On the Structure Sensitivity of Dimethyl Ether Electro-oxidation on Eight FCC Metals: A First-Principles Study

Herron, Jeffrey A.; Ferrin, Peter; Mavrikakis, Manos

doi:10.1007/s11244-015-0495-5

Title: On the Structure Sensitivity of Dimethyl Ether Electro-oxidation on Eight FCC Metals: A First-Principles Study

Abstract

The electro-oxidation of dimethyl ether (DME) was investigated using periodic, self-consistent density functional theory (DFT) calculations on the (111) and (100) facets of eight fcc metals: Au, Ag, Cu, Pt, Pd, Ni, Ir, and Rh. The goal of this study is to understand the experimentally observed structure sensitivity of this reaction on Pt, and to predict trends in structure sensitivity of this reaction across the other seven metals studied. The main conclusion is that the enhanced activity of Pt(100) originates from more facile C–O bond breaking and removal of surface poisoning species, including CO and CH. When comparing C–O bond breaking energetics, we do not find a universal trend where these elementary steps are always more exergonic on the (100) facet. However, we find that, at a given potential, DME can be dehydrogenated (prior to breaking the C–O bond) to a greater extent on the (100) facet. Additionally, we find that the reaction energy for C–O bond breaking in CHxOCHy-type species becomes increasingly exergonic as the species becomes increasingly dehydrogenated. Together, the more facile dehydrogenation on the (100) facets provides more favorable routes to C–O bond activation. Though we calculate a lower onset potential on Au(100), Ag(100), Cu(100), Pt(100), andmore »« less

Authors:

Herron, Jeffrey A. ^[1]; Ferrin, Peter ^[1]; Mavrikakis, Manos ^[1]

Univ. of Wisconsin-Madison, Madison, WI (United States). Dept. of Chemical and Biological Engineering

Publication Date:: Thu Sep 24 00:00:00 EDT 2015

Research Org.:: Univ. of Wisconsin, Madison, WI (United States)

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

Contributing Org.:: EMSL, a National scientific user facility at Pacific Northwest National Laboratory (PNNL); the Center for Nanoscale Materials at Argonne National Laboratory (ANL); and the National Energy Research Scientific Computing Center (NERSC)

OSTI Identifier:: 1405310

Grant/Contract Number:: FG02-05ER15731

Resource Type:: Accepted Manuscript

Journal Name:: Topics in Catalysis

Additional Journal Information:: Journal Volume: 58; Journal Issue: 18-20; Journal ID: ISSN 1022-5528

Publisher:: Springer

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; density functional theory; heterogeneous catalysis; thermochemistry; electrocatalysis; oxidation; dimethyl ether

Citation Formats


                    Herron, Jeffrey A., Ferrin, Peter, and Mavrikakis, Manos. On the Structure Sensitivity of Dimethyl Ether Electro-oxidation on Eight FCC Metals: A First-Principles Study.  United States: N. p., 2015. 
Web.  doi:10.1007/s11244-015-0495-5.

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                    Herron, Jeffrey A., Ferrin, Peter, & Mavrikakis, Manos. On the Structure Sensitivity of Dimethyl Ether Electro-oxidation on Eight FCC Metals: A First-Principles Study.  United States.  https://doi.org/10.1007/s11244-015-0495-5

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                    Herron, Jeffrey A., Ferrin, Peter, and Mavrikakis, Manos. Thu .  
"On the Structure Sensitivity of Dimethyl Ether Electro-oxidation on Eight FCC Metals: A First-Principles Study".  United States.  https://doi.org/10.1007/s11244-015-0495-5.  https://www.osti.gov/servlets/purl/1405310.

