Methanol Synthesis from CO2 Hydrogenation over a Potassium-Promoted Cux O/Cu(111) (x ≤ 2) Model Surface: Rationalizing the Potential of Potassium in Catalysis

Liao, Wenjie; Liu, Ping

doi:10.1021/acscatal.9b05226

Title: Methanol Synthesis from CO₂ Hydrogenation over a Potassium-Promoted Cu_x O/Cu(111) (x ≤ 2) Model Surface: Rationalizing the Potential of Potassium in Catalysis

Abstract

Alkalis have been reported as a promotor in the heterogeneous catalysis, being able to enhance the activity and selectivity of catalysts. The effective utilization of alkalis in catalyst optimization requires the fundamental understanding of the underlying mechanism. In this work, we take a potassium (K)-modified Cu_xO/Cu(111) (x ≤ 2) model surface as a case study to rationalize the nature of K during the carbon dioxide hydrogenation using combined density functional theory (DFT) calculation and the kinetic Monte Carlo (KMC) simulation. Our result demonstrates the significant tuning of selectivity from carbon monoxide to methanol on going from Cu(111) to K-modified Cu_xO/Cu(111). The deposited K⁺ stabilizes the Cu_xO thin film under the reducing condition of carbon dioxide hydrogenation. More importantly, our study reveals that K⁺ acts as an active center for selective tuning in the binding, an accelerator for charge transfer, and a mediator for the electron tunneling. As a result, the K-modified Cu_xO/Cu(111) opens a methanediol [H₂C(OH)₂]-mediated formate pathway to facilitate the selective conversion of carbon dioxide to methanol. Our study develops the intrinsic rules of design to tune the catalytic performance using alkali metals.

Authors:

^[1];

^[2]

State Univ. of New York (SUNY), Stony Brook, NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)

Publication Date:: Fri Mar 20 00:00:00 EDT 2020

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

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1608778

Report Number(s):: BNL-213812-2020-JAAM
Journal ID: ISSN 2155-5435

Grant/Contract Number:: SC0012704

Resource Type:: Accepted Manuscript

Journal Name:: ACS Catalysis

Additional Journal Information:: Journal Volume: 10; Journal Issue: 10; Journal ID: ISSN 2155-5435

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

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

Citation Formats


                    Liao, Wenjie, and Liu, Ping. Methanol Synthesis from CO2 Hydrogenation over a Potassium-Promoted Cux O/Cu(111) (x ≤ 2) Model Surface: Rationalizing the Potential of Potassium in Catalysis.  United States: N. p., 2020. 
Web.  doi:10.1021/acscatal.9b05226.

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                    Liao, Wenjie, & Liu, Ping. Methanol Synthesis from CO2 Hydrogenation over a Potassium-Promoted Cux O/Cu(111) (x ≤ 2) Model Surface: Rationalizing the Potential of Potassium in Catalysis.  United States.  https://doi.org/10.1021/acscatal.9b05226

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                    Liao, Wenjie, and Liu, Ping. Fri .  
"Methanol Synthesis from CO2 Hydrogenation over a Potassium-Promoted Cux O/Cu(111) (x ≤ 2) Model Surface: Rationalizing the Potential of Potassium in Catalysis".  United States.  https://doi.org/10.1021/acscatal.9b05226.  https://www.osti.gov/servlets/purl/1608778.

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@article{osti_1608778,

  title        = {Methanol Synthesis from CO2 Hydrogenation over a Potassium-Promoted Cux O/Cu(111) (x ≤ 2) Model Surface: Rationalizing the Potential of Potassium in Catalysis},

