Highly Selective Methane to Methanol Conversion on Inverse SnO2/Cu2O/Cu(111) Catalysts: Unique Properties of SnO2 Nanostructures and the Inhibition of the Direct Oxidative Combustion of Methane

Huang, Erwei; Rui, Ning; Rosales, Rina; Kang, Jindong; Nemšák, Slavomir; Senanayake, Sanjaya D.; Rodriguez, José A.; Liu, Ping

doi:10.1021/acscatal.2c03060

Title: Highly Selective Methane to Methanol Conversion on Inverse SnO₂/Cu₂O/Cu(111) Catalysts: Unique Properties of SnO₂ Nanostructures and the Inhibition of the Direct Oxidative Combustion of Methane

Abstract

Direct methane to methanol (CH₄ → CH₃OH) conversion in heterogeneous catalysis has been a long-standing challenge due to the difficulties in equalizing the activation of methane and protection of the methanol product at the same reaction conditions. Here, we report an inverse catalyst, consisting of small structures of SnO₂ (0.5-1 nm in size) dispersed on Cu₂O/Cu(111), for highly selective CH₃OH production from CH₄. This system was investigated by combining theoretical [density functional theory calculations (DFT), kinetic Monte Carlo simulations (KMC)] and experimental methods [scanning tunneling microscopy (STM), ambient-pressure X-ray photoelectron spectroscopy (AP-XPS)]. The DFT and AP-XPS studies showed that on SnO₂/Cu₂O/Cu(111) the conversion of CH₄ by oxygen (O₂) preferred complete combustion to carbon dioxide (CO₂). The addition of water (H₂O) enhanced the production of CH₃OH to nearly 100% selectivity in KMC simulations. This trend was consistent with results of AP-XPS. The presence of water in the reaction environment rendered an extremely high amount of methoxy species (*CH₃O), a precursor for CH₃OH production. Further, the high CH₃OH selectivity of SnO₂/Cu₂O/Cu(111) reflected the unique atomic and electronic structure of the supported SnO₂ nanoparticles. As a result, the O₂ adsorption and dissociation, and thus the full combustion of CH₄ to CO₂, was completelymore »« less

Authors:

^[1];

^[2]; Rosales, Rina ^[1]; Kang, Jindong ^[1]; Nemšák, Slavomir ^[3];

^[2];

^[4];

^[4]

Stony Brook Univ., NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Stony Brook Univ., NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)

Publication Date:: Thu Sep 01 00:00:00 EDT 2022

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

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

OSTI Identifier:: 1897497

Report Number(s):: BNL-223669-2022-JAAM
Journal ID: ISSN 2155-5435

Grant/Contract Number:: SC0012704; AC02-05CH11231; BES-ERCAP0019897

Resource Type:: Accepted Manuscript

Journal Name:: ACS Catalysis

Additional Journal Information:: Journal Volume: 12; Journal Issue: 18; Journal ID: ISSN 2155-5435

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 03 NATURAL GAS; tin oxide; copper oxide; selective methane conversion; methanol selectivity; inverse catalysts

Citation Formats


                    Huang, Erwei, Rui, Ning, Rosales, Rina, Kang, Jindong, Nemšák, Slavomir, Senanayake, Sanjaya D., Rodriguez, José A., and Liu, Ping. Highly Selective Methane to Methanol Conversion on Inverse SnO2/Cu2O/Cu(111) Catalysts: Unique Properties of SnO2 Nanostructures and the Inhibition of the Direct Oxidative Combustion of Methane.  United States: N. p., 2022. 
Web.  doi:10.1021/acscatal.2c03060.

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                    Huang, Erwei, Rui, Ning, Rosales, Rina, Kang, Jindong, Nemšák, Slavomir, Senanayake, Sanjaya D., Rodriguez, José A., & Liu, Ping. Highly Selective Methane to Methanol Conversion on Inverse SnO2/Cu2O/Cu(111) Catalysts: Unique Properties of SnO2 Nanostructures and the Inhibition of the Direct Oxidative Combustion of Methane.  United States.  https://doi.org/10.1021/acscatal.2c03060

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                    Huang, Erwei, Rui, Ning, Rosales, Rina, Kang, Jindong, Nemšák, Slavomir, Senanayake, Sanjaya D., Rodriguez, José A., and Liu, Ping. Thu .  
"Highly Selective Methane to Methanol Conversion on Inverse SnO2/Cu2O/Cu(111) Catalysts: Unique Properties of SnO2 Nanostructures and the Inhibition of the Direct Oxidative Combustion of Methane".  United States.  https://doi.org/10.1021/acscatal.2c03060.  https://www.osti.gov/servlets/purl/1897497.

