First-Principles Mechanistic Analysis of Dimethyl Ether Electro-Oxidation on Monometallic Single-Crystal Surfaces

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

doi:10.1021/jp505919x

Title: First-Principles Mechanistic Analysis of Dimethyl Ether Electro-Oxidation on Monometallic Single-Crystal Surfaces

Abstract

Dimethyl ether is an attractive alternative to petroleum fuels due to its physical properties, comparable energy density to methanol and ethanol, and minimal deleterious environmental/toxicological effects. For direct fuel cells, it has a number of advantages over other prominent fuels, including easier storage with respect to hydrogen, lower toxicity and crossover when compared to methanol, and more facile complete oxidation as compared to ethanol (which includes a relatively difficult to break C–C bond). However, the dimethyl ether electro-oxidation reaction is poorly understood, hindering the development of improved electrocatalysts. Using periodic, self-consistent (PW91-GGA) density functional theory calculations, we evaluate the thermochemistry of dimethyl ether (DME) electro-oxidation, at the elementary step level, on 12 model, closed-packed facets of pure transition metals: Au, Ag, Cu, Pt, Pd, Ni, Ir, Rh, Co, Os, Ru, and Re. From the calculated thermochemistry, we determine the most probable reaction paths on each of these surfaces, focusing on Pt as a model system. Our results predict two key electro-oxidation peaks. At lower potentials, there is a peak corresponding to partial oxidation of DME to CO (and other surface poisoning species) or complete oxidation to CO₂ via formic acid as a key intermediate. A second, higher-potential peak is duemore »« 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:: Wed Aug 27 00:00:00 EDT 2014

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:: 1405315

Grant/Contract Number:: FG02-05ER15731

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. C

Additional Journal Information:: Journal Volume: 118; Journal Issue: 42; Journal ID: ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 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. First-Principles Mechanistic Analysis of Dimethyl Ether Electro-Oxidation on Monometallic Single-Crystal Surfaces.  United States: N. p., 2014. 
Web.  doi:10.1021/jp505919x.

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                    Herron, Jeffrey A., Ferrin, Peter, & Mavrikakis, Manos. First-Principles Mechanistic Analysis of Dimethyl Ether Electro-Oxidation on Monometallic Single-Crystal Surfaces.  United States.  https://doi.org/10.1021/jp505919x

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                    Herron, Jeffrey A., Ferrin, Peter, and Mavrikakis, Manos. Wed .  
"First-Principles Mechanistic Analysis of Dimethyl Ether Electro-Oxidation on Monometallic Single-Crystal Surfaces".  United States.  https://doi.org/10.1021/jp505919x.  https://www.osti.gov/servlets/purl/1405315.

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@article{osti_1405315,

  title        = {First-Principles Mechanistic Analysis of Dimethyl Ether Electro-Oxidation on Monometallic Single-Crystal Surfaces},

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

  abstractNote = {Dimethyl ether is an attractive alternative to petroleum fuels due to its physical properties, comparable energy density to methanol and ethanol, and minimal deleterious environmental/toxicological effects. For direct fuel cells, it has a number of advantages over other prominent fuels, including easier storage with respect to hydrogen, lower toxicity and crossover when compared to methanol, and more facile complete oxidation as compared to ethanol (which includes a relatively difficult to break C–C bond). However, the dimethyl ether electro-oxidation reaction is poorly understood, hindering the development of improved electrocatalysts. Using periodic, self-consistent (PW91-GGA) density functional theory calculations, we evaluate the thermochemistry of dimethyl ether (DME) electro-oxidation, at the elementary step level, on 12 model, closed-packed facets of pure transition metals: Au, Ag, Cu, Pt, Pd, Ni, Ir, Rh, Co, Os, Ru, and Re. From the calculated thermochemistry, we determine the most probable reaction paths on each of these surfaces, focusing on Pt as a model system. Our results predict two key electro-oxidation peaks. At lower potentials, there is a peak corresponding to partial oxidation of DME to CO (and other surface poisoning species) or complete oxidation to CO2 via formic acid as a key intermediate. A second, higher-potential peak is due to complete oxidation of adsorbed CO (and other surface poisoning species) to CO2. Assuming the catalysts remain in their metallic state during the DME electro-oxidation process, our results suggest that the onset potential of the surfaces increases in the order Cu < Ni < Os < Rh < Ir < Co < Ru < Pt < Ag < Pd < Re < Au. Using our results, we construct a theoretical phase diagram showing predicted catalyst activity based on two key reactivity descriptors, the free energies of adsorbed CO and OH. Here, we compare all results to methanol electro-oxidation to understand key mechanistic differences and their impacts on optimal catalyst design for direct DME fuel cells.},

  doi          = {10.1021/jp505919x},

  journal      = {Journal of Physical Chemistry. C},

  number       = 42,

  volume       = 118,

  place        = {United States},

  year         = {Wed Aug 27 00:00:00 EDT 2014},

  month        = {Wed Aug 27 00:00:00 EDT 2014}

}

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Title: First-Principles Mechanistic Analysis of Dimethyl Ether Electro-Oxidation on Monometallic Single-Crystal Surfaces

Abstract

Citation Formats

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

Synthesis of dimethyl ether (DME) from methanol over solid-acid catalysts journal, February 1997

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

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

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

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

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

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

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

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

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

Electrochemical and infrared study of electro-oxidation of dimethyl ether (DME) on platinum polycrystalline electrode in acid solutions journal, September 2008