  author       = {Liao, Wenjie and Liu, Ping},

  abstractNote = {Alkalis have been reported as a promotor in the heterogeneous catalysis, being able to enhance the activity and selectivity of catalysts. The effective utilization of alkalis in catalyst optimization requires the fundamental understanding of the underlying mechanism. In this work, we take a potassium (K)-modified CuxO/Cu(111) (x ≤ 2) model surface as a case study to rationalize the nature of K during the carbon dioxide hydrogenation using combined density functional theory (DFT) calculation and the kinetic Monte Carlo (KMC) simulation. Our result demonstrates the significant tuning of selectivity from carbon monoxide to methanol on going from Cu(111) to K-modified CuxO/Cu(111). The deposited K+ stabilizes the CuxO thin film under the reducing condition of carbon dioxide hydrogenation. More importantly, our study reveals that K+ acts as an active center for selective tuning in the binding, an accelerator for charge transfer, and a mediator for the electron tunneling. As a result, the K-modified CuxO/Cu(111) opens a methanediol [H2C(OH)2]-mediated formate pathway to facilitate the selective conversion of carbon dioxide to methanol. Our study develops the intrinsic rules of design to tune the catalytic performance using alkali metals.},

  doi          = {10.1021/acscatal.9b05226},

  journal      = {ACS Catalysis},

  number       = 10,

  volume       = 10,

  place        = {United States},

  year         = {Fri Mar 20 00:00:00 EDT 2020},

  month        = {Fri Mar 20 00:00:00 EDT 2020}

}

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Water-promoted interfacial pathways in methane oxidation to methanol on a CeO ₂ -Cu ₂ O catalyst

Journal Article Liu, Zongyuan ; Huang, Erwei ; Orozco, Ivan ; ... - Science

Highly selective oxidation of methane to methanol has long been challenging in catalysis. Here, we reveal key steps for the promotion of this reaction by water when tuning the selectivity of a well-defined CeO ₂ /Cu ₂ O/Cu(111) catalyst from carbon monoxide and carbon dioxide to methanol under a reaction environment with methane, oxygen, and water. Ambient-pressure x-ray photoelectron spectroscopy showed that water added to methane and oxygen led to surface methoxy groups and accelerated methanol production. These results were consistent with density functional theory calculations and kinetic Monte Carlo simulations, which showed that water preferentially dissociates over the activemore »« less
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https://doi.org/10.1126/science.aba5005

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Title: Methanol Synthesis from CO2 Hydrogenation over a Potassium-Promoted Cux O/Cu(111) (x ≤ 2) Model Surface: Rationalizing the Potential of Potassium in Catalysis

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Valence electronic structure of alkalis adsorbed on free-electron like and transition metals journal, June 1978

Erratum: The full CCSDT model for molecular electronic structure [J. Chem. Phys. 8 6 , 7041 (1987)] journal, September 1988

Projector augmented-wave method journal, December 1994

Theoretical Investigation of Propylene Epoxidation on Ag(111) by Molecular Oxygen: Na(K,Cl) Effects journal, June 2019

Fischer–Tropsch synthesis: induction and steady-state activity of high-alpha potassium promoted iron catalysts journal, January 2003

Formate adsorption and azimuthal orientation on Cu(100) from molecular orbital theory journal, September 1989

The Quantum Theory of the Emission and Absorption of Radiation journal, March 1927

K Atom Promotion of O 2 Chemisorption on Au(111) Surface journal, February 2019

Water dissociation on K 2 O-pre-adsorbed transition metals: a systematic theoretical study journal, January 2018

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

From ultrasoft pseudopotentials to the projector augmented-wave method journal, January 1999

A Systematic Theoretical Study of Water Gas Shift Reaction on Cu(111) and Cu(110): Potassium Effect journal, January 2019

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

IR studies and DFT calculations concerning the status of Cu+ ions in CuZSM-5 and CuMCM-41 journal, June 2004

Global Carbon Budget 2016 journal, January 2016

A complete basis set model chemistry. I. The total energies of closed‐shell atoms and hydrides of the first‐row elements journal, August 1988

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

Theory of Electrical Double Layers in Adsorbed Films journal, March 1935

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

Water–Gas Shift Reaction on K/Cu(111) and Cu/K/TiO 2 (110) Surfaces: Alkali Promotion of Water Dissociation and Production of H 2 journal, October 2019

Porous Graphene-Confined Fe–K as Highly Efficient Catalyst for CO 2 Direct Hydrogenation to Light Olefins journal, June 2018

Potassium-Induced Effect on the Structure and Chemical Activity of the Cu x O/Cu(1 1 1) ( x ≤ 2) Surface: A Combined Scanning Tunneling Microscopy and Density Functional Theory Study journal, November 2015