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@article{osti_1897497,

  title        = {Highly Selective Methane to Methanol Conversion on Inverse SnO2/Cu2O/Cu(111) Catalysts: Unique Properties of SnO2 Nanostructures and the Inhibition of the Direct Oxidative Combustion of Methane},

  author       = {Huang, Erwei and Rui, Ning and Rosales, Rina and Kang, Jindong and Nemšák, Slavomir and Senanayake, Sanjaya D. and Rodriguez, José A. and Liu, Ping},

  abstractNote = {Direct methane to methanol (CH4 → CH3OH) conversion in heterogeneous catalysis has been a long-standing challenge due to the difficulties in equalizing the activation of methane and protection of the methanol product at the same reaction conditions. Here, we report an inverse catalyst, consisting of small structures of SnO2 (0.5-1 nm in size) dispersed on Cu2O/Cu(111), for highly selective CH3OH production from CH4. This system was investigated by combining theoretical [density functional theory calculations (DFT), kinetic Monte Carlo simulations (KMC)] and experimental methods [scanning tunneling microscopy (STM), ambient-pressure X-ray photoelectron spectroscopy (AP-XPS)]. The DFT and AP-XPS studies showed that on SnO2/Cu2O/Cu(111) the conversion of CH4 by oxygen (O2) preferred complete combustion to carbon dioxide (CO2). The addition of water (H2O) enhanced the production of CH3OH to nearly 100% selectivity in KMC simulations. This trend was consistent with results of AP-XPS. The presence of water in the reaction environment rendered an extremely high amount of methoxy species (*CH3O), a precursor for CH3OH production. Further, the high CH3OH selectivity of SnO2/Cu2O/Cu(111) reflected the unique atomic and electronic structure of the supported SnO2 nanoparticles. As a result, the O2 adsorption and dissociation, and thus the full combustion of CH4 to CO2, was completely suppressed; while the H2O dissociative adsorption was still feasible, providing active hydroxyl species for a truly selective CH4 to CH3OH conversion.},

  doi          = {10.1021/acscatal.2c03060},

  journal      = {ACS Catalysis},

  number       = 18,

  volume       = 12,

  place        = {United States},

  year         = {Thu Sep 01 00:00:00 EDT 2022},

  month        = {Thu Sep 01 00:00:00 EDT 2022}

}

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Title: Highly Selective Methane to Methanol Conversion on Inverse SnO2/Cu2O/Cu(111) Catalysts: Unique Properties of SnO2 Nanostructures and the Inhibition of the Direct Oxidative Combustion of Methane

Abstract

Citation Formats

Direct methane conversion routes to chemicals and fuels journal, August 2011

Methane activation: the past and future journal, January 2014

Water enables mild oxidation of methane to methanol on gold single-atom catalysts journal, February 2021

Direct Conversion of Methane to Value-Added Chemicals over Heterogeneous Catalysts: Challenges and Prospects journal, March 2017

The“Rebound Controversy”: An Overview and Theoretical Modeling of the Rebound Step in C−H Hydroxylation by Cytochrome P450 journal, January 2004

Abstraction of the Hydrogen Atom of Methane by Iron−Oxo Species: The Concerted Reaction Path Is Energetically More Favorable journal, June 1998

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

Anthropogenic Chemical Carbon Cycle for a Sustainable Future journal, August 2011

The Direct Catalytic Oxidation of Methane to Methanol-A Critical Assessment journal, November 2017

Single Step Oxidation of Methane to Methanol–Towards Better Understanding journal, January 2013

The direct conversion of methane to methanol by controlled oxidation journal, August 1985

Strategies for the Direct Catalytic Valorization of Methane Using Heterogeneous Catalysis: Challenges and Opportunities journal, April 2016

Enzymatic Oxidation of Methane journal, March 2015

Alkane Oxidation: Methane Monooxygenases, Related Enzymes, and Their Biomimetics journal, February 2017

Controlled Oxidation of Hydrocarbons by the Membrane-Bound Methane Monooxygenase: The Case for a Tricopper Cluster journal, August 2008

Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts journal, November 2017

Particulate methane monooxygenase contains only mononuclear copper centers journal, May 2019

Iron and Copper Active Sites in Zeolites and Their Correlation to Metalloenzymes journal, December 2017

