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

Title: Exploring the ternary interactions in Cu–ZnO–ZrO2 catalysts for efficient CO2 hydrogenation to methanol

Journal Article · · Nature Communications
 [1];  [2];  [1];  [3];  [2];  [4];  [5]
  1. Kunming Univ. of Science and Technology (China). State Key Lab. of Complex Nonferrous Metal Resources Clean Utilization Engineering. Faculty of Metallurgical and Energy Engineering
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division
  3. Kunming Univ. of Science and Technology (China). State Key Lab. of Complex Nonferrous Metal Resources Clean Utilization Engineering; Columbia Univ., New York, NY (United States). Dept. of Earth and Environmental Engineering
  4. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division; Columbia Univ., New York, NY (United States). Dept. of Chemical Engineering
  5. Kunming Univ. of Science and Technology (China). State Key Lab. of Complex Nonferrous Metal Resources Clean Utilization Engineering; Dali Univ. (China). School of Pharmacy and Chemistry
+ Show Author Affiliations

The synergistic interaction among different components in complex catalysts is one of the crucial factors in determining catalytic performance. Here we report the interactions among the three components in controlling the catalytic performance of Cu–ZnO–ZrO2 (CZZ) catalyst for CO2 hydrogenation to methanol. The in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) measurements under the activity test pressure (3 MPa) reveal that the CO2 hydrogenation to methanol on the CZZ catalysts follows the formate pathway. Density functional theory (DFT) calculations agree with the in situ DRIFTS measurements, showing that the ZnO–ZrO2 interfaces are the active sites for CO2 adsorption and conversion, while the presence of metallic Cu is also necessary to facilitate H2 dissociation and to provide hydrogen resource. The combined experiment and DFT results reveal that tuning the interaction between ZnO and ZrO2 can be considered as another important factor for designing high performance catalysts for methanol generation from CO2.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States); Kunming Univ. of Science and Technology (China)
Sponsoring Organization:
USDOE Office of Science (SC); National Natural Science Foundation of China (NSFC); National Key Technologies R & D Program of China; Candidate Talents Training Fund of Yunnan Province (China)
Grant/Contract Number:
SC0012704; AC02-05CH11231; 51774159; 51304099; 51404122; 2011BAC01B03; 2014HB006
OSTI ID:
1504379
Report Number(s):
BNL-211494-2019-JAAM
Journal Information:
Nature Communications, Vol. 10; ISSN 2041-1723
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 188 works
Citation information provided by
Web of Science

References (60)

