skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: 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

Journal Article · · Journal of Physical Chemistry. C
 [1];  [2];  [1];  [1];  [1];  [3];  [4];  [4];  [1];  [2];  [5]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Dept.
  2. Central Univ. of Venezuela, Caracas (Venezuela). Faculty of Science
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Dept. ; SUNY Stony Brook, Stony Brook, NY (United States). Dept. of Chemistry
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  5. Brookhaven National Lab. (BNL). Chemistry Dept. , Upton, NY (United States); SUNY Stony Brook, Stony Brook, NY (United States). Dept. of Chemistry
+ Show Author Affiliations

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 intermediate for the production of methanol. The inverse oxide/metal configuration favors strong metal-oxide interactions and makes possible reaction channels not seen in conventional metal/oxide catalysts.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
Grant/Contract Number:
SC00112704; AC02-05CH11231
OSTI ID:
1246804
Alternate ID(s):
OSTI ID: 1456931
Report Number(s):
BNL-111983-2016-JA; R&D Project: CO009; KC0302010
Journal Information:
Journal of Physical Chemistry. C, Vol. 120, Issue 3; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 143 works
Citation information provided by
Web of Science

References (34)

How to make the most of carbon dioxide journal October 2015
Modern Global Climate Change journal December 2003
Status and perspectives of CO2 conversion into fuels and chemicals by catalytic, photocatalytic and electrocatalytic processes journal January 2013
Carbon Dioxide Recycling: Emerging Large-Scale Technologies with Industrial Potential journal September 2011
Carbon Dioxide as Chemical Feedstock book January 2010
Feature: There’s too much carbon dioxide in the air. Why not turn it back into fuel? journal September 2015
Direct CO2 hydrogenation to methane or methanol from post-combustion exhaust streams – A thermodynamic study journal January 2015
Formation of hydrocarbons via CO2 hydrogenation – A thermodynamic study journal June 2014
Activity and Selectivity Trends in Synthesis Gas Conversion to Higher Alcohols journal October 2013
Promoting Strong Metal Support Interaction: Doping ZnO for Enhanced Activity of Cu/ZnO:M (M = Al, Ga, Mg) Catalysts journal April 2015
Hydrogenation of CO 2 to Methanol: Importance of Metal–Oxide and Metal–Carbide Interfaces in the Activation of CO 2 journal October 2015
The Mechanism of CO and CO 2 Hydrogenation to Methanol over Cu-Based Catalysts journal March 2015
Formation of a ZnO Overlayer in Industrial Cu/ZnO/Al 2 O 3 Catalysts Induced by Strong Metal-Support Interactions journal February 2015
The synthesis of higher alcohols using modified Cu/ZnO/Al2O3 catalysts journal May 1992
A Surface Science Investigation of Methanol Synthesis over a Zn-Deposited Polycrystalline Cu Surface journal April 1996
Fundamental studies of methanol synthesis from CO2 hydrogenation on Cu(111), Cu clusters, and Cu/ZnO(0001̄) journal January 2010
Methanol Synthesis and Reverse Water–Gas Shift Kinetics over Cu(110) Model Catalysts: Structural Sensitivity journal July 1996
Methanol synthesis on Cu(100) from a binary gas mixture of CO2 and H2 journal January 1994
Methanol synthesis on a Cu(100) catalyst journal January 1991
Mechanism of Methanol Synthesis on Cu through CO 2 and CO Hydrogenation journal February 2011
Microstructural and Defect Analysis of Metal Nanoparticles in Functional Catalysts by Diffraction and Electron Microscopy: The Cu/ZnO Catalyst for Methanol Synthesis journal October 2013
Highly active copper-ceria and copper-ceria-titania catalysts for methanol synthesis from CO2 journal July 2014
A differentially pumped electrostatic lens system for photoemission studies in the millibar range journal November 2002
Adsorbate-Driven Morphological Changes of a Gold Surface at Low Temperatures journal December 2008
Ultrathin metal films and particles on oxide surfaces: structural, electronic and chemisorptive properties journal January 1997
Surface studies of supported model catalysts journal January 1998
Density functional study of water-gas shift reaction on M3O3x/Cu(111) journal January 2012
Electron Transfer at Oxide Surfaces. The MgO Paradigm: from Defects to Ultrathin Films journal November 2012
Cu/ZnO(0001̄) and ZnOx/Cu(111): Model catalysts for methanol synthesis journal April 1987
Conversion of methanol, formaldehyde and formic acid on the polar faces of zinc oxide journal October 1986
The electronic structure of stoichiometric and reduced CeO2 surfaces: an XPS, UPS and HREELS study journal December 1994
Activity of CeOx and TiOx Nanoparticles Grown on Au(111) in the Water-Gas Shift Reaction journal December 2007
Unraveling the Nature of the Oxide–Metal Interaction in Ceria-Based Noble Metal Inverse Catalysts journal November 2014
Importance of the Metal-Oxide Interface in Catalysis: In Situ Studies of the Water-Gas Shift Reaction by Ambient-Pressure X-ray Photoelectron Spectroscopy journal April 2013