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@article{osti_1405310,

  title        = {On the Structure Sensitivity of Dimethyl Ether Electro-oxidation on Eight FCC Metals: A First-Principles Study},

  author       = {Herron, Jeffrey A. and Ferrin, Peter and Mavrikakis, Manos},

  abstractNote = {The electro-oxidation of dimethyl ether (DME) was investigated using periodic, self-consistent density functional theory (DFT) calculations on the (111) and (100) facets of eight fcc metals: Au, Ag, Cu, Pt, Pd, Ni, Ir, and Rh. The goal of this study is to understand the experimentally observed structure sensitivity of this reaction on Pt, and to predict trends in structure sensitivity of this reaction across the other seven metals studied. The main conclusion is that the enhanced activity of Pt(100) originates from more facile C–O bond breaking and removal of surface poisoning species, including CO and CH. When comparing C–O bond breaking energetics, we do not find a universal trend where these elementary steps are always more exergonic on the (100) facet. However, we find that, at a given potential, DME can be dehydrogenated (prior to breaking the C–O bond) to a greater extent on the (100) facet. Additionally, we find that the reaction energy for C–O bond breaking in CHxOCHy-type species becomes increasingly exergonic as the species becomes increasingly dehydrogenated. Together, the more facile dehydrogenation on the (100) facets provides more favorable routes to C–O bond activation. Though we calculate a lower onset potential on Au(100), Ag(100), Cu(100), Pt(100), and Pd(100) than their respective (111) facets, the calculated onset potential for Ni(100), Ir(100), and Rh(100) are actually higher than for their respective (111) facets. Lastly, by constructing theoretical volcano plots, we conclude that Au(100), Ag(100), Cu(100), Pt(100), and Pd(100) should be more active than their respective (111) facets, while Ni(100), Rh(100), and Ir(100) will show the opposite trend.},

  doi          = {10.1007/s11244-015-0495-5},

  journal      = {Topics in Catalysis},

  number       = 18-20,

  volume       = 58,

  place        = {United States},

  year         = {Thu Sep 24 00:00:00 EDT 2015},

  month        = {Thu Sep 24 00:00:00 EDT 2015}

}

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Title: On the Structure Sensitivity of Dimethyl Ether Electro-oxidation on Eight FCC Metals: A First-Principles Study

Abstract

Citation Formats

Dimethyl ether (DME) as an alternative fuel journal, June 2006

Anode reaction mechanism and crossover in direct dimethyl ether fuel cell journal, June 2006

Carbon Monoxide Dissociation on Planar and Stepped Ru(0001) Surfaces journal, April 2003

Electrocatalytic Oxidation of Ammonia on Transition-Metal Surfaces: A First-Principles Study journal, February 2015

Accurate coverage-dependence incorporated into first-principles kinetic models: Catalytic NO oxidation on Pt (111) journal, February 2012

Structure sensitivity of the methanation reaction: H2-induced CO dissociation on nickel surfaces journal, April 2008

Universality in Heterogeneous Catalysis journal, July 2002

Methanol oxidation and direct methanol fuel cells: a selective review journal, January 1999

Configurational correlations in the coverage dependent adsorption energies of oxygen atoms on late transition metal fcc(111) surfaces journal, March 2011

Structure and Bonding of Water on Pt(111) journal, December 2002

Thermodynamic theory of multi-electron transfer reactions: Implications for electrocatalysis journal, September 2011

Electro-oxidation of dimethyl ether on Pt/C and PtMe/C catalysts in sulfuric acid journal, September 2006

General Rules for Predicting Where a Catalytic Reaction Should Occur on Metal Surfaces: A Density Functional Theory Study of C−H and C−O Bond Breaking/Making on Flat, Stepped, and Kinked Metal Surfaces journal, February 2003

Competitive Paths for Methanol Decomposition on Pt(111) journal, March 2004

A first principles analysis of CO oxidation over Pt and Pt66.7%Ru33.3% (111) surfaces journal, November 2003

First-Principles Mechanistic Analysis of Dimethyl Ether Electro-Oxidation on Monometallic Single-Crystal Surfaces journal, September 2014

Intermetallic Alloys as CO Electroreduction Catalysts—Role of Isolated Active Sites journal, May 2014

