016/J.APSUSC.2012.08.074
Can methanol be synthesized from CO by direct hydrogenation over Cu/ZnO catalysts?
Zhi-jun Zuo (2012)
10.1016/J.JCAT.2015.12.016
The effect of sodium on the structure–activity relationships of cobalt-modified Cu/ZnO/Al2O3 catalysts applied in the hydrogenation of carbon monoxide to higher alcohols
J. Anton (2016)
10.1016/J.APSUSC.2010.12.040
Adsorption and dissociation of O2 on the Cu2O(1 1 1) surface: Thermochemistry, reaction barrier
R. Zhang (2011)
10.1016/0927-0256(96)00008-0
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
G. Kresse (1996)
10.1103/PHYSREVLETT.77.3865
Generalized Gradient Approximation Made Simple.
Perdew (1996)
10.1016/0021-9517(85)90378-1
The role of CO2 in methanol synthesis on CuZn oxide: An isotope labeling study
G. Liu (1985)
10.1021/JP504977P
XPS and DFT Studies on the Autoxidation Process of Cu Sheet at Room Temperature
Zhi-jun Zuo (2014)
10.1002/cctc.201500123
The Mechanism of CO and CO2 Hydrogenation to Methanol over Cu‐Based Catalysts
Felix Studt (2015)
10.1021/JP412694Y
Small Cu Clusters Adsorbed on ZnO(10(1)over-bar0) Show Even-Odd Alternations in Stability and Charge Transfer
M. Hellström (2014)
10.1016/J.APSUSC.2013.11.092
Methanol synthesis by CO and CO2 hydrogenation on Cu/γ-Al2O3 surface in liquid paraffin solution
Zhi-jun Zuo (2014)
10.1016/0021-9517(82)90040-9
Catalytic synthesis of methanol from COH2: IV. The effects of carbon dioxide
K. Klier (1982)
10.1103/PHYSREVB.85.235142
Importance of reference Hamiltonians containing exact exchange for accurate one-shot GW calculations of Cu 2 O
Leah Y. Isseroff (2012)
10.1006/JCAT.2002.3586
Methanol Decomposition on Cu(111): A DFT Study
Jeffrey P Greeley (2002)
10.1023/A:1018916806816
Effects of zirconia promotion on the activity of Cu/SiO2 for methanol synthesis from CO/H2 and CO2/H2
I. A. Fisher (1997)
10.1016/J.JCAT.2015.12.019
CO2 hydrogenation on Pt, Pt/SiO2 and Pt/TiO2: Importance of synergy between Pt and oxide support
Shyam Kattel (2016)
10.1021/CS501698W
Density Functional Theory Comparison of Methanol Decomposition and Reverse Reactions on Metal Surfaces
Rodrigo García-Muelas (2015)
10.1002/anie.201301419
The role of the oxide component in the development of copper composite catalysts for methanol synthesis.
S. Zander (2013)
10.1039/c5cp01267h
CO2 conversion to methanol on Cu(I) oxide nanolayers and clusters: an electronic structure insight into the reaction mechanism.
Ellie L Uzunova (2015)
10.1016/J.SURFREP.2013.01.001
Theoretical perspective of alcohol decomposition and synthesis from CO2 hydrogenation
P. Liu (2013)
10.1021/JP208448C
Theoretical Study of Methanol Synthesis from CO2 Hydrogenation on Metal-Doped Cu(111) Surfaces
Y. Yang (2012)
10.1016/S0920-5861(00)00490-9
Active sites in Cu/ZnO/ZrO2 catalysts for methanol synthesis from CO/H2
Y. Suh (2000)
10.1016/S0926-860X(99)00313-0
The chemical modification seen in the Cu/ZnO methanol synthesis catalysts
T. Fujitani (2000)
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)
10.1021/ACS.JPCC.6B10261
Density Functional Theory (DFT) and Kinetic Monte Carlo (KMC) Study of the Reaction Mechanism of Hydrogen Production from Methanol on ZnCu(111)
Zhi-jun Zuo (2016)
10.1021/JP407468T
CO2 Adsorption on Cu2O(111): A DFT+U and DFT-D Study
Leah Isseroff Bendavid (2013)
10.1021/CS5014909
Highly Dispersed Copper Oxide Clusters as Active Species in Copper-Ceria Catalyst for Preferential Oxidation of Carbon Monoxide
W. Wang (2015)
10.1023/A:1020697129629
Methanol Synthesis from Carbon Monoxide and Hydrogen over Ceria-Supported Copper Catalyst Prepared by a Coprecipitation Method
Wenjie Shen (2002)
10.1063/1.1329672
A climbing image nudged elastic band method for finding saddle points and minimum energy paths
G. Henkelman (2000)
10.1021/ja0768237
On the mechanism of low-temperature water gas shift reaction on copper.
