Interfacial and Alloying Effects on Activation of Ethanol from First-Principles

An, Wei; Men, Yong; Wang, Jinguo; Liu, Ping

doi:10.1021/acs.jpcc.6b12720

Title: Interfacial and Alloying Effects on Activation of Ethanol from First-Principles

Abstract

Here, we present a first-principles density-functional theory study of ethanol activation at oxide/Rh(111) interface and the alloying effect on mitigating carbon deposition, which are essential to direct ethanol fuel cell (DEFC) anode reaction and steam reforming of ethanol (SRE) reaction. Our calculated results show that charge can transfer from Rh(111) substrate to MO_x chain (e.g., MoO₃ and MnO₂), or from MO_x chain (e.g., MgO, SnO₂, ZrO₂, and TiO₂) to Rh(111) substrate. The OH-binding strength is increased exponentially with M^δ+ charge ranging from 1.4 to 2.2, which renders MnO₂/Rh(111) and MgO/Rh(111) interfaces weaker OH-binding, and thereby enhanced oxidizing functionality of OH* for promoting ethanol oxidation reaction (EOR) at DEFC anode. For efficient C–C bond breaking, a large number of Rh ensemble sizes are critically needed at the interface of MO_x/Rh(111). We found that Rh₁Au₃ near surface alloy has the weakest C* and CO* binding, followed by Rh₁Cu₃ and Rh₁Pd₃ near surface alloys, while Rh₁Ir₃ and Rh₁Ru₃ surface alloys have C* and CO* binding strength similar to that of pure Rh metal. The general implication of this study is that by engineering alloyed structure of weakened C* and CO* binding complemented with metal oxides of weakened OH-binding, high-performance DEFC anode or SREmore » catalysts can be identified.« less

Authors:

^[1]; Men, Yong ^[1]; Wang, Jinguo ^[1];

^[2]

Shanghai Univ. of Engineering Science, Shanghai (China). College of Chemistry and Chemical Engineering
Brookhaven National Lab. (BNL), Upton, NY (United States). Dept. of Chemistry

Publication Date:: Fri Feb 24 00:00:00 EST 2017

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

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Natural Science Foundation of China (NSFC)

OSTI Identifier:: 1361266

Report Number(s):: BNL-113897-2017-JA
Journal ID: ISSN 1932-7447; R&D Project: CO040; KC0302010

Grant/Contract Number:: SC0012704; 21673137; 16ZR1413900; nhrc-2015- 01; AC02-05CH11231

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. C

Additional Journal Information:: Journal Volume: 121; Journal Issue: 10; Journal ID: ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats


                    An, Wei, Men, Yong, Wang, Jinguo, and Liu, Ping. Interfacial and Alloying Effects on Activation of Ethanol from First-Principles.  United States: N. p., 2017. 
Web.  doi:10.1021/acs.jpcc.6b12720.

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                    An, Wei, Men, Yong, Wang, Jinguo, & Liu, Ping. Interfacial and Alloying Effects on Activation of Ethanol from First-Principles.  United States.  https://doi.org/10.1021/acs.jpcc.6b12720

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                    An, Wei, Men, Yong, Wang, Jinguo, and Liu, Ping. Fri .  
"Interfacial and Alloying Effects on Activation of Ethanol from First-Principles".  United States.  https://doi.org/10.1021/acs.jpcc.6b12720.  https://www.osti.gov/servlets/purl/1361266.

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@article{osti_1361266,

  title        = {Interfacial and Alloying Effects on Activation of Ethanol from First-Principles},

  author       = {An, Wei and Men, Yong and Wang, Jinguo and Liu, Ping},

  abstractNote = {Here, we present a first-principles density-functional theory study of ethanol activation at oxide/Rh(111) interface and the alloying effect on mitigating carbon deposition, which are essential to direct ethanol fuel cell (DEFC) anode reaction and steam reforming of ethanol (SRE) reaction. Our calculated results show that charge can transfer from Rh(111) substrate to MOx chain (e.g., MoO3 and MnO2), or from MOx chain (e.g., MgO, SnO2, ZrO2, and TiO2) to Rh(111) substrate. The OH-binding strength is increased exponentially with Mδ+ charge ranging from 1.4 to 2.2, which renders MnO2/Rh(111) and MgO/Rh(111) interfaces weaker OH-binding, and thereby enhanced oxidizing functionality of OH* for promoting ethanol oxidation reaction (EOR) at DEFC anode. For efficient C–C bond breaking, a large number of Rh ensemble sizes are critically needed at the interface of MOx/Rh(111). We found that Rh1Au3 near surface alloy has the weakest C* and CO* binding, followed by Rh1Cu3 and Rh1Pd3 near surface alloys, while Rh1Ir3 and Rh1Ru3 surface alloys have C* and CO* binding strength similar to that of pure Rh metal. The general implication of this study is that by engineering alloyed structure of weakened C* and CO* binding complemented with metal oxides of weakened OH-binding, high-performance DEFC anode or SRE catalysts can be identified.},

