← Back to Search
Optimizing Binding Energies Of Key Intermediates For CO2 Hydrogenation To Methanol Over Oxide-Supported Copper.
Shyam Kattel, Binhang Yan, Y. Yang, J. Chen, P. Liu
Published 2016 · Medicine, Chemistry
Download PDFAnalyze on Scholarcy
Rational optimization of catalytic performance has been one of the major challenges in catalysis. Here we report a bottom-up study on the ability of TiO2 and ZrO2 to optimize the CO2 conversion to methanol on Cu, using combined density functional theory (DFT) calculations, kinetic Monte Carlo (KMC) simulations, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) measurements, and steady-state flow reactor tests. The theoretical results from DFT and KMC agree with in situ DRIFTS measurements, showing that both TiO2 and ZrO2 help to promote methanol synthesis on Cu via carboxyl intermediates and the reverse water-gas-shift (RWGS) pathway; the formate intermediates, on the other hand, likely act as a spectator eventually. The origin of the superior promoting effect of ZrO2 is associated with the fine-tuning capability of reduced Zr(3+) at the interface, being able to bind the key reaction intermediates, e.g. *CO2, *CO, *HCO, and *H2CO, moderately to facilitate methanol formation. This study demonstrates the importance of synergy between theory and experiments to elucidate the complex reaction mechanisms of CO2 hydrogenation for the realization of a better catalyst by design.
This paper references
Ionic Liquid–Mediated Selective Conversion of CO2 to CO at Low Overpotentials
Brian A Rosen (2011)
Comments on: the activity and state of the copper surface in methanolsynthesis catalysts 
C. Campbell (1987)
Interface-Confined Ferrous Centers for Catalytic Oxidation
Q. Fu (2010)
CO2 Hydrogenation over Oxide-Supported PtCo Catalysts: The Role of the Oxide Support in Determining the Product Selectivity.
Shyam Kattel (2016)
Recent advances in catalysts for methanol synthesis via hydrogenation of CO and CO2
X. Liu (2003)
Enhanced electrochemical methanation of carbon dioxide with a dispersible nanoscale copper catalyst.
Karthish Manthiram (2014)
Particle size effects in the catalytic electroreduction of CO₂ on Cu nanoparticles.
Rulle Reske (2014)
Decomposition and combined reforming of methanol to hydrogen: a FTIR and QMS study on Cu and Au catalysts supported on ZnO and TiO2
M. Manzoli (2005)
A theoretical study for methanol synthesis by CO2 hydrogenation
T. Kakumoto (1997)
Dissociative adsorption of hydrogen on strained Cu surfaces
S. Sakong (2003)
The Active Site of Methanol Synthesis over Cu/ZnO/Al2O3 Industrial Catalysts
M. Behrens (2012)
Spillover in Heterogeneous Catalysis
W. C. Conner (1995)
Spectroscopic Observation of Dual Catalytic Sites During Oxidation of CO on a Au/TiO2 Catalyst
I. X. Green (2011)
CO2 fixation into methanol at Cu/ZrO2 interface from first principles kinetic Monte Carlo
Qian-Lin Tang (2009)
Catalysis for CO2 conversion: a key technology for rapid introduction of renewable energy in the value chain of chemical industries
G. Centi (2013)
Mechanism of Methanol Synthesis on Cu through CO2 and CO Hydrogenation
L. Grabow (2011)
Projector augmented-wave method.
Influence of ZrO2 Structure and Copper Electronic State on Activity of Cu/ZrO2 Catalysts in Methanol Synthesis from CO2
K. Samson (2014)
Formation of a ZnO overlayer in industrial Cu/ZnO/Al2 O3 catalysts induced by strong metal-support interactions.
T. Lunkenbein (2015)
Fundamental studies of methanol synthesis from CO(2) hydrogenation on Cu(111), Cu clusters, and Cu/ZnO(0001).
