Reactivity of a Zirconia–Copper Inverse Catalyst for CO2 Hydrogenation

Ma, Yilin; Wang, Jason; Goodman, Kenneth R.; Head, Ashley R.; Tong, Xiao; Stacchiola, Dario J.; White, Michael G.

doi:10.1021/acs.jpcc.0c06624

Title: Reactivity of a Zirconia–Copper Inverse Catalyst for CO₂ Hydrogenation

Abstract

Copper–zirconia catalysts have been shown to be effective for methanol synthesis via CO₂ hydrogenation, yet the active phases and reaction mechanism remain uncertain. Here, an inverse model catalyst ZrO₂/CuO₂/Cu(111) was prepared by mass-selected ion deposition and tested for CO₂ hydrogenation under near-ambient pressure (AP) reaction conditions by using X-ray photoelectron spectroscopy (NAP-XPS) and infrared reflection–absorption spectroscopy (NAP-IRAS). The spatial resolution afforded by the small entrance cone of the AP-XPS spectrometer was used to resolve regions of the surface with and without Zr deposition. Carbon 1s core level spectra of the ZrO₂/Cu₂O/Cu(111) regions of the surface under 500 mTorr of CO₂ + H₂ (1:3 ratio) show evidence for reaction intermediates including carbonate (CO₃*), formate (HCOO*), and H_xCO* species, with methoxy having the highest surface concentration at 500–600 K. These intermediates are confirmed by IRAS vibrational spectra. In regions of the surface without Zr, the Cu₂O/Cu(111) is reduced to metallic Cu, and the surface intermediates are different and are present at much lower concentrations. The observed surface intermediates and their temperature dependence suggest a mechanism in which CO₂ is adsorbed on zirconia as carbonate (CO₃*) and then converted to HCOO* and H_xCO* hydrogenated intermediates that ultimately lead to methoxy (CH₃O*), the finalmore »« less

Authors:

Ma, Yilin ^[1]; Wang, Jason ^[1]; Goodman, Kenneth R. ^[1];

^[2]; Tong, Xiao ^[2];

^[2];

^[3]

Stony Brook Univ., NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Stony Brook Univ., NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)

Publication Date:: Mon Sep 14 00:00:00 EDT 2020

Research Org.:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Defense Threat Reduction Agency (DTRA)

OSTI Identifier:: 1670666

Report Number(s):: BNL-219917-2020-JAAM
Journal ID: ISSN 1932-7447

Grant/Contract Number:: SC0012704; SC0012573; HDTRA11510005

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. C

Additional Journal Information:: Journal Volume: 124; Journal Issue: 40; Journal ID: ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY

Citation Formats


                    Ma, Yilin, Wang, Jason, Goodman, Kenneth R., Head, Ashley R., Tong, Xiao, Stacchiola, Dario J., and White, Michael G. Reactivity of a Zirconia–Copper Inverse Catalyst for CO2 Hydrogenation.  United States: N. p., 2020. 
Web.  doi:10.1021/acs.jpcc.0c06624.

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                    Ma, Yilin, Wang, Jason, Goodman, Kenneth R., Head, Ashley R., Tong, Xiao, Stacchiola, Dario J., & White, Michael G. Reactivity of a Zirconia–Copper Inverse Catalyst for CO2 Hydrogenation.  United States.  https://doi.org/10.1021/acs.jpcc.0c06624

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                    Ma, Yilin, Wang, Jason, Goodman, Kenneth R., Head, Ashley R., Tong, Xiao, Stacchiola, Dario J., and White, Michael G. Mon .  
"Reactivity of a Zirconia–Copper Inverse Catalyst for CO2 Hydrogenation".  United States.  https://doi.org/10.1021/acs.jpcc.0c06624.  https://www.osti.gov/servlets/purl/1670666.