  doi          = {10.1021/acs.jpcc.6b12720},

  journal      = {Journal of Physical Chemistry. C},

  number       = 10,

  volume       = 121,

  place        = {United States},

  year         = {Fri Feb 24 00:00:00 EST 2017},

  month        = {Fri Feb 24 00:00:00 EST 2017}

}

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Title: Interfacial and Alloying Effects on Activation of Ethanol from First-Principles

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The complex behavior of the Pd 7 cluster supported on TiO 2 (110) during CO oxidation: adsorbate-driven promoting effect journal, January 2016

Significance of β-dehydrogenation in ethanol electro-oxidation on platinum doped with Ru, Rh, Pd, Os and Ir journal, January 2014

Palladium–Tin Alloyed Catalysts for the Ethanol Oxidation Reaction in an Alkaline Medium journal, January 2012

Density Functional Theory Studies of Ethanol Decomposition on Rh(211) journal, October 2011

Activity of CeOx and TiOx Nanoparticles Grown on Au(111) in the Water-Gas Shift Reaction journal, December 2007

Insight into steam reforming of ethanol to produce hydrogen for fuel cells journal, March 2006

Electro-Oxidation of Ethanol on Pt, Rh, and PtRh Electrodes. A Study Using DEMS and in-Situ FTIR Techniques journal, September 2002

Toward Understanding Metal-Catalyzed Ethanol Reforming journal, May 2015

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

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

Iridium–Ruthenium Alloyed Nanoparticles for the Ethanol Oxidation Fuel Cell Reactions journal, May 2012

Role of Water and Adsorbed Hydroxyls on Ethanol Electrochemistry on Pd: New Mechanism, Active Centers, and Energetics for Direct Ethanol Fuel Cell Running in Alkaline Medium journal, March 2014

Alloy catalysts designed from first principles journal, October 2004

Ternary Pt/Rh/SnO2 electrocatalysts for oxidizing ethanol to CO2 journal, January 2009

Platinum-Tin Oxide Core–Shell Catalysts for Efficient Electro-Oxidation of Ethanol journal, July 2014

Current Status of Hydrogen Production Techniques by Steam Reforming of Ethanol: A Review journal, September 2005

Ab initiomolecular dynamics for liquid metals journal, January 1993

Highly active and selective binary MgO–SiO 2 catalysts for the production of 1,3-butadiene from ethanol journal, January 2017

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

Ethanol Steam Reforming on Rh Catalysts: Theoretical and Experimental Understanding journal, December 2013

Interfacial Effects in Iron-Nickel Hydroxide-Platinum Nanoparticles Enhance Catalytic Oxidation journal, May 2014

High-precision sampling for Brillouin-zone integration in metals journal, August 1989

Synergistic Effect of Tungsten Carbide and Palladium on Graphene for Promoted Ethanol Electrooxidation journal, July 2013

H2 Production from Ethanol over Rh–Pt/CeO2 Catalysts: The Role of Rh for the Efficient Dissociation of the Carbon–Carbon Bond journal, June 2002

Ethanol steam reforming over MgxNi1−xAl2O3 spinel oxide-supported Rh catalysts journal, July 2005

Renewable Hydrogen from Ethanol by Autothermal Reforming journal, February 2004

Design of Nanocatalysts for Green Hydrogen Production from Bioethanol journal, December 2011

Ternary Electrocatalysts for Oxidizing Ethanol to Carbon Dioxide: Making Ir Capable of Splitting C–C Bond journal, December 2012

Highly Active Iridium/Iridium–Tin/Tin Oxide Heterogeneous Nanoparticles as Alternative Electrocatalysts for the Ethanol Oxidation Reaction journal, September 2011

Ternary PtSnRh–SnO2 nanoclusters: synthesis and electroactivity for ethanol oxidation fuel cell reaction journal, January 2011

Understanding of ethanol decomposition on Rh(111) from density functional theory and kinetic Monte Carlo simulations journal, May 2011

Electrochemical dissolution of surface alloys in acids: Thermodynamic trends from first-principles calculations journal, May 2007

Theoretical Calculation of the Dehydrogenation of Ethanol on a Rh/CeO 2 (111) Surface journal, August 2006

Water-gas shift reaction on oxide/Cu(111): Rational catalyst screening from density functional theory journal, November 2010

First Principle Study of Ethanol Adsorption and Formation of Hydrogen Bond on Rh(111) Surface journal, May 2007

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

Special points for Brillouin-zone integrations journal, June 1976

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

Production of Hydrogen from Ethanol: Review of Reaction Mechanism and Catalyst Deactivation journal, April 2012

Mechanism of Ethanol Reforming: Theoretical Foundations journal, March 2009

Early stages in the oxidation of ethanol at low index single crystal platinum electrodes journal, November 1997

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

Surface segregation energies in transition-metal alloys journal, June 1999

Rationalization of Au Concentration and Distribution in AuNi@Pt Core–Shell Nanoparticles for Oxygen Reduction Reaction journal, September 2015

Reversible work transition state theory: application to dissociative adsorption of hydrogen journal, February 1995

In Situ Probing of the Active Site Geometry of Ultrathin Nanowires for the Oxygen Reduction Reaction journal, September 2015

Design of a Surface Alloy Catalyst for Steam Reforming journal, March 1998

Bio-ethanol catalytic steam reforming over supported metal catalysts journal, June 2002

First-principles study of methane dehydrogenation on a bimetallic Cu/Ni(111) surface journal, November 2009

A review on reforming bio-ethanol for hydrogen production journal, October 2007

A dems and FTir spectroscopic investigation of adsorbed ethanol on polycrystalline platinum journal, March 1994

Towards the computational design of solid catalysts journal, April 2009

Catalysts for direct ethanol fuel cells journal, June 2007

Ab Initio Study of CO Hydrogenation to Oxygenates on Reduced Rh Terraces and Stepped Surfaces journal, May 2010

Influence of Cluster–Support Interactions on Reactivity of Size-Selected Nb x O y Clusters journal, April 2015

In situ FTIR spectroscopic studies of electrooxidation of ethanol on Pd electrode in alkaline media journal, November 2010

Ethanol Steam Reforming in a Microchannel Reactor journal, January 2007

High Activity of Ce1−xNixO2−y for H2 Production through Ethanol Steam Reforming: Tuning Catalytic Performance through Metal-Oxide Interactions journal, November 2010

Ethanol Activation on Closed-Packed Surfaces journal, December 2014

C 2 N-graphene supported single-atom catalysts for CO 2 electrochemical reduction reaction: mechanistic insight and catalyst screening journal, January 2018

Nanocatalysts for Electrocatalytic Oxidation of Ethanol journal, April 2019

Intrinsic composition and electronic effects of multicomponent platinum nanocatalysts with high activity and selectivity for ethanol oxidation reaction journal, January 2018

Comparative study on hydrogenation of propanal on Ni(111) and Cu(111) from density functional theory
journal, February 2017

Hydrogen production from ethanol over bimetallic Rh-M/CeO2 (M=Pd or Pt)
journal, December 2007

One-Dimensional Ni-Based Nanostructures and Their Application as Solid Oxide Fuel Cell Anodes: A DFT Investigation
journal, January 2013

Catalytic activity of bimetallic nickel alloys for solid-oxide fuel cell anode reactions from density-functional theory
journal, May 2011

The complex behavior of the Pd ₇ cluster supported on TiO ₂ (110) during CO oxidation: adsorbate-driven promoting effect
journal, January 2016

Significance of β-dehydrogenation in ethanol electro-oxidation on platinum doped with Ru, Rh, Pd, Os and Ir
journal, January 2014

Palladium–Tin Alloyed Catalysts for the Ethanol Oxidation Reaction in an Alkaline Medium
journal, January 2012

Density Functional Theory Studies of Ethanol Decomposition on Rh(211)
journal, October 2011

Activity of CeOx and TiOx Nanoparticles Grown on Au(111) in the Water-Gas Shift Reaction
journal, December 2007

Insight into steam reforming of ethanol to produce hydrogen for fuel cells
journal, March 2006

Electro-Oxidation of Ethanol on Pt, Rh, and PtRh Electrodes. A Study Using DEMS and in-Situ FTIR Techniques
journal, September 2002

Toward Understanding Metal-Catalyzed Ethanol Reforming
journal, May 2015

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

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

Iridium–Ruthenium Alloyed Nanoparticles for the Ethanol Oxidation Fuel Cell Reactions
journal, May 2012