Y. Yang (2010)
Gold, copper, and platinum nanoparticles dispersed on CeO(x)/TiO(2)(110) surfaces: high water-gas shift activity and the nature of the mixed-metal oxide at the nanometer level.
J. B. Park (2010)
Selectivity of CO(2) reduction on copper electrodes: the role of the kinetics of elementary steps.
X. Nie (2013)
IR study on migration of 18OCH3 species on ZrO2
F. Ouyang (1998)
Efficient Monte Carlo methods for the simulation of catalytic surface reactions
J. J. Lukkien (1998)
Understanding the Behavior of TiO2(110)-Supported Pd7 Cluster: A Density Functional Study
P. Liu (2012)
Adsorption of formic acid on rutile TiO2 (110) revisited: an infrared reflection-absorption spectroscopy and density functional theory study.
Andreas Mattsson (2014)
Effect of supports on copper Catalysts for Methanol Synthesis from CO2 + H2
T. Tagawa (1995)
Glycine–nitrate combustion synthesis of CuO–ZnO–ZrO2 catalysts for methanol synthesis from CO2 hydrogenation
X. Guo (2010)
Catalysis for the valorization of exhaust carbon: from CO2 to chemicals, materials, and fuels. technological use of CO2.
M. Aresta (2014)
The effects of zirconia morphology on methanol synthesis from CO and H2 over Cu/ZrO2 catalysts: Part II -- Transient-Response Infrared Studies
M. Rhodes (2005)
Mechanistic Study of Methanol Synthesis from CO2 and H2 on a Modified Model Mo6S8 Cluster
Cheng Liu (2015)
A climbing image nudged elastic band method for finding saddle points and minimum energy paths
G. Henkelman (2000)
A case of strong metal-support interactions: combining advanced microscopy and model systems to elucidate the atomic structure of interfaces.
M. Willinger (2014)
Highly active copper-ceria and copper-ceria-titania catalysts for methanol synthesis from CO2
J. Graciani (2014)
SPECIAL POINTS FOR BRILLOUIN-ZONE INTEGRATIONS
H. J. Monkhorst (1976)
A highly selective copper-indium bimetallic electrocatalyst for the electrochemical reduction of aqueous CO2 to CO.
Shahid Rasul (2015)
FTIR study of formic acid interaction with TiO
J. Araña (2004)
Surface modification of TiO2 with metal oxide nanoclusters: a route to composite photocatalytic materials.
M. Nolan (2011)
Accurate and simple analytic representation of the electron-gas correlation energy.
Non)formation of Methanol by Direct Hydrogenation of Formate on Copper Catalysts
Yong Yang (2010)
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set.
Interface-confined oxide nanostructures for catalytic oxidation reactions.
Q. Fu (2013)
A theoretical study for the CO2 hydrogenation mechanism on Cu/ZnO catalyst
T. Kakumoto (1995)
CO2 hydrogenation to methanol over Cu/ZrO2 catalysts: Effects of zirconia phases
Thongthai Witoon (2016)
Mechanism of CO2 reduction by H2 on Ru(0 0 0 1) and general selectivity descriptors for late-transition metal catalysts
Talin Avanesian (2016)
The critical role of water at the gold-titania interface in catalytic CO oxidation
J. Saavedra (2014)
Controlling Catalytic Selectivities during CO2 Electroreduction on Thin Cu Metal Overlayers
Rulle Reske (2013)
Effective conversion of carbon dioxide and hydrogen to hydrocarbons
T. Inui (1991)
Intermediate species on zirconia supported methanol aerogel catalysts: II. Adsorption of carbon monoxide on pure zirconia and on zirconia containing zinc oxide
D. Bianchi (1993)
Reversible structural transformation of FeO(x) nanostructures on Pt under cycling redox conditions and its effect on oxidation catalysis.