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@article{osti_1670666,

  title        = {Reactivity of a Zirconia–Copper Inverse Catalyst for CO2 Hydrogenation},

  author       = {Ma, Yilin and Wang, Jason and Goodman, Kenneth R. and Head, Ashley R. and Tong, Xiao and Stacchiola, Dario J. and White, Michael G.},

  abstractNote = {Copper–zirconia catalysts have been shown to be effective for methanol synthesis via CO2 hydrogenation, yet the active phases and reaction mechanism remain uncertain. Here, an inverse model catalyst ZrO2/CuO2/Cu(111) was prepared by mass-selected ion deposition and tested for CO2 hydrogenation under near-ambient pressure (AP) reaction conditions by using X-ray photoelectron spectroscopy (NAP-XPS) and infrared reflection–absorption spectroscopy (NAP-IRAS). The spatial resolution afforded by the small entrance cone of the AP-XPS spectrometer was used to resolve regions of the surface with and without Zr deposition. Carbon 1s core level spectra of the ZrO2/Cu2O/Cu(111) regions of the surface under 500 mTorr of CO2 + H2 (1:3 ratio) show evidence for reaction intermediates including carbonate (CO3*), formate (HCOO*), and HxCO* species, with methoxy having the highest surface concentration at 500–600 K. These intermediates are confirmed by IRAS vibrational spectra. In regions of the surface without Zr, the Cu2O/Cu(111) is reduced to metallic Cu, and the surface intermediates are different and are present at much lower concentrations. The observed surface intermediates and their temperature dependence suggest a mechanism in which CO2 is adsorbed on zirconia as carbonate (CO3*) and then converted to HCOO* and HxCO* hydrogenated intermediates that ultimately lead to methoxy (CH3O*), the final surface-bound precursor for methanol. Overall, the results clearly demonstrate the promotional effects of small ZrO2 particles for enhancing the reactivity of Cu surfaces for CO2 hydrogenation.},

  doi          = {10.1021/acs.jpcc.0c06624},

  journal      = {Journal of Physical Chemistry. C},

  number       = 40,

  volume       = 124,

  place        = {United States},

  year         = {Mon Sep 14 00:00:00 EDT 2020},

  month        = {Mon Sep 14 00:00:00 EDT 2020}

}

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Title: Reactivity of a Zirconia–Copper Inverse Catalyst for CO2 Hydrogenation

Abstract

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Title: Reactivity of a Zirconia–Copper Inverse Catalyst for CO₂ Hydrogenation

Challenges in the Greener Production of Formates/Formic Acid, Methanol, and DME by Heterogeneously Catalyzed CO ₂ Hydrogenation Processes
journal, May 2017

Formic acid as a hydrogen source – recent developments and future trends
journal, January 2012

Growth, Structure, and Stability of Au on Ordered ZrO ₂ (111) Thin Films
journal, May 2011

Methanol Synthesis
journal, May 1992

Recent Advances in Catalysts for Methanol Synthesis via Hydrogenation of CO and CO ₂
journal, December 2003

Beyond Oil and Gas: The Methanol Economy
journal, April 2005

Active sites for CO ₂ hydrogenation to methanol on Cu/ZnO catalysts
journal, March 2017

Methanol synthesis over a Zn-deposited copper model catalyst
journal, January 1995

Synthesis, characterization and activity pattern of Cu–ZnO/ZrO2 catalysts in the hydrogenation of carbon dioxide to methanol
journal, July 2007

Methanol synthesis from CO2 hydrogenation over Cu/γ-Al2O3 catalysts modified by ZnO, ZrO2 and MgO
journal, August 2015

Effective conversion of carbon dioxide and hydrogen to hydrocarbons
journal, August 1991

Efficient Conversion of Carbon Dioxide to Methanol Using Copper Catalyst by a New Low-temperature Hydrogenation Process
journal, September 2007

Catalytic reduction of CO ₂ by H ₂ for synthesis of CO, methanol and hydrocarbons: challenges and opportunities
journal, January 2016

Structure and function of Cu-based composite catalysts for highly effective synthesis of methanol by hydrogenation of CO2 and CO
journal, April 1997

Effect of Mg and Mn oxide additions on structural and adsorptive properties of Cu/ZnO/ZrO2 catalysts for the methanol synthesis from CO2
journal, August 2003