Combining experiment and theory for understanding electrocatalysis journal, January 2005

Iron single crystals as ammonia synthesis catalysts: Effect of surface structure on catalyst activity journal, March 1982

A review of the state-of-the-art of the methanol crossover in direct methanol fuel cells journal, November 1999

Electro-oxidation of dimethyl ether on platinum nanocubes with preferential {100} surfaces journal, August 2009

Reactivity descriptors for direct methanol fuel cell anode catalysts journal, November 2008

Electrolysis of water on (oxidized) metal surfaces journal, December 2005

A first-principles study of surface and subsurface H on and in Ni(111): diffusional properties and coverage-dependent behavior journal, August 2003

Surface Structure Dependent Electro-oxidation of Dimethyl Ether on Platinum Single-Crystal Electrodes journal, December 2007

CO activation pathways and the mechanism of Fischer–Tropsch synthesis journal, June 2010

Structure Dependence of NO Adsorption and Dissociation on Platinum Surfaces journal, February 2004

Electro-oxidation of Dimethyl Ether in a Polymer-Electrolyte-Membrane Fuel Cell journal, January 2000

Bond-Making and Breaking between Carbon, Nitrogen, and Oxygen in Electrocatalysis journal, October 2014

Understanding Trends in Catalytic Activity: The Effect of Adsorbate–Adsorbate Interactions for CO Oxidation Over Transition Metals journal, February 2010

Why (1 0 0) Terraces Break and Make Bonds: Oxidation of Dimethyl Ether on Platinum Single-Crystal Electrodes journal, September 2013

Performance of direct dimethyl ether fuel cells at low temperature journal, December 2005

E LECTRONIC S TRUCTURE AND C ATALYSIS ON M ETAL S URFACES journal, October 2002

Exceptional Size-Dependent Activity Enhancement in the Electroreduction of CO 2 over Au Nanoparticles journal, November 2014

Electrolysis of water on oxide surfaces journal, September 2007

A First-Principles Study of Methanol Decomposition on Pt(111) journal, June 2002

Estimations of electric field effects on the oxygen reduction reaction based on the density functional theory journal, January 2007

Role of Crystalline Defects in Electrocatalysis: CO Adsorption and Oxidation on Stepped Platinum Electrodes As Studied by in situ Infrared Spectroscopy journal, September 2002

Special points for Brillouin-zone integrations journal, June 1976

Structure Sensitivity of Methanol Electrooxidation on Transition Metals journal, October 2009

Electrochemical behaviors of dimethyl ether on platinum single crystal electrodes. Part I: Pt(111) journal, July 2008

Thermodynamics of Environment-Dependent Oxygen Chemisorption on Pt(111) journal, June 2008

Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals journal, March 1999

Hybrid and single feedstock energy processes for liquid transportation fuels: A critical review journal, June 2012

Energy of Molecularly Adsorbed Water on Clean Pt(111) and Pt(111) with Coadsorbed Oxygen by Calorimetry journal, April 2011

Scaling Properties of Adsorption Energies for Hydrogen-Containing Molecules on Transition-Metal Surfaces journal, July 2007

Complementary Structure Sensitive and Insensitive Catalytic Relationships journal, January 2009

Methoxy methane (dimethyl ether) as an alternative fuel for direct fuel cells journal, June 2006

Structure sensitivity for NO dissociation on palladium and rhodium surfaces journal, January 2003

Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation journal, September 1992

Mechanism of di(methyl)ether (DME) electrooxidation at platinum electrodes in acid medium journal, December 2005

Fuel cells using dimethyl ether journal, December 2006

Electrochemical behaviors of dimethyl ether on platinum single crystal electrodes. Part II: Pt(100) journal, April 2010

Soft self-consistent pseudopotentials in a generalized eigenvalue formalism journal, April 1990

Special Points in the Brillouin Zone journal, December 1973

Adsorbate-substrate and adsorbate-adsorbate interactions of Na and K adlayers on Al(111) journal, December 1992

Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode journal, November 2004

Structure sensitivity and nanoscale effects in electrocatalysis journal, January 2011

Direct liquid-feed fuel cells: Thermodynamic and environmental concerns journal, June 2007

Role of Steps in N 2 Activation on Ru(0001) journal, August 1999

The Brønsted–Evans–Polanyi Relation and the Volcano Plot for Ammonia Synthesis over Transition Metal Catalysts journal, January 2001

Progress in development of direct dimethyl ether fuel cells journal, September 2009

Graphether: a two-dimensional oxocarbon as a direct wide-band-gap semiconductor with high mechanical and electrical performances journal, January 2019

Structure Sensitivity of Formic Acid Electrooxidation on Transition Metal Surfaces: A First-Principles Study journal, January 2018

Graphether: A Two-Dimensional Oxocarbon as a Direct Wide-Gap Semiconductor with High Mechanical and Electrical Performances text, January 2019

Dimethyl ether (DME) as an alternative fuel
journal, June 2006

Anode reaction mechanism and crossover in direct dimethyl ether fuel cell
journal, June 2006

Carbon Monoxide Dissociation on Planar and Stepped Ru(0001) Surfaces
journal, April 2003

Electrocatalytic Oxidation of Ammonia on Transition-Metal Surfaces: A First-Principles Study
journal, February 2015

Accurate coverage-dependence incorporated into first-principles kinetic models: Catalytic NO oxidation on Pt (111)
journal, February 2012

Structure sensitivity of the methanation reaction: H2-induced CO dissociation on nickel surfaces
journal, April 2008

Universality in Heterogeneous Catalysis
journal, July 2002

Methanol oxidation and direct methanol fuel cells: a selective review
journal, January 1999

Configurational correlations in the coverage dependent adsorption energies of oxygen atoms on late transition metal fcc(111) surfaces
journal, March 2011

Structure and Bonding of Water on Pt(111)
journal, December 2002

Thermodynamic theory of multi-electron transfer reactions: Implications for electrocatalysis
journal, September 2011

Electro-oxidation of dimethyl ether on Pt/C and PtMe/C catalysts in sulfuric acid
journal, September 2006

General Rules for Predicting Where a Catalytic Reaction Should Occur on Metal Surfaces: A Density Functional Theory Study of C−H and C−O Bond Breaking/Making on Flat, Stepped, and Kinked Metal Surfaces
journal, February 2003

Competitive Paths for Methanol Decomposition on Pt(111)
journal, March 2004

A first principles analysis of CO oxidation over Pt and Pt66.7%Ru33.3% (111) surfaces
journal, November 2003

First-Principles Mechanistic Analysis of Dimethyl Ether Electro-Oxidation on Monometallic Single-Crystal Surfaces
journal, September 2014

Intermetallic Alloys as CO Electroreduction Catalysts—Role of Isolated Active Sites
journal, May 2014

Combining experiment and theory for understanding electrocatalysis
journal, January 2005

Iron single crystals as ammonia synthesis catalysts: Effect of surface structure on catalyst activity
journal, March 1982

A review of the state-of-the-art of the methanol crossover in direct methanol fuel cells
journal, November 1999

Electro-oxidation of dimethyl ether on platinum nanocubes with preferential {100} surfaces
journal, August 2009

Reactivity descriptors for direct methanol fuel cell anode catalysts
journal, November 2008

Electrolysis of water on (oxidized) metal surfaces
journal, December 2005

A first-principles study of surface and subsurface H on and in Ni(111): diffusional properties and coverage-dependent behavior
journal, August 2003

Surface Structure Dependent Electro-oxidation of Dimethyl Ether on Platinum Single-Crystal Electrodes
journal, December 2007

CO activation pathways and the mechanism of Fischer–Tropsch synthesis
journal, June 2010

Structure Dependence of NO Adsorption and Dissociation on Platinum Surfaces
journal, February 2004