A. A. Gokhale (2008)
10.1016/J.APCATA.2010.01.014
Surface properties of copper in different solvent mother solutions: A density functional theory study
Zhi-jun Zuo (2010)
10.1021/ACSCATAL.5B00877
Zinc-Rich Copper Catalysts Promoted by Gold for Methanol Synthesis
O. Martin (2015)
10.1016/S0166-9834(00)84123-8
Mechanism of methanol synthesis from CO2/CO/H2 mixtures over copper/zinc oxide/alumina catalysts: use of14C-labelled reactants
G. Chinchen (1987)
10.1016/0021-9517(90)90104-R
Hydrogenation of CO2 and CO2/CO mixtures over copper-containing catalysts
J. A. B. Bourzutschky (1990)
10.1103/PHYSREVE.58.2598
Efficient Monte Carlo methods for the simulation of catalytic surface reactions
J. J. Lukkien (1998)
10.1126/science.1219831
The Active Site of Methanol Synthesis over Cu/ZnO/Al2O3 Industrial Catalysts
M. Behrens (2012)
10.1021/JP1029079
Autocatalytic reduction of a Cu2O/Cu (111) surface by CO: STM, XPS, and DFT studies
Fan Yang (2010)
10.1021/CS200055D
Mechanism of Methanol Synthesis on Cu through CO2 and CO Hydrogenation
L. Grabow (2011)
10.1006/JCAT.1995.1173
An Infrared Study of Methanol Synthesis from CO2 on Clean and Potassium-Promoted Cu/SiO2
D. Clarke (1995)
10.1039/c001484b
Fundamental studies of methanol synthesis from CO(2) hydrogenation on Cu(111), Cu clusters, and Cu/ZnO(0001).
Y. Yang (2010)
10.1021/IE00003A023
Kinetic model for alcohol synthesis over a promoted copper/zinc oxide/chromium oxide (Cr2O3) catalyst
E. M. Calverley (1992)
10.1103/PHYSREVB.13.5188
SPECIAL POINTS FOR BRILLOUIN-ZONE INTEGRATIONS
H. J. Monkhorst (1976)
10.1023/A:1023588322846
On the Issue of the Active Site and the Role of ZnO in Cu/ZnO Methanol Synthesis Catalysts
J. Nakamura (2003)
10.1016/J.IJHYDENE.2013.11.048
Insights into the reaction mechanisms of methanol decomposition, methanol oxidation and steam reforming of methanol on Cu(111): A density functional theory study
Zhi-jun Zuo (2014)
10.1103/PHYSREVB.54.11169
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set.
Kresse (1996)
10.1039/c6cp00967k
Different routes to methanol: inelastic neutron scattering spectroscopy of adsorbates on supported copper catalysts.
Timur Kandemir (2016)
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.2012.10.028
Mechanistic studies of methanol synthesis over Cu from CO/CO2/H2/H2O mixtures: The source of C in methanol and the role of water
Y. Yang (2013)
10.1021/jp103703n
Magnetic properties of Cu(m)O(n) clusters: a first principles study.
F. Yang (2010)
10.1007/s10562-014-1407-1
On the Kinetic Interpretation of DFT-Derived Energy Profiles: Cu-Catalyzed Methanol Synthesis
W. Janse van Rensburg (2014)
10.1016/0926-860X(92)80340-I
Copper/zirconia catalysts for the synthesis of methanol from carbon dioxide
R. Koeppel (1992)
10.1016/J.JCAT.2012.06.004
CO hydrogenation to methanol on Cu–Ni catalysts: Theory and experiment
F. Studt (2012)
10.1021/JP2034467
Mechanistic Studies of Water–Gas-Shift Reaction on Transition Metals
C. H. Lin (2011)
10.1021/JP809517F
Copper Deposition and Growth over ZnO Nonpolar (101̅0) and (112̅0) Surfaces: A Density Functional Theory Study
J. Hu (2009)
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)
10.1016/J.JCOU.2016.06.001
Fluorinated Cu/Zn/Al/Zr hydrotalcites derived nanocatalysts for CO2 hydrogenation to methanol
P. Gao (2016)
10.1002/9783527610044
Handbook of Heterogeneous Catalysis
G. Ertl (1997)
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)
10.1016/J.JCOU.2016.02.008
Mechanistic insights into the Cu(I) oxide-catalyzed conversion of CO2 to fuels and chemicals: A DFT approach
Abhishek Kumar Mishra (2016)
10.1021/CS2001048
Heterogeneous Catalytic Conversion of Dry Syngas to Ethanol and Higher Alcohols on Cu-Based Catalysts
Mayank Gupta (2011)
10.1016/J.JCAT.2014.12.016
Hydrogenation of CO2 to methanol and CO on Cu/ZnO/Al2O3: Is there a common intermediate or not?