Active sites and mechanisms in the direct conversion of methane to methanol using Cu in zeolitic hosts: a critical examination journal, January 2020

Direct Conversion of Methane to Methanol under Mild Conditions over Cu-Zeolites and beyond journal, January 2017

Selective anaerobic oxidation of methane enables direct synthesis of methanol journal, May 2017

Low Temperature Activation of Methane on Metal-Oxides and Complex Interfaces: Insights from Surface Science journal, July 2020

Low-temperature activation of methane on the IrO 2 (110) surface journal, April 2017

Surface characterization and methane activation on SnO x /Cu 2 O/Cu(111) inverse oxide/metal catalysts journal, January 2021

Breaking Simple Scaling Relations through Metal–Oxide Interactions: Understanding Room-Temperature Activation of Methane on M/CeO 2 (M = Pt, Ni, or Co) Interfaces journal, October 2020

Low-temperature activation of methane on doped single atoms: descriptor and prediction journal, January 2018

Direct Conversion of Methane to Methanol on Ni-Ceria Surfaces: Metal–Support Interactions and Water-Enabled Catalytic Conversion by Site Blocking journal, May 2018

Low-Temperature Conversion of Methane to Methanol on CeO x /Cu 2 O Catalysts: Water Controlled Activation of the C–H Bond journal, October 2016

Water-promoted interfacial pathways in methane oxidation to methanol on a CeO 2 -Cu 2 O catalyst journal, April 2020

Selective Methane Oxidation to Methanol on ZnO/Cu2O/Cu(111) Catalysts: Multiple Site-Dependent Behaviors journal, November 2021

Inverse oxide/metal catalysts: A versatile approach for activity tests and mechanistic studies journal, February 2010

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

Inverse Oxide/Metal Catalysts in Fundamental Studies and Practical Applications: A Perspective of Recent Developments journal, June 2016

Ceria-based model catalysts: fundamental studies on the importance of the metal–ceria interface in CO oxidation, the water–gas shift, CO 2 hydrogenation, and methane and alcohol reforming journal, January 2017

Water-Gas Shift Reaction on a Highly Active Inverse CeO x /Cu(111) Catalyst: Unique Role of Ceria Nanoparticles journal, October 2009

Hydroxylation of ZnO/Cu(1 1 1) inverse catalysts under ambient water vapor and the water–gas shift reaction journal, August 2019

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

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

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

Methanol Synthesis from CO 2 Hydrogenation over a Potassium-Promoted Cu x O/Cu(111) ( x ≤ 2) Model Surface: Rationalizing the Potential of Potassium in Catalysis journal, March 2020

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

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

The Unique Properties of the Oxide-Metal Interface: Reaction of Ethanol on an Inverse Model CeO x –Au(111) Catalyst journal, October 2014

In Situ Studies of Methanol Decomposition Over Cu(111) and Cu 2 O/Cu(111): Effects of Reactant Pressure, Surface Morphology, and Hot Spots of Active Sites journal, December 2020

Surface Science Studies of Gas Sensing Materials: SnO2 journal, October 2006

Cation-exchanged zeolites for the selective oxidation of methane to methanol journal, January 2018

Growth, Structure, and Catalytic Properties of ZnO x Grown on CuO x /Cu(111) Surfaces journal, October 2018

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

Inhomogeneous Electron Gas journal, November 1964

Self-Consistent Equations Including Exchange and Correlation Effects journal, November 1965

Selective molecular adsorption in sub-nanometer cages of a Cu2O surface oxide journal, January 2013

Title: Highly Selective Methane to Methanol Conversion on Inverse SnO₂/Cu₂O/Cu(111) Catalysts: Unique Properties of SnO₂ Nanostructures and the Inhibition of the Direct Oxidative Combustion of Methane

Direct methane conversion routes to chemicals and fuels
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Methane activation: the past and future
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Water enables mild oxidation of methane to methanol on gold single-atom catalysts
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Direct Conversion of Methane to Value-Added Chemicals over Heterogeneous Catalysts: Challenges and Prospects
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The“Rebound Controversy”: An Overview and Theoretical Modeling of the Rebound Step in C−H Hydroxylation by Cytochrome P450
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Abstraction of the Hydrogen Atom of Methane by Iron−Oxo Species: The Concerted Reaction Path Is Energetically More Favorable
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Beyond Oil and Gas: The Methanol Economy
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Anthropogenic Chemical Carbon Cycle for a Sustainable Future
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The Direct Catalytic Oxidation of Methane to Methanol-A Critical Assessment
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Single Step Oxidation of Methane to Methanol–Towards Better Understanding
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The direct conversion of methane to methanol by controlled oxidation
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Strategies for the Direct Catalytic Valorization of Methane Using Heterogeneous Catalysis: Challenges and Opportunities
journal, April 2016