Cited By (21)

Thermal reduction of ceria nanostructures on rhodium(111) and re-oxidation by CO 2 journal January 2018
Reducible Inverse CeOx-Based Catalyst as a Potential Candidate for Electroreduction journal December 2018
Surface chemistry of group IB metals and related oxides journal January 2017
Active sites for CO 2 hydrogenation to methanol on Cu/ZnO catalysts journal March 2017
The Synergistic Effect of CuZnCeO x in Controlling the Formation of Methanol and CO from CO 2 Hydrogenation journal August 2018
Response to Comment on “Active sites for CO 2 hydrogenation to methanol on Cu/ZnO catalysts” journal August 2017
CO2 Hydrogenation over Nanoceria-Supported Transition Metal Catalysts: Role of Ceria Morphology (Nanorods versus Nanocubes) and Active Phase Nature (Co versus Cu) journal December 2019
Recent progress in improving the stability of copper-based catalysts for hydrogenation of carbon–oxygen bonds journal January 2018
Cu-Mo2C/MCM-41: An Efficient Catalyst for the Selective Synthesis of Methanol from CO2 journal May 2016
Ambient Pressure Photoelectron Spectroscopy: Opportunities in Catalysis from Solids to Liquids and Introducing Time Resolution journal January 2018
Efficient Hydrogenation of CO 2 to Methanol over Supported Subnanometer Gold Catalysts at Low Temperature journal August 2017
Cylindrical shaped ZnO combined Cu catalysts for the hydrogenation of CO 2 to methanol journal January 2019
Structure–function relationship for CO 2 methanation over ceria supported Rh and Ni catalysts under atmospheric pressure conditions journal January 2019
Exotic electronic structures of Sm x Ce 3−x O y (x = 0-3; y = 2-4) clusters and the effect of high neutral density of low-lying states on photodetachment transition intensities journal August 2018
Cu@ZIF-8 derived inverse ZnO/Cu catalyst with sub-5 nm ZnO for efficient CO 2 hydrogenation to methanol journal January 2019
Metal Clusters Dispersed on Oxide Supports: Preparation Methods and Metal-Support Interactions journal May 2018
Hydrogen plasma reduced potassium titanate as a high power and ultralong lifespan anode material for sodium-ion batteries journal January 2018
H 2 Adsorption on Wurtzite ZnO and on ZnO/M(111) (M=Cu, Ag and Au) Bilayer Films journal May 2019
In situ environmental TEM observation of two-stage shrinking of Cu 2 O islands on Cu(100) during methanol reduction journal January 2020
A mini review of in situ near-ambient pressure XPS studies on non-noble, late transition metal catalysts journal January 2019
CO 2 hydrogenation to methanol over CuO–ZnO–TiO2–ZrO2: a comparison of catalysts prepared by sol–gel, solid-state reaction and solution-combustion journal May 2018

Similar Records

CO2 Hydrogenation to Methanol over Inverse ZrO2/Cu(111) Catalysts: The Fate of Methoxy under Dry and Wet Conditions
Journal Article · Thu Aug 18 00:00:00 EDT 2022 · Journal of Physical Chemistry. C · OSTI ID:1246804
+9 more
CO2 Hydrogenation on ZrO2/Cu(111) Surfaces: Production of Methane and Methanol
Journal Article · Wed Oct 20 00:00:00 EDT 2021 · Industrial and Engineering Chemistry Research · OSTI ID:1246804
+6 more
Understanding Methanol Synthesis on Inverse ZnO/CuOx/Cu Catalysts: Stability of CH3O Species and Dynamic Nature of the Surface
Journal Article · Fri Mar 19 00:00:00 EDT 2021 · Journal of Physical Chemistry. C · OSTI ID:1246804
+7 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY