Theoretical Investigation of H₂ Oxidation on the Sr2Fe1.5Mo0.5O6 (001) Perovskite Surface Under Anodic Solid Oxide Fuel Cell Conditions

Suthirakun, Suwit; Ammal, Salai Cheettu; Munoz-Garcia, Ana B.; Xiao, Guoliang; Chen, Fanglin; zur Loye, Hans-Conrad; Carter, Emily A.; Heyden, Andreas

doi:10.1021/ja502629j

Title: Theoretical Investigation of H₂ Oxidation on the Sr₂Fe_1.5Mo_0.5O₆ (001) Perovskite Surface Under Anodic Solid Oxide Fuel Cell Conditions

Abstract

Periodic density functional theory (DFT) calculations and microkinetic modeling are used to investigate the electrochemical oxidation of H₂ fuel on the (001) surface of Sr₂Fe_1.5Mo_0.5O₆ (SFMO) perovskite under anodic solid oxide fuel cell conditions. Three surface models with different Fe/Mo ratios in the topmost layer-identified by ab initio thermodynamic analysis-are used to investigate the H₂ oxidation mechanism. A microkinetic analysis that considers the effects of anode bias potential suggests that a higher Mo concentration in the surface increases the activity of the surface toward H₂ oxidation. At operating voltage and anodic SOFC conditions, the model predicts that water desorption is rate-controlling and that stabilizing the oxygen vacancy structure increases the overall rate for H₂ oxidation. Although we find that Mo plays a crucial role in improving catalytic activity of SFMO, under fuel cell operating conditions, the Mo content in the surface layer tends to be very low. On the basis of these results and in agreement with previous experimental observations, a strategy for improving the overall electrochemical performance of SFMO is increasing the Mo content or adding small amounts of an active transition metal, such as Ni, to the surface to lower the oxygen vacancy formation energy of the SFMOmore » surface.« less

Authors:: Suthirakun, Suwit; Ammal, Salai Cheettu; Munoz-Garcia, Ana B.; Xiao, Guoliang; Chen, Fanglin; zur Loye, Hans-Conrad; Carter, Emily A.; Heyden, Andreas

Publication Date:: Wed Jun 11 00:00:00 EDT 2014

Research Org.:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL)

Sponsoring Org.:: USDOE

OSTI Identifier:: 1222135

DOE Contract Number:: AC05-76RL01830

Resource Type:: Journal Article

Journal Name:: Journal of the American Chemical Society, 136(23):8374–8386

Additional Journal Information:: Journal Name: Journal of the American Chemical Society, 136(23):8374–8386

Country of Publication:: United States

Language:: English

Subject:: Environmental Molecular Sciences Laboratory

Citation Formats


                    Suthirakun, Suwit, Ammal, Salai Cheettu, Munoz-Garcia, Ana B., Xiao, Guoliang, Chen, Fanglin, zur Loye, Hans-Conrad, Carter, Emily A., and Heyden, Andreas. Theoretical Investigation of H₂ Oxidation on the Sr2Fe1.5Mo0.5O6 (001) Perovskite Surface Under Anodic Solid Oxide Fuel Cell Conditions.  United States: N. p., 2014. 
        Web.  doi:10.1021/ja502629j.

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                    Suthirakun, Suwit, Ammal, Salai Cheettu, Munoz-Garcia, Ana B., Xiao, Guoliang, Chen, Fanglin, zur Loye, Hans-Conrad, Carter, Emily A., & Heyden, Andreas. Theoretical Investigation of H₂ Oxidation on the Sr2Fe1.5Mo0.5O6 (001) Perovskite Surface Under Anodic Solid Oxide Fuel Cell Conditions.  United States.  https://doi.org/10.1021/ja502629j

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                    Suthirakun, Suwit, Ammal, Salai Cheettu, Munoz-Garcia, Ana B., Xiao, Guoliang, Chen, Fanglin, zur Loye, Hans-Conrad, Carter, Emily A., and Heyden, Andreas. 2014.  
        "Theoretical Investigation of H₂ Oxidation on the Sr2Fe1.5Mo0.5O6 (001) Perovskite Surface Under Anodic Solid Oxide Fuel Cell Conditions".  United States.  https://doi.org/10.1021/ja502629j.