Enzymatic Oxidation of Methane
journal, March 2015

Alkane Oxidation: Methane Monooxygenases, Related Enzymes, and Their Biomimetics
journal, February 2017

Controlled Oxidation of Hydrocarbons by the Membrane-Bound Methane Monooxygenase: The Case for a Tricopper Cluster
journal, August 2008

Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts
journal, November 2017

Particulate methane monooxygenase contains only mononuclear copper centers
journal, May 2019

Iron and Copper Active Sites in Zeolites and Their Correlation to Metalloenzymes
journal, December 2017

Active sites and mechanisms in the direct conversion of methane to methanol using Cu in zeolitic hosts: a critical examination
journal, January 2020

Direct Conversion of Methane to Methanol under Mild Conditions over Cu-Zeolites and beyond
journal, January 2017

Selective anaerobic oxidation of methane enables direct synthesis of methanol
journal, May 2017

Low Temperature Activation of Methane on Metal-Oxides and Complex Interfaces: Insights from Surface Science
journal, July 2020

Low-temperature activation of methane on the IrO ₂ (110) surface
journal, April 2017

Surface characterization and methane activation on SnO _x /Cu ₂ O/Cu(111) inverse oxide/metal catalysts
journal, January 2021

Breaking Simple Scaling Relations through Metal–Oxide Interactions: Understanding Room-Temperature Activation of Methane on M/CeO ₂ (M = Pt, Ni, or Co) Interfaces
journal, October 2020

Low-temperature activation of methane on doped single atoms: descriptor and prediction
journal, January 2018

Direct Conversion of Methane to Methanol on Ni-Ceria Surfaces: Metal–Support Interactions and Water-Enabled Catalytic Conversion by Site Blocking
journal, May 2018

Low-Temperature Conversion of Methane to Methanol on CeO _x /Cu ₂ O Catalysts: Water Controlled Activation of the C–H Bond
journal, October 2016

Water-promoted interfacial pathways in methane oxidation to methanol on a CeO ₂ -Cu ₂ O catalyst
journal, April 2020

Selective Methane Oxidation to Methanol on ZnO/Cu₂O/Cu(111) Catalysts: Multiple Site-Dependent Behaviors
journal, November 2021

Inverse oxide/metal catalysts: A versatile approach for activity tests and mechanistic studies
journal, February 2010

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

Inverse Oxide/Metal Catalysts in Fundamental Studies and Practical Applications: A Perspective of Recent Developments
journal, June 2016

Ceria-based model catalysts: fundamental studies on the importance of the metal–ceria interface in CO oxidation, the water–gas shift, CO ₂ hydrogenation, and methane and alcohol reforming
journal, January 2017

Water-Gas Shift Reaction on a Highly Active Inverse CeO x /Cu(111) Catalyst: Unique Role of Ceria Nanoparticles
journal, October 2009

Hydroxylation of ZnO/Cu(1 1 1) inverse catalysts under ambient water vapor and the water–gas shift reaction
journal, August 2019

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

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

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

Methanol Synthesis from CO ₂ Hydrogenation over a Potassium-Promoted Cu _x O/Cu(111) ( x ≤ 2) Model Surface: Rationalizing the Potential of Potassium in Catalysis
journal, March 2020

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

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

The Unique Properties of the Oxide-Metal Interface: Reaction of Ethanol on an Inverse Model CeO _x –Au(111) Catalyst
journal, October 2014

In Situ Studies of Methanol Decomposition Over Cu(111) and Cu ₂ O/Cu(111): Effects of Reactant Pressure, Surface Morphology, and Hot Spots of Active Sites
journal, December 2020

Surface Science Studies of Gas Sensing Materials: SnO2
journal, October 2006

Cation-exchanged zeolites for the selective oxidation of methane to methanol
journal, January 2018

Growth, Structure, and Catalytic Properties of ZnO _x Grown on CuO _x /Cu(111) Surfaces
journal, October 2018

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

Inhomogeneous Electron Gas
journal, November 1964

Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965

Selective molecular adsorption in sub-nanometer cages of a Cu2O surface oxide
journal, January 2013