Solid-state interactions, adsorption sites and functionality of Cu-ZnO/ZrO2 catalysts in the CO2 hydrogenation to CH3OH journal November 2008
Mechanistic study of a new low-temperature methanol synthesis on Cu/MgO catalysts journal July 2005
In situ IR studies on the mechanism of methanol synthesis over an ultrafine Cu/ZnO/Al2O3 catalyst journal July 1998
Projector augmented-wave method journal December 1994
Challenges in the Greener Production of Formates/Formic Acid, Methanol, and DME by Heterogeneously Catalyzed CO 2 Hydrogenation Processes journal May 2017
From CO2 to Methanol by Hybrid QM/MM Embedding This work was supported by EU Esprit IV project 25047. S.A.F. is grateful to ICI and Synetix for funding. K. Waugh, L. Whitmore, S. Cristol, and P. Sushko are thanked for their helpful insights. QM/MM=quantum mechanics/molecular mechanics. journal December 2001
Highly selective hydrogenation of CO2 to methanol over CuO–ZnO–ZrO2 catalysts prepared by a surfactant-assisted co-precipitation method journal April 2015
Mixing Copper Nanoparticles and ZnO Nanocrystals: A Route towards Understanding the Hydrogenation of CO2 to Methanol? journal March 2011
Influence of Zr on the performance of Cu/Zn/Al/Zr catalysts via hydrotalcite-like precursors for CO2 hydrogenation to methanol journal February 2013
Au/3DOM Co3O4: highly active nanocatalysts for the oxidation of carbon monoxide and toluene journal January 2013
Tuning Selectivity of CO 2 Hydrogenation Reactions at the Metal/Oxide Interface journal July 2017
Adsorption of CO 2 at ZnO: A Surface Structure Effect from DFT+ U Calculations journal October 2013
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study journal January 1998
Quantifying the promotion of Cu catalysts by ZnO for methanol synthesis journal May 2016
Optimizing Binding Energies of Key Intermediates for CO 2 Hydrogenation to Methanol over Oxide-Supported Copper journal September 2016
In-SituInfrared Study of Methanol Synthesis from H2/CO2over Cu/SiO2and Cu/ZrO2/SiO2 journal November 1997
Active Sites on Oxide Surfaces: ZnO-Catalyzed Synthesis of Methanol from CO and H 2 journal April 2005
Active sites for CO 2 hydrogenation to methanol on Cu/ZnO catalysts journal March 2017
Reverse water-gas shift reaction at the Cu/ZnO interface: Influence of the Cu/Zn ratio on structure-activity correlations journal October 2016
CO2 hydrogenation to methanol over Cu/ZnO/ZrO2 catalysts prepared by precipitation-reduction method journal August 2016
A climbing image nudged elastic band method for finding saddle points and minimum energy paths journal December 2000
Synthesis, characterization and activity pattern of Cu–ZnO/ZrO2 catalysts in the hydrogenation of carbon dioxide to methanol journal July 2007
Structure–activity relationships of Cu–ZrO 2 catalysts for CO 2 hydrogenation to methanol: interaction effects and reaction mechanism journal January 2017
Theoretical Study of Methanol Synthesis from CO 2 Hydrogenation on Metal-Doped Cu(111) Surfaces journal December 2011
Morphology-Dependent Interactions of ZnO with Cu Nanoparticles at the Materials’ Interface in Selective Hydrogenation of CO2 to CH3OH journal January 2011
Effects of oxide carriers on surface functionality and process performance of the Cu–ZnO system in the synthesis of methanol via CO2 hydrogenation journal April 2013
In Situ Investigations of Structural Changes in Cu/ZnO Catalysts journal September 2000
Formation of a ZnO Overlayer in Industrial Cu/ZnO/Al 2 O 3 Catalysts Induced by Strong Metal-Support Interactions journal February 2015
Recent advances in catalytic hydrogenation of carbon dioxide journal January 2011
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set journal July 1996
Effect of the ZrO2 phase on the structure and behavior of supported Cu catalysts for ethanol conversion journal November 2013
Glycine–nitrate combustion synthesis of CuO–ZnO–ZrO2 catalysts for methanol synthesis from CO2 hydrogenation journal May 2010
Biaxially strained PtPb/Pt core/shell nanoplate boosts oxygen reduction catalysis journal December 2016
Highly active copper-ceria and copper-ceria-titania catalysts for methanol synthesis from CO2 journal July 2014
Special points for Brillouin-zone integrations journal June 1976
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal October 1996
Transient behavior of Cu/ZnO-based methanol synthesis catalysts journal February 2009
Inhomogeneous Electron Gas journal November 1964
CO 2 hydrogenation to methanol over CuO–ZnO–ZrO 2 –SiO 2 catalysts: Effects of SiO 2 contents journal May 2017
The Active Site of Methanol Synthesis over Cu/ZnO/Al2O3 Industrial Catalysts journal April 2012
Accurate and simple analytic representation of the electron-gas correlation energy journal June 1992
The Influence of the Precipitation/Ageing Temperature on a Cu/ZnO/ZrO 2 Catalyst for Methanol Synthesis from H 2 and CO 2 journal April 2014
Tuning of catalytic CO2 hydrogenation by changing composition of CuO–ZnO–ZrO2 catalysts journal June 2016
Reversible Hydrogenation of Carbon Dioxide to Formic Acid and Methanol: Lewis Acid Enhancement of Base Metal Catalysts journal February 2017
Structure sensitivity of Cu and CuZn catalysts relevant to industrial methanol synthesis journal October 2016
The effects of zirconia morphology on methanol synthesis from CO and H2H2 over Cu/ZrO2Cu/ZrO2 catalystsPart I. Steady-state studies journal July 2005
The effects of zirconia morphology on methanol synthesis from CO and H2 over Cu/ZrO2 catalystsPart II. Transient-response infrared studies journal July 2005
Role of the Cu-ZrO 2 Interfacial Sites for Conversion of Ethanol to Ethyl Acetate and Synthesis of Methanol from CO 2 and H 2 journal September 2016
Electronic Modulation of a Copper/Zinc Oxide Catalyst by a Heterojunction for Selective Hydrogenation of Carbon Dioxide to Methanol journal March 2012
The changing nature of the active site of Cu-Zn-Zr catalysts for the CO2 hydrogenation reaction to methanol journal June 2014
In Situ FTIR Spectroscopic Analysis of Carbonate Transformations during Adsorption and Desorption of CO 2 in K-Promoted HTlc journal June 2010
The Cu–ZnO synergy in methanol synthesis from CO2, Part 1: Origin of active site explained by experimental studies and a sphere contact quantification model on Cu + ZnO mechanical mixtures journal April 2015
A highly selective and stable ZnO-ZrO 2 solid solution catalyst for CO 2 hydrogenation to methanol journal October 2017
Formation of a ZnO Overlayer in Industrial Cu/ZnO/Al 2 O 3 Catalysts Induced by Strong Metal-Support Interactions journal February 2015
Inhomogeneous Electron Gas journal March 1973
Electronic Modulation of a Copper/Zinc Oxide Catalyst by a Heterojunction for Selective Hydrogenation of Carbon Dioxide to Methanol journal March 2012
Morphology-Dependent Interactions of ZnO with Cu Nanoparticles at the Materials’ Interface in Selective Hydrogenation of CO2 to CH3OH journal January 2011
Voltage- and time-dependent valence state transition in cobalt oxide catalysts during the oxygen evolution reaction journal April 2020
High-resolution X-ray luminescence extension imaging journal February 2021
Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect journal February 2020

Cited By (3)

Rational Engineering of Multilayered Co 3 O 4 /ZnO Nanocatalysts through Chemical Transformations from Matryoshka‐Type ZIFs journal August 2019
CO2 hydrogenation to high-value products via heterogeneous catalysis journal December 2019
Selective hydrogenation of CO 2 over a Ce promoted Cu-based catalyst confined by SBA-15 journal January 2019

Similar Records

Strong Evidence of the Role of H2O in Affecting Methanol Selectivity from CO2 Hydrogenation over Cu-ZnO-ZrO2
Journal Article · Thu Nov 21 00:00:00 EST 2019 · Chem · OSTI ID:1504379
+5 more
Optimization and understanding of ZnO nanoarray supported Cu-ZnO-Al2O3 catalyst for enhanced CO2 -methanol conversion at low temperature and pressure
Journal Article · Thu Feb 02 00:00:00 EST 2023 · Chemical Engineering Journal · OSTI ID:1504379
+11 more
Effect of operating parameters on H2/CO2 conversion to methanol over Cu-Zn oxide supported on ZrO2 polymorph catalysts: Characterization and kinetics
Journal Article · Wed Jun 23 00:00:00 EDT 2021 · Chemical Engineering Journal · OSTI ID:1504379
+7 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
catalytic mechanisms
chemical engineering
heterogeneous catalysis