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@article{osti_1222135,

  title        = {Theoretical Investigation of H₂ Oxidation on the Sr2Fe1.5Mo0.5O6 (001) Perovskite Surface Under Anodic Solid Oxide Fuel Cell Conditions},

  author       = {Suthirakun, Suwit and Ammal, Salai Cheettu and Munoz-Garcia, Ana B. and Xiao, Guoliang and Chen, Fanglin and zur Loye, Hans-Conrad and Carter, Emily A. and Heyden, Andreas},

  abstractNote = {Periodic density functional theory (DFT) calculations and microkinetic modeling are used to investigate the electrochemical oxidation of H₂ fuel on the (001) surface of Sr2Fe1.5Mo0.5O6 (SFMO) perovskite under anodic solid oxide fuel cell conditions. Three surface models with different Fe/Mo ratios in the topmost layer-identified by ab initio thermodynamic analysis-are used to investigate the H₂ oxidation mechanism. A microkinetic analysis that considers the effects of anode bias potential suggests that a higher Mo concentration in the surface increases the activity of the surface toward H₂ oxidation. At operating voltage and anodic SOFC conditions, the model predicts that water desorption is rate-controlling and that stabilizing the oxygen vacancy structure increases the overall rate for H₂ oxidation. Although we find that Mo plays a crucial role in improving catalytic activity of SFMO, under fuel cell operating conditions, the Mo content in the surface layer tends to be very low. On the basis of these results and in agreement with previous experimental observations, a strategy for improving the overall electrochemical performance of SFMO is increasing the Mo content or adding small amounts of an active transition metal, such as Ni, to the surface to lower the oxygen vacancy formation energy of the SFMO surface.},

  doi          = {10.1021/ja502629j},

  url          = {https://www.osti.gov/biblio/1222135},
  journal      = {Journal of the American Chemical Society, 136(23):8374–8386},
number       = ,

  volume       = ,

  place        = {United States},

  year         = {Wed Jun 11 00:00:00 EDT 2014},

  month        = {Wed Jun 11 00:00:00 EDT 2014}

}

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Title: Theoretical Investigation of H₂ Oxidation on the Sr2Fe1.5Mo0.5O6 (001) Perovskite Surface Under Anodic Solid Oxide Fuel Cell Conditions

Abstract

Citation Formats

Advanced anodes for high-temperature fuel cells journal, January 2004

Solid oxide fuel cell technology?features and applications journal, October 2004

Ceramic Fuel Cells journal, March 1993

Solid Oxide Fuel Cells: Technology Status journal, January 2004

Redox Cycling of Ni-Based Solid Oxide Fuel Cell Anodes: A Review journal, June 2007

Characterization of Ni-YSZ Anode Degradation for Substrate-Type Solid Oxide Fuel Cells journal, January 1996

Wettability and interfacial reactions in the systems and Ni/Ti-TiO2/YSZ journal, September 1996

Nickel coarsening in annealed Ni/8YSZ anode substrates for solid oxide fuel cells journal, July 2000

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Improving the stability of direct-methane solid oxide fuel cells using anode barrier layers journal, August 2006

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Unveiling Structure–Property Relationships in Sr 2 Fe 1.5 Mo 0.5 O 6−δ , an Electrode Material for Symmetric Solid Oxide Fuel Cells journal, April 2012

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Synthesis and characterization of Mo-doped SrFeO3−δ as cathode materials for solid oxide fuel cells journal, March 2012

Sr2Fe1+xMo1-xO6- as Anode Materials for Solid Oxide Fuel Cells journal, April 2012

A Novel Electrode Material for Symmetrical SOFCs journal, October 2010

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

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

Generalized Gradient Approximation Made Simple journal, October 1996

Projector augmented-wave method journal, December 1994

Effect of Antisite Defects on the Formation of Oxygen Vacancies in Sr 2 FeMoO 6 : Implications for Ion and Electron Transport journal, October 2011

Special points for Brillouin-zone integrations journal, June 1976

Periodic boundary conditions in ab initio calculations journal, February 1995

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

Efficient methods for finding transition states in chemical reactions: Comparison of improved dimer method and partitioned rational function optimization method journal, December 2005

A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives journal, October 1999

Comparison of methods for finding saddle points without knowledge of the final states journal, November 2004

Degree of Rate Control: How Much the Energies of Intermediates and Transition States Control Rates journal, September 2009

Degree of Rate Control: How Much the Energies of Intermediates and Transition States Control Rates journal, June 2009

Modeling the noble metal/TiO2 (110) interface with hybrid DFT functionals: A periodic electrostatic embedded cluster model study journal, October 2010

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

Strong Chemical Interactions Between Au and Off-Stoichiometric Defects on TiO 2 as a Possible Source of Chemical Activity of Nanosized Au Supported on the Oxide journal, March 2009

Geometric and electronic characteristics of active sites on TiO2-supported Au nano-catalysts: insights from first principles journal, January 2009

CO oxidation at Pd ( 100 ) : A first-principles constrained thermodynamics study journal, May 2007

Recent anode advances in solid oxide fuel cells journal, September 2007

Relations between the Concentrations of Imperfections in Crystalline Solids book, January 1956