Q. Fu (2013)
Heterogeneous catalytic CO2 conversion to value-added hydrocarbons
R. Dorner (2010)
Isotope Effects in Methanol Synthesis and the Reactivity of Copper Formates on a Cu/SiO2 Catalyst
Yong Yang (2008)
Acidic Properties of Alumina-Supported Metal Oxide Catalysts: An Infrared Spectroscopy Study
A. Turek (1992)
Self-Consistent Equations Including Exchange and Correlation Effects
W. Kohn (1965)
Low Pressure CO2 Hydrogenation to Methanol over Gold Nanoparticles Activated on a CeO(x)/TiO2 Interface.
Xiaofang Yang (2015)
Progress in carbon dioxide separation and capture: a review.
H. Yang (2008)
Carbon Dioxide Conversion to Methanol over Size-Selected Cu4 Clusters at Low Pressures.
C. Liu (2015)
Discovery of a Ni-Ga catalyst for carbon dioxide reduction to methanol.
F. Studt (2014)
THE INHOMOGENEOUS ELECTRON GAS.
P. Hohenberg (1964)
Theoretical Study of Methanol Synthesis from CO2 Hydrogenation on Metal-Doped Cu(111) Surfaces
Y. Yang (2012)
Molybdenum carbide as alternative catalysts to precious metals for highly selective reduction of CO2 to CO.
Marc D. Porosoff (2014)
Electronic Structure of Partially Reduced Rutile TiO2(110) Surface: Where Are the Unpaired Electrons Located?
S. Chrétien (2011)
In-situ FT-IR study on CO2 hydrogenation over Cu catalysts supported on SiO2, Al2O3, and TiO2
K. Bando (1997)
Infrared study of syngas adsorption on zirconia
E. Guglielminotti (1990)
Electron-energy-loss spectra and the structural stability of nickel oxide : An LSDA+U study
S. Dudarev (1998)
Catalytic reduction of CO2 by H2 for synthesis of CO, methanol and hydrocarbons: challenges and opportunities
Marc D. Porosoff (2016)
CO and CO2 hydrogenation over metal oxides: a comparison of ZnO, TiO2 and ZrO2
M. He (1985)
Catalyst-support interactions: Electronic perturbations.
C. Campbell (2012)
Status and perspectives of CO2 conversion into fuels and chemicals by catalytic, photocatalytic and electrocatalytic processes
E. Kondratenko (2013)
Simultaneous MS-IR Studies of Surface Formate Reactivity Under Methanol Synthesis Conditions on Cu/SiO2
Yong Yang (2009)
Comments on electronic effects in strong metal-support interactions on titania-deposited metal catalysts
F. Solymosi (1985)
Intermediate species on zirconia supported methanol aerogel catalysts V. Adsorption of methanol
D. Bianchi (1995)
How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels
A. A. Peterson (2010)
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)
Methanol synthesis from CO2 hydrogenation over copper based catalysts
H. Ahouari (2013)
From ultrasoft pseudopotentials to the projector augmented-wave method
G. Kresse (1999)
This paper is referenced by
Capsule-structured copper-zinc catalyst for highly efficient hydrogenation of carbon dioxide to methanol.
Yongle Guo (2019)
Developing new understanding of photoelectrochemical water splitting via in-situ techniques: A review on recent progress
Jiajie Cen (2017)
Gas fermentation: cellular engineering possibilities and scale up
Björn D. Heijstra (2017)
Effect of Ag loading on CO2-to-methanol hydrogenation over Ag/CuO/ZrO2
Shohei Tada (2018)
Confinement of Ultrasmall Cu/ZnOx Nanoparticles in Metal-Organic Frameworks for Selective Methanol Synthesis from Catalytic Hydrogenation of CO2.
B. An (2017)
Highly Selective Conversion of Carbon Dioxide to Aromatics over Tandem Catalysts
Zelong Li (2019)
CO2 -to-Methanol Hydrogenation on Zirconia-Supported Copper Nanoparticles: Reaction Intermediates and the Role of the Metal-Support Interface.