Edward L. Kunkes (2015)
10.1016/J.APSUSC.2008.09.005
Roles of oxygen vacancy in the adsorption properties of CO and NO on Cu2O(111) surface: Results of a first-principles study
B. Sun (2008)
10.1016/J.CPLETT.2013.03.032
Adsorption of CO2 on Cu2O (111) oxygen-vacancy surface: First-principles study
H. Wu (2013)
10.1021/ACSCATAL.5B00442
Reaction Network of Methanol Synthesis over Cu/ZnO Nanocatalysts
Luis Martínez-Suárez (2015)
10.1016/J.APSUSC.2009.10.067
Solvent effects for CO and H2 adsorption on Cu2O (1 1 1) surface: A density functional theory study
Zhijun Zuo (2010)
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)
10.1016/J.JCOU.2016.11.016
Co-synthesis of methanol and methyl formate from CO2 hydrogenation over oxalate ligand functionalized ZSM-5 supported Cu/ZnO catalyst
O. B. Ayodele (2017)



This paper is referenced by
10.1007/s00894-018-3587-x
A DFT study of the catalytic pyrolysis of benzaldehyde on ZnO, γ-Al2O3, and CaO models
Li-ping Cui (2018)
10.1080/08927022.2019.1632448
Predicting CO2 adsorption and reactivity on transition metal surfaces using popular density functional theory methods
O. Mohan (2019)
10.1016/J.JCOU.2019.05.036
Recent developments on heterogeneous catalytic CO2 reduction to methanol
I. U. Din (2019)
10.1016/j.mcat.2019.110667
Density-functional theory study on hydrogenation of dimethyl oxalate to methyl glycolate over copper catalyst: Effect of copper valence state
Jiangwei An (2020)
10.1016/j.fuel.2020.118987
Effect of lanthanum group promoters on Cu/(mixture of ZnO and Zn-Al-spinnel-oxides) catalyst for methanol synthesis by hydrogenation of CO and CO2 mixtures
Hyun-tae Song (2021)
10.3390/catal10020183
CO2 Hydrogenation to Methanol over La2O3-Promoted CuO/ZnO/Al2O3 Catalysts: A Kinetic and Mechanistic Study
Marios Kourtelesis (2020)
10.1016/J.JCOU.2017.07.010
Carbon nanofiber-based copper/zirconia catalyst for hydrogenation of CO2 to methanol
I. U. Din (2017)
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)
10.1016/J.CATTOD.2019.01.015
Hydrogenation of CO2 to methanol over Cu/AlCeO catalyst
S. Li (2020)
10.1016/J.CJCHE.2020.05.009
density functional theory and kinetic Monte Carlo simulation study the strong metal–support interaction of dry reforming of methane reaction over Ni based catalysts
Xue-Yan Zou (2020)
10.1002/cctc.201901879
Recent Developments in the Modelling of Heterogeneous Catalysts for CO2 Conversion to Chemicals
N. Podrojková (2020)
10.1134/S0023158420010115
Modern View of the Mechanism of Methanol Synthesis on Cu-Containing Catalysts
E. A. Volnina (2020)
10.1088/1361-648X/ab2b66
Interaction of CO, O, and CO2 with Cu cluster supported on Cu(111): A density functional theory study.
A. A. B. Padama (2019)
10.1016/J.JCOU.2018.04.010
Rhenium-promoted selective CO2 methanation on Ni-based catalyst
H. Yuan (2018)
10.1007/978-3-030-28638-5_5
Selective Hydrogenation of Carbon Dioxide into Methanol
D. Minh (2020)
10.1007/s00894-020-04502-5
DFT study the water-gas shift reaction over Cu/α-MoC surface
X. Zou (2020)
10.1016/J.JCOU.2017.10.013
Highly selective conversion of CO2 into ethanol on Cu/ZnO/Al2O3 catalyst with the assistance of plasma
Binran Zhao (2018)
10.1016/J.APSUSC.2017.09.170
The role of catalysts in the decomposition of phenoxy compounds in coal: A density functional theory study
Jiangtao Liu (2018)
10.1155/2019/4341056
Study on the Adsorption and Activation Behaviours of Carbon Dioxide over Copper Cluster (Cu4) and Alumina-Supported Copper Catalyst (Cu4/Al2O3) by means of Density Functional Theory
N. T. Hà (2019)
10.1039/c9cp02970b
DFT and microkinetic investigation of methanol synthesis via CO2 hydrogenation on Ni(111)-based surfaces.
A. Maulana (2019)
Semantic Scholar Logo Some data provided by SemanticScholar