Sr2Fe1.5Mo0.5O6 as Cathodes for Intermediate-Temperature Solid Oxide Fuel Cells with La0.8Sr0.2Ga0.87Mg0.13O3 Electrolyte journal, January 2011

Cathode materials for solid oxide fuel cells: a review journal, October 2009

A rapid analytical assessment tool for three dimensional electrode microstructural networks with geometric sensitivity journal, January 2014

First-Principles Analysis of the Activity of Transition and Noble Metals in the Direct Utilization of Hydrocarbon Fuels at Solid Oxide Fuel Cell Operating Conditions journal, January 2009

First-Principles Investigations of Electrochemical Oxidation of Hydrogen at Solid Oxide Fuel Cell Operating Conditions journal, January 2007

Correction to “Nature of Pt n /TiO 2 (110) Interface under Water-Gas Shift Reaction Conditions: A Constrained ab Initio Thermodynamics Study” journal, December 2011

Nature of Pt n /TiO 2 (110) Interface under Water-Gas Shift Reaction Conditions: A Constrained ab Initio Thermodynamics Study journal, September 2011

Nature of Pt n /CeO 2 (111) Surface under Water–Gas Shift Reaction Conditions: A Constrained ab Initio Thermodynamics Study journal, April 2012

Combined DFT and Microkinetic Modeling Study of Hydrogen Oxidation at the Ni/YSZ Anode of Solid Oxide Fuel Cells journal, September 2012

The Electronic Structure and Chemical Properties of a Ni/CeO 2 Anode in a Solid Oxide Fuel Cell: A DFT + U Study journal, November 2010

Three-Dimensional Heteroatom-Doped Nanocarbon for Metal-Free Oxygen Reduction Electrocatalysis: A Review journal, July 2018

A Multiscale Model for Electrochemical Reactions in LSCF Based Solid Oxide Cells journal, January 2018

Nanometric Fe-Substituted ZrO 2 on Carbon Black as PGM-Free ORR Catalyst for PEMFCs journal, January 2019

Perovskite Oxyfluoride Electrode Enabling Direct Electrolyzing Carbon Dioxide with Excellent Electrochemical Performances journal, November 2018

A novel fuel electrode enabling direct CO 2 electrolysis with excellent and stable cell performance journal, January 2017

Sr 2 Fe 1.4 Mn 0.1 Mo 0.5 O 6−δ perovskite cathode for highly efficient CO 2 electrolysis journal, January 2019

Oxygen vacancy formation and migration in double perovskite Sr 2 CrMoO 6 : a first-principles study journal, January 2016

First principles analysis of oxygen vacancy formation and migration in Sr 2 BMoO 6 (B = Mg, Co, Ni) journal, January 2016

Nanometric Fe-Substituted ZrO₂ on Carbon Black as PGM-Free ORR Catalyst for PEMFCs text, January 2019

Title: Theoretical Investigation of H₂ Oxidation on the Sr₂Fe_1.5Mo_0.5O₆ (001) Perovskite Surface Under Anodic Solid Oxide Fuel Cell Conditions

Advanced anodes for high-temperature fuel cells
journal, January 2004

Solid oxide fuel cell technology?features and applications
journal, October 2004

Ceramic Fuel Cells
journal, March 1993

Solid Oxide Fuel Cells: Technology Status
journal, January 2004

Redox Cycling of Ni-Based Solid Oxide Fuel Cell Anodes: A Review
journal, June 2007

Characterization of Ni-YSZ Anode Degradation for Substrate-Type Solid Oxide Fuel Cells
journal, January 1996

Wettability and interfacial reactions in the systems and Ni/Ti-TiO2/YSZ
journal, September 1996

Nickel coarsening in annealed Ni/8YSZ anode substrates for solid oxide fuel cells
journal, July 2000

Electrochemical properties of Ni–YSZ cermet in solid oxide fuel cells Effect of current collecting
journal, January 2000

Improving the stability of direct-methane solid oxide fuel cells using anode barrier layers
journal, August 2006

Ni modified ceramic anodes for direct-methane solid oxide fuel cells
journal, January 2011

Unveiling Structure–Property Relationships in Sr ₂ Fe _1.5 Mo _0.5 O _6−δ , an Electrode Material for Symmetric Solid Oxide Fuel Cells
journal, April 2012

Oxide ion transport in Sr2Fe1.5Mo0.5O6−δ, a mixed ion-electron conductor: new insights from first principles modeling
journal, January 2013

Synthesis and characterization of Mo-doped SrFeO3−δ as cathode materials for solid oxide fuel cells
journal, March 2012

Sr2Fe1+xMo1-xO6- as Anode Materials for Solid Oxide Fuel Cells
journal, April 2012

A Novel Electrode Material for Symmetrical SOFCs
journal, October 2010

Structural transition and atomic ordering in the non-stoichiometric double perovskite Sr2FexMo2−xO6
journal, April 2003