Electro-oxidation of Dimethyl Ether in a Polymer-Electrolyte-Membrane Fuel Cell
journal, January 2000

Bond-Making and Breaking between Carbon, Nitrogen, and Oxygen in Electrocatalysis
journal, October 2014

Understanding Trends in Catalytic Activity: The Effect of Adsorbate–Adsorbate Interactions for CO Oxidation Over Transition Metals
journal, February 2010

Why (1 0 0) Terraces Break and Make Bonds: Oxidation of Dimethyl Ether on Platinum Single-Crystal Electrodes
journal, September 2013

Performance of direct dimethyl ether fuel cells at low temperature
journal, December 2005

E LECTRONIC S TRUCTURE AND C ATALYSIS ON M ETAL S URFACES
journal, October 2002

Exceptional Size-Dependent Activity Enhancement in the Electroreduction of CO ₂ over Au Nanoparticles
journal, November 2014

Electrolysis of water on oxide surfaces
journal, September 2007

A First-Principles Study of Methanol Decomposition on Pt(111)
journal, June 2002

Estimations of electric field effects on the oxygen reduction reaction based on the density functional theory
journal, January 2007

Role of Crystalline Defects in Electrocatalysis: CO Adsorption and Oxidation on Stepped Platinum Electrodes As Studied by in situ Infrared Spectroscopy
journal, September 2002

Special points for Brillouin-zone integrations
journal, June 1976

Structure Sensitivity of Methanol Electrooxidation on Transition Metals
journal, October 2009

Electrochemical behaviors of dimethyl ether on platinum single crystal electrodes. Part I: Pt(111)
journal, July 2008

Thermodynamics of Environment-Dependent Oxygen Chemisorption on Pt(111)
journal, June 2008

Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals
journal, March 1999

Hybrid and single feedstock energy processes for liquid transportation fuels: A critical review
journal, June 2012

Energy of Molecularly Adsorbed Water on Clean Pt(111) and Pt(111) with Coadsorbed Oxygen by Calorimetry
journal, April 2011

Scaling Properties of Adsorption Energies for Hydrogen-Containing Molecules on Transition-Metal Surfaces
journal, July 2007

Complementary Structure Sensitive and Insensitive Catalytic Relationships
journal, January 2009

Methoxy methane (dimethyl ether) as an alternative fuel for direct fuel cells
journal, June 2006

Structure sensitivity for NO dissociation on palladium and rhodium surfaces
journal, January 2003

Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation
journal, September 1992

Mechanism of di(methyl)ether (DME) electrooxidation at platinum electrodes in acid medium
journal, December 2005

Fuel cells using dimethyl ether
journal, December 2006

Electrochemical behaviors of dimethyl ether on platinum single crystal electrodes. Part II: Pt(100)
journal, April 2010

Soft self-consistent pseudopotentials in a generalized eigenvalue formalism
journal, April 1990

Special Points in the Brillouin Zone
journal, December 1973

Adsorbate-substrate and adsorbate-adsorbate interactions of Na and K adlayers on Al(111)
journal, December 1992

Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode
journal, November 2004

Structure sensitivity and nanoscale effects in electrocatalysis
journal, January 2011

Direct liquid-feed fuel cells: Thermodynamic and environmental concerns
journal, June 2007

Role of Steps in $N_{2}$ Activation on Ru(0001)
journal, August 1999

The Brønsted–Evans–Polanyi Relation and the Volcano Plot for Ammonia Synthesis over Transition Metal Catalysts
journal, January 2001

Progress in development of direct dimethyl ether fuel cells
journal, September 2009

Graphether: a two-dimensional oxocarbon as a direct wide-band-gap semiconductor with high mechanical and electrical performances
journal, January 2019

Structure Sensitivity of Formic Acid Electrooxidation on Transition Metal Surfaces: A First-Principles Study
journal, January 2018

Graphether: A Two-Dimensional Oxocarbon as a Direct Wide-Gap Semiconductor with High Mechanical and Electrical Performances
text, January 2019