Glycine–nitrate combustion synthesis of CuO–ZnO–ZrO2 catalysts for methanol synthesis from CO2 hydrogenation
journal, May 2010

Effect of TiO2, ZrO2, and TiO2–ZrO2 on the performance of CuO–ZnO catalyst for CO2 hydrogenation to methanol
journal, May 2015

Tuning of catalytic CO2 hydrogenation by changing composition of CuO–ZnO–ZrO2 catalysts
journal, June 2016

Effect of Zr and pH in the preparation of Cu/ZnO catalysts for the methanol synthesis by CO2 hydrogenation
journal, April 2012

Influence of Zr on the performance of Cu/Zn/Al/Zr catalysts via hydrotalcite-like precursors for CO2 hydrogenation to methanol
journal, February 2013

Solid-state interactions, adsorption sites and functionality of Cu-ZnO/ZrO2 catalysts in the CO2 hydrogenation to CH3OH
journal, November 2008

Development of highly stable catalyst for methanol synthesis from carbon dioxide
journal, January 2014

The effect of ageing time on co-precipitated Cu/ZnO/ZrO2 catalysts used in methanol synthesis from CO2 and H2
journal, August 2007

Bimetallic Pd–Cu catalysts for selective CO2 hydrogenation to methanol
journal, July 2015

Study of CuZnMOx oxides (M=Al, Zr, Ce, CeZr) for the catalytic hydrogenation of CO2 into methanol
journal, March 2015

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journal, November 2006

On the mechanism of CO and CO2 hydrogenation reactions on zirconia-supported catalysts: a diffuse reflectance FTIR study
journal, December 1990

Surface species in CO2 methanation over amorphous palladium/zirconia catalysts
journal, November 1991

Influence of ZrO ₂ Structure and Copper Electronic State on Activity of Cu/ZrO ₂ Catalysts in Methanol Synthesis from CO ₂
journal, September 2014

Exploring the ternary interactions in Cu–ZnO–ZrO2 catalysts for efficient CO2 hydrogenation to methanol
journal, March 2019

CO ₂ Hydrogenation to Methanol over ZrO ₂ -Containing Catalysts: Insights into ZrO ₂ Induced Synergy
journal, July 2019

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journal, January 1994

Recent advances in catalytic hydrogenation of carbon dioxide
journal, January 2011

Basic evidences for methanol-synthesis catalyst design
journal, May 2009

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

Morphology-Dependent Interactions of ZnO with Cu Nanoparticles at the Materials’ Interface in Selective Hydrogenation of CO2 to CH3OH
journal, January 2011

A highly selective and stable ZnO-ZrO ₂ solid solution catalyst for CO ₂ hydrogenation to methanol
journal, October 2017

Methanol synthesis from CO2-rich syngas over a ZrO2 doped CuZnO catalyst
journal, June 2006

The changing nature of the active site of Cu-Zn-Zr catalysts for the CO2 hydrogenation reaction to methanol
journal, June 2014

Formation of a ZnO Overlayer in Industrial Cu/ZnO/Al ₂ O ₃ Catalysts Induced by Strong Metal-Support Interactions
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

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

Methanol synthesis from CO2 hydrogenation over La–M–Cu–Zn–O (M = Y, Ce, Mg, Zr) catalysts derived from perovskite-type precursors
journal, April 2014

Effects of Zirconia Phase on the Synthesis of Methanol over Zirconia-Supported Copper
journal, January 2002

In SituInfrared Study of Methanol Synthesis from CO2/H2on Titania and Zirconia Promoted Cu/SiO2
journal, May 1999

Development of copper/zinc oxide-based multicomponent catalysts for methanol synthesis from carbon dioxide and hydrogen
journal, May 1996

CO2 hydrogenation to methanol over Cu/ZnO/ZrO2 catalysts prepared by precipitation-reduction method
journal, August 2016

Influences of particle size and crystallinity of highly loaded CuO/ZrO ₂ on CO ₂ hydrogenation to methanol
journal, July 2019

Cu Species Incorporated into Amorphous ZrO ₂ with High Activity and Selectivity in CO ₂ -to-Methanol Hydrogenation
journal, February 2018