Alkali-metal-affected adsorption of molecules on metal surfaces journal, January 1988

Anomalous C-O Bond Weakening of Side-On-Bonded Carbon Monoxide on a Potassium-Promoted Ru(001) Surface journal, May 1984

Theory of molecular orbital energy shifting induced by electrostatic external effects journal, March 1990

A climbing image nudged elastic band method for finding saddle points and minimum energy paths journal, December 2000

Potassium's promotional effect of unsupported copper catalysts for methanol synthesis journal, February 1989

Theoretical perspective of alcohol decomposition and synthesis from CO2 hydrogenation journal, June 2013

Energetics of the Water–Gas-Shift Reaction on the Active Sites of the Industrially Used Cu/ZnO/Al2O3 Catalyst journal, September 2014

Effect of Na Promoter on Fe-Based Catalyst for CO 2 Hydrogenation to Alkenes journal, November 2018

A theoretical explanation of the effect of oxygen poisoning on industrial Haber-Bosch catalysts journal, April 2019

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

A new implementation of the full CCSDT model for molecular electronic structure journal, November 1988

The adsorption of CO on clean and potassium promoted FeO surfaces journal, September 1982

Methanol Synthesis journal, May 1992

Hydrocarbons via CO2 Hydrogenation Over Iron Catalysts: The Effect of Potassium on Structure and Performance journal, December 2015

In-situ DRIFTS study of two-step CO2 capture and catalytic methanation over Ru,“Na2O”/Al2O3 Dual Functional Material journal, June 2019

The Role of Sodium in Tuning Product Distribution in Syngas Conversion by Rh Catalysts journal, October 2017

Mechanism of Ethanol Synthesis from Syngas on Rh(111) journal, September 2009

Insight into methanol synthesis from CO2 hydrogenation on Cu(111): Complex reaction network and the effects of H2O journal, July 2011

On the Mechanism of Low-Temperature Water Gas Shift Reaction on Copper journal, January 2008

Promoting role of potassium in the reverse water gas shift reaction on Pt/mullite catalyst journal, March 2017

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

A review of research progress on heterogeneous catalysts for methanol synthesis from carbon dioxide hydrogenation journal, June 2019

Highly active copper-ceria and copper-ceria-titania catalysts for methanol synthesis from CO2 journal, July 2014

Charging Effects on Bonding and Catalyzed Oxidation of CO on Au8 Clusters on MgO journal, January 2005

Synthesis of higher alcohols on copper catalysts supported on alkali-promoted basic oxides journal, May 1998

Special points for Brillouin-zone integrations journal, June 1976

Recent Advances in Preferential Oxidation of CO Reaction over Platinum Group Metal Catalysts journal, April 2012

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal, October 1996

An Infrared Study of Methanol Synthesis from CO2 on Clean and Potassium-Promoted Cu/SiO2 journal, July 1995

Development of alkali-promoted ruthenium as a novel catalyst for ammonia synthesis journal, January 1981

DFT Investigation on the Competition of the Water-Gas Shift Reaction Versus Methanation on Clean and Potassium-Modified Nickel(1 1 1) Surfaces journal, November 2015

Water Dissociation on Clean and Potassium Preadsorbed Transition Metals: A Systematic Theoretical Study journal, June 2018

Inhomogeneous Electron Gas journal, November 1964

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

The Active Site of Methanol Synthesis over Cu/ZnO/Al2O3 Industrial Catalysts journal, April 2012

Potassium-Promoted Reduction of Cu 2 O/Cu(111) by CO journal, October 2018

Accurate and simple analytic representation of the electron-gas correlation energy journal, June 1992

Adsorption of the formate species on copper surfaces: a DFT study journal, July 1999

Study of reverse water gas shift reaction by TPD, TPR and CO2 hydrogenation over potassium-promoted Cu/SiO2 catalyst journal, January 2003

Methanation of CO2 over alkali-promoted Ru/TiO2 catalysts: II. Effect of alkali additives on the reaction pathway journal, November 2018

How to stabilize highly active Cu+ cations in a mixed-oxide catalyst journal, April 2016

