Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Inverse ZrO2/Cu as a highly efficient methanol synthesis catalyst from CO2 hydrogenation

Journal Article · · Nature Communications
 [1];  [2];  [3];  [4];  [5];  [6];  [7];  [7];  [1];  [1];  [8];  [6];  [1];  [4];  [3];  [9];  [1]
  1. Peking Univ., Beijing (China). Beijing National Lab. for Molecular Sciences
  2. Brookhaven National Lab. (BNL), Upton, NY (United States); Zhejiang Univ. of Technology, Hangzhou (China)
  3. Chinese Academy of Sciences (CAS), Taiyuan (China). State Key Lab. of Coal Conversion; Synfuels China Co. Ltd., Beijing (China). National Center for Coal to Liquids
  4. Tsinghua Univ., Beijing (China)
  5. State Univ. of New York (SUNY), Stony Brook, NY (United States)
  6. Tianjin Univ. of Technology, Tianjin (China). Center for Electron Microscopy
  7. Brookhaven National Lab. (BNL), Upton, NY (United States)
  8. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  9. Brookhaven National Lab. (BNL), Upton, NY (United States); State Univ. of New York (SUNY), Stony Brook, NY (United States)
+ Show Author Affiliations
Enhancing the intrinsic activity and space time yield of Cu based heterogeneous methanol synthesis catalysts through CO2 hydrogenation is one of the major topics in CO2 conversion into value-added liquid fuels and chemicals. Here we report inverse ZrO2/Cu catalysts with a tunable Zr/Cu ratio have been prepared via an oxalate co-precipitation method, showing excellent performance for CO2 hydrogenation to methanol. Under optimal condition, the catalyst composed by 10% of ZrO2 supported over 90% of Cu exhibits the highest mass-specific methanol formation rate of 524 gMeOHkgcat-1h-1 at 220°C, 3.3 times higher than the activity of traditional Cu/ZrO2 catalysts (159 gMeOHkgcat-1h-1). In situ XRD-PDF, XAFS and AP-XPS structural studies reveal that the inverse ZrO2/Cu catalysts are composed of islands of partially reduced 1–2 nm amorphous ZrO2 supported over metallic Cu particles. The ZrO2 islands are highly active for the CO2 activation. Meanwhile, an intermediate of formate adsorbed on the Cu at 1350 cm-1 is discovered by the in situ DRIFTS. This formate intermediate exhibits fast hydrogenation conversion to methoxy. The activation of CO2 and hydrogenation of all the surface oxygenate intermediates are significantly accelerated over the inverse ZrO2/Cu configuration, accounting for the excellent methanol formation activity observed.
Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
National Key R&D Program of China; National Natural Science Foundation of China (NNSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-06CH11357; SC0012704
OSTI ID:
1717902
Alternate ID(s):
OSTI ID: 1798203
Report Number(s):
BNL--220639-2020-JAAM
Journal Information:
Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 11; ISSN 2041-1723
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English

References (49)