Frontiers, Opportunities, and Challenges in Biochemical and Chemical Catalysis of CO ₂ Fixation
journal, June 2013

Reaction Network of Methanol Synthesis over Cu/ZnO Nanocatalysts
journal, June 2015

CO2 fixation into methanol at Cu/ZrO2 interface from first principles kinetic Monte Carlo
journal, April 2009

Optimizing Binding Energies of Key Intermediates for CO ₂ Hydrogenation to Methanol over Oxide-Supported Copper
journal, September 2016

In Situ Infrared Study of Methanol Synthesis from H2/CO over Cu/SiO2and Cu/ZrO2/SiO2
journal, August 1998

Theoretical Study of Methanol Synthesis from CO ₂ Hydrogenation on Metal-Doped Cu(111) Surfaces
journal, December 2011

Mechanism of CO2 hydrogenation over Cu/ZrO2(2̅12) interface from first-principles kinetics Monte Carlo simulations
journal, October 2010

Mechanism of Methanol Synthesis on Cu through CO ₂ and CO Hydrogenation
journal, February 2011

CO ₂ -to-Methanol Hydrogenation on Zirconia-Supported Copper Nanoparticles: Reaction Intermediates and the Role of the Metal-Support Interface
journal, January 2017

Tuning Selectivity of CO ₂ Hydrogenation Reactions at the Metal/Oxide Interface
journal, July 2017

Surface active structure of ultra-fine Cu/ZrO2 catalysts used for the CO2+H2 to methanol reaction
journal, September 2001

Gas-Phase Reactivity of the Ti ₈ C ₁₂ ⁺ Met-car with Triatomic Sulfur-Containing Molecules: CS ₂ , SCO, and SO ₂
journal, March 2006

Catalysis Applications of Size-Selected Cluster Deposition
journal, November 2015

Oxidation of Cu(111): two new oxygen induced reconstructions
journal, December 1991

Two new oxygen induced reconstructions on Cu(111)
journal, May 1992

Scanning tunneling microscopy studies of oxygen adsorption on Cu(111)
journal, January 2001

Autocatalytic Reduction of a Cu ₂ O/Cu(111) Surface by CO: STM, XPS, and DFT Studies
journal, July 2010

Mechanistic Study of CO Titration on Cu _x O/Cu(1 1 1) ( x ≤2) Surfaces
journal, June 2014

Growth of an Ultrathin Zirconia Film on Pt ₃ Zr Examined by High-Resolution X-ray Photoelectron Spectroscopy, Temperature-Programmed Desorption, Scanning Tunneling Microscopy, and Density Functional Theory
journal, January 2015

Oxygen adsorption and stability of surface oxides on $Cu (111)$ : A first-principles investigation
journal, April 2006

CO ₂ Adsorption on Cu ₂ O(111): A DFT+U and DFT-D Study
journal, November 2013

Investigation of CO and CO ₂ Adsorption on Tetragonal and Monoclinic Zirconia
journal, July 2001

Surface Chemistry of Cu in the Presence of CO ₂ and H ₂ O
journal, September 2008

In-situ FT-IR study on CO2 hydrogenation over Cu catalysts supported on SiO2, Al2O3, and TiO2
journal, December 1997

Probing Surface Structures of CeO ₂ , TiO ₂ , and Cu ₂ O Nanocrystals with CO and CO ₂ Chemisorption
journal, September 2016

The effects of zirconia morphology on methanol synthesis from CO and H2 over Cu/ZrO2 catalystsPart II. Transient-response infrared studies
journal, July 2005

Intermediate species on zirconia supported methanol aerogel catalysts
journal, November 1993

Structure–activity relationships of Cu–ZrO ₂ catalysts for CO ₂ hydrogenation to methanol: interaction effects and reaction mechanism
journal, January 2017

Infrared study of syngas adsorption on zirconia
journal, September 1990

In-SituInfrared Study of Methanol Synthesis from H2/CO2over Cu/SiO2and Cu/ZrO2/SiO2
journal, November 1997