Potassium Promotion of Cobalt Spinel Catalyst for N2O Decomposition—Accounted by Work Function Measurements and DFT Modelling journal, September 2008

Residual sodium effect on the catalytic activity of Cu/ZnO/Al2O3 in methanol synthesis from CO2 hydrogenation journal, November 1998

Nature of Lone-Pair–Surface Bonds and Their Scaling Relations journal, June 2018

Hydrogenation of CO2 to value-added products—A review and potential future developments journal, March 2014

Differences in the promotional effect of the group IA elements on unsupported copper catalysts for carbon monoxide hydrogenation journal, April 1989

Fundamental studies of methanol synthesis from CO2 hydrogenation on Cu(111), Cu clusters, and Cu/ZnO(0001̄) journal, January 2010

Mechanistic Study of Methanol Synthesis from CO 2 and H 2 on a Modified Model Mo 6 S 8 Cluster journal, January 2015

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

Title: Methanol Synthesis from CO₂ Hydrogenation over a Potassium-Promoted Cu_x O/Cu(111) (x ≤ 2) Model Surface: Rationalizing the Potential of Potassium in Catalysis

Valence electronic structure of alkalis adsorbed on free-electron like and transition metals
journal, June 1978

Erratum: The full CCSDT model for molecular electronic structure [J. Chem. Phys. 8 6 , 7041 (1987)]
journal, September 1988

Projector augmented-wave method
journal, December 1994

Theoretical Investigation of Propylene Epoxidation on Ag(111) by Molecular Oxygen: Na(K,Cl) Effects
journal, June 2019

Fischer–Tropsch synthesis: induction and steady-state activity of high-alpha potassium promoted iron catalysts
journal, January 2003

Formate adsorption and azimuthal orientation on Cu(100) from molecular orbital theory
journal, September 1989

The Quantum Theory of the Emission and Absorption of Radiation
journal, March 1927

K Atom Promotion of O ₂ Chemisorption on Au(111) Surface
journal, February 2019

Water dissociation on K ₂ O-pre-adsorbed transition metals: a systematic theoretical study
journal, January 2018

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

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

A Systematic Theoretical Study of Water Gas Shift Reaction on Cu(111) and Cu(110): Potassium Effect
journal, January 2019

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

IR studies and DFT calculations concerning the status of Cu+ ions in CuZSM-5 and CuMCM-41
journal, June 2004

Global Carbon Budget 2016
journal, January 2016

A complete basis set model chemistry. I. The total energies of closed‐shell atoms and hydrides of the first‐row elements
journal, August 1988

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

Theory of Electrical Double Layers in Adsorbed Films
journal, March 1935

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

Water–Gas Shift Reaction on K/Cu(111) and Cu/K/TiO ₂ (110) Surfaces: Alkali Promotion of Water Dissociation and Production of H ₂
journal, October 2019

Porous Graphene-Confined Fe–K as Highly Efficient Catalyst for CO ₂ Direct Hydrogenation to Light Olefins
journal, June 2018

Potassium-Induced Effect on the Structure and Chemical Activity of the Cu _x O/Cu(1 1 1) ( x ≤ 2) Surface: A Combined Scanning Tunneling Microscopy and Density Functional Theory Study
journal, November 2015

Alkali-metal-affected adsorption of molecules on metal surfaces
journal, January 1988

Anomalous C-O Bond Weakening of Side-On-Bonded Carbon Monoxide on a Potassium-Promoted Ru(001) Surface
journal, May 1984

Theory of molecular orbital energy shifting induced by electrostatic external effects
journal, March 1990

A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000

Potassium's promotional effect of unsupported copper catalysts for methanol synthesis
journal, February 1989

Theoretical perspective of alcohol decomposition and synthesis from CO2 hydrogenation
journal, June 2013

Energetics of the Water–Gas-Shift Reaction on the Active Sites of the Industrially Used Cu/ZnO/Al2O3 Catalyst
journal, September 2014

Effect of Na Promoter on Fe-Based Catalyst for CO ₂ Hydrogenation to Alkenes
journal, November 2018

A theoretical explanation of the effect of oxygen poisoning on industrial Haber-Bosch catalysts
journal, April 2019