Beyond Oil and Gas: The Methanol Economy journal April 2005
Water-Gas Shift Reaction on a Highly Active Inverse CeO x /Cu(111) Catalyst: Unique Role of Ceria Nanoparticles journal October 2009
Formation of a ZnO Overlayer in Industrial Cu/ZnO/Al 2 O 3 Catalysts Induced by Strong Metal-Support Interactions journal February 2015
Indium Oxide as a Superior Catalyst for Methanol Synthesis by CO 2 Hydrogenation journal March 2016
CO 2 -to-Methanol Hydrogenation on Zirconia-Supported Copper Nanoparticles: Reaction Intermediates and the Role of the Metal-Support Interface journal January 2017
The Mechanism of CO and CO 2 Hydrogenation to Methanol over Cu-Based Catalysts journal March 2015
Effect of the damping function in dispersion corrected density functional theory journal March 2011
In-SituInfrared Study of Methanol Synthesis from H2/CO2over Cu/SiO2and Cu/ZrO2/SiO2 journal November 1997
Role of Hydrogen Spillover in Methanol Synthesis over Cu/ZrO2 journal July 2000
An XPS study of the interaction of oxygen with zirconium journal August 1989
Intermediate species on zirconia supported methanol aerogel catalysts journal November 1993
Intermediate species on zirconia supported methanol aerogel catalysts journal August 1993
Intermediate species on zirconia supported methanol aerogel catalysts V. Adsorption of methanol journal March 1995
Intermediate species on zirconia supported methanol aerogel catalysts journal May 1994
CO 2 hydrogenation to methanol over Cu/ZrO 2 catalysts: Effects of zirconia phases journal June 2016
Conversion of methanol to hydrocarbons over zeolite H-ZSM-5: On the origin of the olefinic species journal July 2007
Structural analysis of Y3+-doped Mg–Cd ferrites prepared by oxalate co-precipitation method journal April 2009
Challenges in the Greener Production of Formates/Formic Acid, Methanol, and DME by Heterogeneously Catalyzed CO 2 Hydrogenation Processes journal May 2017
When Density Functional Approximations Meet Iron Oxides journal September 2016
Structure and Properties of Zirconia Nanoparticles from Density Functional Theory Calculations journal February 2016
Cu Species Incorporated into Amorphous ZrO 2 with High Activity and Selectivity in CO 2 -to-Methanol Hydrogenation journal February 2018
In Situ Characterization of Cu/CeO 2 Nanocatalysts for CO 2 Hydrogenation: Morphological Effects of Nanostructured Ceria on the Catalytic Activity journal May 2018
Copper Nanocrystals Encapsulated in Zr-based Metal–Organic Frameworks for Highly Selective CO 2 Hydrogenation to Methanol journal November 2016
Methanol to Olefins (MTO): From Fundamentals to Commercialization journal February 2015
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
CO 2 Activation on Ni/γ–Al 2 O 3 Catalysts by First-Principles Calculations: From Ideal Surfaces to Supported Nanoparticles journal June 2016
Rationally Designing Bifunctional Catalysts as an Efficient Strategy To Boost CO 2 Hydrogenation Producing Value-Added Aromatics journal December 2018
Design of Interfacial Sites between Cu and Amorphous ZrO 2 Dedicated to CO 2 -to-Methanol Hydrogenation journal July 2018
Unique Properties of Ceria Nanoparticles Supported on Metals: Novel Inverse Ceria/Copper Catalysts for CO Oxidation and the Water-Gas Shift Reaction journal January 2013
Optimizing Binding Energies of Key Intermediates for CO 2 Hydrogenation to Methanol over Oxide-Supported Copper journal September 2016
Integrative CO 2 Capture and Hydrogenation to Methanol with Reusable Catalyst and Amine: Toward a Carbon Neutral Methanol Economy journal January 2018
Isolated Zr Surface Sites on Silica Promote Hydrogenation of CO 2 to CH 3 OH in Supported Cu Catalysts journal July 2018
Understanding of Enhanced Oxygen Storage Capacity in Ce 0.5 Zr 0.5 O 2 :  The Presence of an Anharmonic Pair Distribution Function in the Zr−O 2 Subshell as Analyzed by XAFS Spectroscopy journal May 2001
Model estimates of CO2 emissions from soil in response to global warming journal May 1991
George Andrew Olah (1927–2017) journal April 2017
Low-temperature hydrogen production from water and methanol using Pt/α-MoC catalysts journal March 2017
Non-syngas direct steam reforming of methanol to hydrogen and carbon dioxide at low temperature journal January 2012
Exploring the ternary interactions in Cu–ZnO–ZrO2 catalysts for efficient CO2 hydrogenation to methanol journal March 2019
Atomic-scale engineering of indium oxide promotion by palladium for methanol production via CO2 hydrogenation journal July 2019
Reducibility of ZrO 2 /Pt 3 Zr and ZrO 2 /Pt 2D films compared to bulk zirconia: a DFT+U study of oxygen removal and H 2 adsorption journal January 2017
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu journal April 2010
Global temperature change journal September 2006
Projector augmented-wave method journal December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal October 1996
Generalized Gradient Approximation Made Simple journal October 1996
A highly selective and stable ZnO-ZrO 2 solid solution catalyst for CO 2 hydrogenation to methanol journal October 2017
Atomic Resolution Imaging of a Carbon Nanotube from Diffraction Intensities journal May 2003
Impact of CO 2 -Induced Warming on Simulated Hurricane Intensity and Precipitation: Sensitivity to the Choice of Climate Model and Convective Parameterization journal September 2004

Similar Records

Insights into the methanol synthesis mechanism via CO2 hydrogenation over Cu-ZnO-ZrO2 catalysts: Effects of surfactant/Cu-Zn-Zr molar ratio
Journal Article · Thu Jun 25 20:00:00 EDT 2020 · Journal of CO2 Utilization · OSTI ID:1637476

Related Subjects

36 MATERIALS SCIENCE
CO2 hydrogenation
Copper
Copper oxide
Zirconium oxide