Kim Larmier (2017)
Direct synthesis of dimethyl carbonate from CO2 and methanol over CaO–CeO2 catalysts: the role of acid–base properties and surface oxygen vacancies
B. Liu (2017)
LaCuZnX (X=Al, Zr, Al+Zr) perovskite-like catalysts treated by NaBH4 and their catalytic performance for CO2 hydrogenation to methanol
Zhi-qi Kuang (2020)
GCEP Final Progress Report 2.4.2. Sustainable Fuel Production from CO2 and CO: Higher Alcohol Synthesis on Transition Metal Catalysts
J. Nørskov (2019)
A short review of recent advances in CO2 hydrogenation to hydrocarbons over heterogeneous catalysts
Wenhui Li (2018)
Ethanol and Higher Alcohols Synthesis from Syngas over CuCoM (M=Fe, Cr, Ga and Al) Nanoplates Derived From Hydrotalcite‐Like Precursors
Kai Sun (2019)
ZnO-ZrO 2 solid solution catalyst for highly selective hydrogenation of CO 2 to methanol
T. Zhang (2017)
Universal Strategy for Ultrathin Pt-M (M = Fe, Co, Ni) Nanowires for Efficient Catalytic Hydrogen Generation.
Shuxing Bai (2018)
Recent In Situ/Operando Spectroscopy Studies of Heterogeneous Catalysis with Reducible Metal Oxides as Supports
F. Wang (2019)
Photocatalytic conversion of CO2 into light olefins over TiO2 nanotube confined Cu clusters with high ratio of Cu
Hui-bin Ge (2020)
Selective hydrogenation of CO2 to methanol catalyzed by Cu supported on rod-like La2O2CO3
K. Chen (2018)
Selective Hydrogenation of CO2 to CH3 OH on Supported Cu Nanoparticles Promoted by Isolated TiIV Surface Sites on SiO2.
Gina Noh (2019)
Active sites for tandem reactions of CO2 reduction and ethane dehydrogenation
Binhang Yan (2018)
Understanding the Dual Active Sites of the FeO/Pt(111) Interface and Reaction Kinetics: Density Functional Theory Study on Methanol Oxidation to Formaldehyde
Zongjia Chen (2017)
Activation of CO2 by supported Cu clusters.
Satish Kumar Iyemperumal (2017)
Origin of Pd-Cu bimetallic effect for synergetic promotion of methanol formation from CO2 hydrogenation
X. Jiang (2019)
Silica accelerates the selective hydrogenation of CO2 to methanol on cobalt catalysts
Lingxiang Wang (2020)
Synergistic ultraviolet and visible light photo-activation enables intensified low-temperature methanol synthesis over copper/zinc oxide/alumina
Bingqiao Xie (2020)
Direct conversion of CO2 into methanol over promoted indium oxide-based catalysts
Chen-Yu Chou (2019)
Hydrogenation of CO2 to formic acid on the single atom catalysis Cu/C2N: A first principles study
Junmei Ma (2019)
Hydrogenation of CO to Methanol on Ni(110) through Subsurface Hydrogen.
Adam P. Ashwell (2017)
Enhanced CO2 hydrogenation to methanol over TiO2 nanotubes-supported CuO-ZnO-CeO2 catalyst
Z. Shi (2019)
Core electron binding energies of adsorbates on Cu(111) from first-principles calculations.
J. M. Kahk (2018)
Highly active subnanometer Rh clusters derived from Rh-doped SrTiO3 for CO2 reduction
Binhang Yan (2018)
Zr(IV) surface sites determine CH3OH formation rate on Cu/ZrO2/SiO2 - CO2 hydrogenation catalysts
Erwin Lam (2019)
Ab initio study of CO 2 hydrogenation mechanisms on inverse ZnO/Cu catalysts
Thomas Reichenbach (2018)See more