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

A new implementation of the full CCSDT model for molecular electronic structure
journal, November 1988

The adsorption of CO on clean and potassium promoted FeO surfaces
journal, September 1982

Methanol Synthesis
journal, May 1992

Hydrocarbons via CO2 Hydrogenation Over Iron Catalysts: The Effect of Potassium on Structure and Performance
journal, December 2015

In-situ DRIFTS study of two-step CO2 capture and catalytic methanation over Ru,“Na2O”/Al2O3 Dual Functional Material
journal, June 2019

The Role of Sodium in Tuning Product Distribution in Syngas Conversion by Rh Catalysts
journal, October 2017

Mechanism of Ethanol Synthesis from Syngas on Rh(111)
journal, September 2009

Insight into methanol synthesis from CO2 hydrogenation on Cu(111): Complex reaction network and the effects of H2O
journal, July 2011

On the Mechanism of Low-Temperature Water Gas Shift Reaction on Copper
journal, January 2008

Promoting role of potassium in the reverse water gas shift reaction on Pt/mullite catalyst
journal, March 2017

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

A review of research progress on heterogeneous catalysts for methanol synthesis from carbon dioxide hydrogenation
journal, June 2019

Highly active copper-ceria and copper-ceria-titania catalysts for methanol synthesis from CO2
journal, July 2014

Charging Effects on Bonding and Catalyzed Oxidation of CO on Au₈ Clusters on MgO
journal, January 2005

Synthesis of higher alcohols on copper catalysts supported on alkali-promoted basic oxides
journal, May 1998

Special points for Brillouin-zone integrations
journal, June 1976

Recent Advances in Preferential Oxidation of CO Reaction over Platinum Group Metal Catalysts
journal, April 2012

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996

An Infrared Study of Methanol Synthesis from CO2 on Clean and Potassium-Promoted Cu/SiO2
journal, July 1995

Development of alkali-promoted ruthenium as a novel catalyst for ammonia synthesis
journal, January 1981

DFT Investigation on the Competition of the Water-Gas Shift Reaction Versus Methanation on Clean and Potassium-Modified Nickel(1 1 1) Surfaces
journal, November 2015

Water Dissociation on Clean and Potassium Preadsorbed Transition Metals: A Systematic Theoretical Study
journal, June 2018

Inhomogeneous Electron Gas
journal, November 1964

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

The Active Site of Methanol Synthesis over Cu/ZnO/Al₂O₃ Industrial Catalysts
journal, April 2012

Potassium-Promoted Reduction of Cu ₂ O/Cu(111) by CO
journal, October 2018

Accurate and simple analytic representation of the electron-gas correlation energy
journal, June 1992

Adsorption of the formate species on copper surfaces: a DFT study
journal, July 1999

Study of reverse water gas shift reaction by TPD, TPR and CO2 hydrogenation over potassium-promoted Cu/SiO2 catalyst
journal, January 2003

Methanation of CO2 over alkali-promoted Ru/TiO2 catalysts: II. Effect of alkali additives on the reaction pathway
journal, November 2018

How to stabilize highly active Cu+ cations in a mixed-oxide catalyst
journal, April 2016

Potassium Promotion of Cobalt Spinel Catalyst for N2O Decomposition—Accounted by Work Function Measurements and DFT Modelling
journal, September 2008

Residual sodium effect on the catalytic activity of Cu/ZnO/Al2O3 in methanol synthesis from CO2 hydrogenation
journal, November 1998

Nature of Lone-Pair–Surface Bonds and Their Scaling Relations
journal, June 2018

Hydrogenation of CO2 to value-added products—A review and potential future developments
journal, March 2014

Differences in the promotional effect of the group IA elements on unsupported copper catalysts for carbon monoxide hydrogenation
journal, April 1989

Fundamental studies of methanol synthesis from CO2 hydrogenation on Cu(111), Cu clusters, and Cu/ZnO(0001̄)
journal, January 2010

Mechanistic Study of Methanol Synthesis from CO ₂ and H ₂ on a Modified Model Mo ₆ S ₈ Cluster
journal, January 2015

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