DME Dissociation Reaction on Platinum Electrode Surface: A Quantitative Kinetic Analysis by In Situ IR Spectroscopy journal, January 2010

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

Alloy catalysts designed from first principles journal, October 2004

Combinatorial Electrochemistry: A Highly Parallel, Optical Screening Method for Discovery of Better Electrocatalysts journal, June 1998

Catalytic consequences of acid strength in the conversion of methanol to dimethyl ether journal, February 2011

Direct Type Polymer Electrolyte Fuel Cells using Methoxy Fuel journal, January 2002

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

Electrocatalytic oxidation of dimethyl ether on ruthenium modified platinum single crystal electrodes journal, February 2009

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

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

Fuel cells using dimethyl ether journal, December 2006

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

Identification of Non-Precious Metal Alloy Catalysts for Selective Hydrogenation of Acetylene journal, June 2008

Trends in Atomic Adsorption on Pt 3 M(111) Transition Metal Bimetallic Surface Overlayers journal, April 2014

Disentangling ensemble, electronic and coverage effects on alloy catalysts: Vinyl acetate synthesis on Au/Pd(111) journal, April 2014

Monolayer bimetallic surfaces: Experimental and theoretical studies of trends in electronic and chemical properties journal, May 2008

Mixed-Metal Pt Monolayer Electrocatalysts for Enhanced Oxygen Reduction Kinetics journal, September 2005

Mixed-Metal Pt Monolayer Electrocatalysts with Improved CO Tolerance journal, November 2011

Alloys of platinum and early transition metals as oxygen reduction electrocatalysts journal, September 2009

Bifunctional anode catalysts for direct methanol fuel cells journal, January 2012

Selectivity driven design of bimetallic ethylene epoxidation catalysts from first principles journal, June 2004

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

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

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

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

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

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

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

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

Special Points in the Brillouin Zone journal, December 1973

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

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

Electrolysis of water on oxide surfaces journal, September 2007

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

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

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

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

Universality in Heterogeneous Catalysis journal, July 2002

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

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

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

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

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

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

Combining experiment and theory for understanding electrocatalysis journal, January 2005

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

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

Density-Functional Based Modeling of the Intermediate in the Water Production Reaction on Pt(111) journal, April 2004

Catalysts for direct formic acid fuel cells journal, April 2003

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

Modeling Ethanol Decomposition on Transition Metals: A Combined Application of Scaling and Brønsted−Evans−Polanyi Relations journal, April 2009

A review of anode catalysis in the direct methanol fuel cell journal, April 2006

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

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

Synthesis of dimethyl ether (DME) from methanol over solid-acid catalysts
journal, February 1997

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

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

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

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

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

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

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

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

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

Electrochemical and infrared study of electro-oxidation of dimethyl ether (DME) on platinum polycrystalline electrode in acid solutions
journal, September 2008

DME Dissociation Reaction on Platinum Electrode Surface: A Quantitative Kinetic Analysis by In Situ IR Spectroscopy
journal, January 2010

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

Alloy catalysts designed from first principles
journal, October 2004

Combinatorial Electrochemistry: A Highly Parallel, Optical Screening Method for Discovery of Better Electrocatalysts
journal, June 1998

Catalytic consequences of acid strength in the conversion of methanol to dimethyl ether
journal, February 2011

Direct Type Polymer Electrolyte Fuel Cells using Methoxy Fuel
journal, January 2002

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

Electrocatalytic oxidation of dimethyl ether on ruthenium modified platinum single crystal electrodes
journal, February 2009

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

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

Fuel cells using dimethyl ether
journal, December 2006

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

Identification of Non-Precious Metal Alloy Catalysts for Selective Hydrogenation of Acetylene
journal, June 2008

Trends in Atomic Adsorption on Pt ₃ M(111) Transition Metal Bimetallic Surface Overlayers
journal, April 2014

Disentangling ensemble, electronic and coverage effects on alloy catalysts: Vinyl acetate synthesis on Au/Pd(111)
journal, April 2014

Monolayer bimetallic surfaces: Experimental and theoretical studies of trends in electronic and chemical properties
journal, May 2008

Mixed-Metal Pt Monolayer Electrocatalysts for Enhanced Oxygen Reduction Kinetics
journal, September 2005

Mixed-Metal Pt Monolayer Electrocatalysts with Improved CO Tolerance
journal, November 2011

Alloys of platinum and early transition metals as oxygen reduction electrocatalysts
journal, September 2009

Bifunctional anode catalysts for direct methanol fuel cells
journal, January 2012

Selectivity driven design of bimetallic ethylene epoxidation catalysts from first principles
journal, June 2004

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

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

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

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

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

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

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

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

Special Points in the Brillouin Zone
journal, December 1973

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

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

Electrolysis of water on oxide surfaces
journal, September 2007

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

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

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

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

Universality in Heterogeneous Catalysis
journal, July 2002

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

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

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

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

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

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

Combining experiment and theory for understanding electrocatalysis
journal, January 2005

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

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

Density-Functional Based Modeling of the Intermediate in the Water Production Reaction on Pt(111)
journal, April 2004

Catalysts for direct formic acid fuel cells
journal, April 2003

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

Modeling Ethanol Decomposition on Transition Metals: A Combined Application of Scaling and Brønsted−Evans−Polanyi Relations
journal, April 2009

A review of anode catalysis in the direct methanol fuel cell
journal, April 2006

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