Investigation of the high-temperature redox chemistry of Sr ₂ Fe _1.5 Mo _0.5 O _6−δ via in situ neutron diffraction
journal, January 2014

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

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

Generalized Gradient Approximation Made Simple
journal, October 1996

Projector augmented-wave method
journal, December 1994

Effect of Antisite Defects on the Formation of Oxygen Vacancies in Sr ₂ FeMoO ₆ : Implications for Ion and Electron Transport
journal, October 2011

Special points for Brillouin-zone integrations
journal, June 1976

Periodic boundary conditions in ab initio calculations
journal, February 1995

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

Efficient methods for finding transition states in chemical reactions: Comparison of improved dimer method and partitioned rational function optimization method
journal, December 2005

A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives
journal, October 1999

Comparison of methods for finding saddle points without knowledge of the final states
journal, November 2004

Degree of Rate Control: How Much the Energies of Intermediates and Transition States Control Rates
journal, September 2009

Degree of Rate Control: How Much the Energies of Intermediates and Transition States Control Rates
journal, June 2009

Modeling the noble metal/TiO2 (110) interface with hybrid DFT functionals: A periodic electrostatic embedded cluster model study
journal, October 2010

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

Strong Chemical Interactions Between Au and Off-Stoichiometric Defects on TiO ₂ as a Possible Source of Chemical Activity of Nanosized Au Supported on the Oxide
journal, March 2009

Geometric and electronic characteristics of active sites on TiO2-supported Au nano-catalysts: insights from first principles
journal, January 2009

$CO$ oxidation at $Pd (100)$ : A first-principles constrained thermodynamics study
journal, May 2007

Recent anode advances in solid oxide fuel cells
journal, September 2007

Relations between the Concentrations of Imperfections in Crystalline Solids
book, January 1956

Sr2Fe1.5Mo0.5O6 as Cathodes for Intermediate-Temperature Solid Oxide Fuel Cells with La0.8Sr0.2Ga0.87Mg0.13O3 Electrolyte
journal, January 2011

Cathode materials for solid oxide fuel cells: a review
journal, October 2009

A rapid analytical assessment tool for three dimensional electrode microstructural networks with geometric sensitivity
journal, January 2014

First-Principles Analysis of the Activity of Transition and Noble Metals in the Direct Utilization of Hydrocarbon Fuels at Solid Oxide Fuel Cell Operating Conditions
journal, January 2009

First-Principles Investigations of Electrochemical Oxidation of Hydrogen at Solid Oxide Fuel Cell Operating Conditions
journal, January 2007

Correction to “Nature of Pt _n /TiO ₂ (110) Interface under Water-Gas Shift Reaction Conditions: A Constrained ab Initio Thermodynamics Study”
journal, December 2011

Nature of Pt _n /TiO ₂ (110) Interface under Water-Gas Shift Reaction Conditions: A Constrained ab Initio Thermodynamics Study
journal, September 2011

Nature of Pt _n /CeO ₂ (111) Surface under Water–Gas Shift Reaction Conditions: A Constrained ab Initio Thermodynamics Study
journal, April 2012

Combined DFT and Microkinetic Modeling Study of Hydrogen Oxidation at the Ni/YSZ Anode of Solid Oxide Fuel Cells
journal, September 2012

The Electronic Structure and Chemical Properties of a Ni/CeO ₂ Anode in a Solid Oxide Fuel Cell: A DFT + U Study
journal, November 2010

Three-Dimensional Heteroatom-Doped Nanocarbon for Metal-Free Oxygen Reduction Electrocatalysis: A Review
journal, July 2018

A Multiscale Model for Electrochemical Reactions in LSCF Based Solid Oxide Cells
journal, January 2018

Nanometric Fe-Substituted ZrO ₂ on Carbon Black as PGM-Free ORR Catalyst for PEMFCs
journal, January 2019

Perovskite Oxyfluoride Electrode Enabling Direct Electrolyzing Carbon Dioxide with Excellent Electrochemical Performances
journal, November 2018

A novel fuel electrode enabling direct CO ₂ electrolysis with excellent and stable cell performance
journal, January 2017

Sr ₂ Fe _1.4 Mn _0.1 Mo _0.5 O _6−δ perovskite cathode for highly efficient CO ₂ electrolysis
journal, January 2019

Oxygen vacancy formation and migration in double perovskite Sr ₂ CrMoO ₆ : a first-principles study
journal, January 2016

First principles analysis of oxygen vacancy formation and migration in Sr ₂ BMoO ₆ (B = Mg, Co, Ni)
journal, January 2016

Nanometric Fe-Substituted ZrO₂ on Carbon Black as PGM-Free ORR Catalyst for PEMFCs
text, January 2019