Role of Water and Adsorbed Hydroxyls on Ethanol Electrochemistry on Pd: New Mechanism, Active Centers, and Energetics for Direct Ethanol Fuel Cell Running in Alkaline Medium
journal, March 2014

Alloy catalysts designed from first principles
journal, October 2004

Ternary Pt/Rh/SnO₂ electrocatalysts for oxidizing ethanol to CO₂
journal, January 2009

Platinum-Tin Oxide Core–Shell Catalysts for Efficient Electro-Oxidation of Ethanol
journal, July 2014

Current Status of Hydrogen Production Techniques by Steam Reforming of Ethanol: A Review
journal, September 2005

Ab initiomolecular dynamics for liquid metals
journal, January 1993

Highly active and selective binary MgO–SiO ₂ catalysts for the production of 1,3-butadiene from ethanol
journal, January 2017

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

Ethanol Steam Reforming on Rh Catalysts: Theoretical and Experimental Understanding
journal, December 2013

Interfacial Effects in Iron-Nickel Hydroxide-Platinum Nanoparticles Enhance Catalytic Oxidation
journal, May 2014

High-precision sampling for Brillouin-zone integration in metals
journal, August 1989

Synergistic Effect of Tungsten Carbide and Palladium on Graphene for Promoted Ethanol Electrooxidation
journal, July 2013

H2 Production from Ethanol over Rh–Pt/CeO2 Catalysts: The Role of Rh for the Efficient Dissociation of the Carbon–Carbon Bond
journal, June 2002

Ethanol steam reforming over MgxNi1−xAl2O3 spinel oxide-supported Rh catalysts
journal, July 2005

Renewable Hydrogen from Ethanol by Autothermal Reforming
journal, February 2004

Design of Nanocatalysts for Green Hydrogen Production from Bioethanol
journal, December 2011

Ternary Electrocatalysts for Oxidizing Ethanol to Carbon Dioxide: Making Ir Capable of Splitting C–C Bond
journal, December 2012

Highly Active Iridium/Iridium–Tin/Tin Oxide Heterogeneous Nanoparticles as Alternative Electrocatalysts for the Ethanol Oxidation Reaction
journal, September 2011

Ternary PtSnRh–SnO2 nanoclusters: synthesis and electroactivity for ethanol oxidation fuel cell reaction
journal, January 2011

Understanding of ethanol decomposition on Rh(111) from density functional theory and kinetic Monte Carlo simulations
journal, May 2011

Electrochemical dissolution of surface alloys in acids: Thermodynamic trends from first-principles calculations
journal, May 2007

Theoretical Calculation of the Dehydrogenation of Ethanol on a Rh/CeO ₂ (111) Surface
journal, August 2006

Water-gas shift reaction on oxide/Cu(111): Rational catalyst screening from density functional theory
journal, November 2010

First Principle Study of Ethanol Adsorption and Formation of Hydrogen Bond on Rh(111) Surface
journal, May 2007

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

Special points for Brillouin-zone integrations
journal, June 1976

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

Production of Hydrogen from Ethanol: Review of Reaction Mechanism and Catalyst Deactivation
journal, April 2012

Mechanism of Ethanol Reforming: Theoretical Foundations
journal, March 2009

Early stages in the oxidation of ethanol at low index single crystal platinum electrodes
journal, November 1997

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

Surface segregation energies in transition-metal alloys
journal, June 1999

Rationalization of Au Concentration and Distribution in AuNi@Pt Core–Shell Nanoparticles for Oxygen Reduction Reaction
journal, September 2015

Reversible work transition state theory: application to dissociative adsorption of hydrogen
journal, February 1995

In Situ Probing of the Active Site Geometry of Ultrathin Nanowires for the Oxygen Reduction Reaction
journal, September 2015

Design of a Surface Alloy Catalyst for Steam Reforming
journal, March 1998

Bio-ethanol catalytic steam reforming over supported metal catalysts
journal, June 2002

First-principles study of methane dehydrogenation on a bimetallic Cu/Ni(111) surface
journal, November 2009

A review on reforming bio-ethanol for hydrogen production
journal, October 2007

A dems and FTir spectroscopic investigation of adsorbed ethanol on polycrystalline platinum
journal, March 1994

Towards the computational design of solid catalysts
journal, April 2009

Catalysts for direct ethanol fuel cells
journal, June 2007

Ab Initio Study of CO Hydrogenation to Oxygenates on Reduced Rh Terraces and Stepped Surfaces
journal, May 2010

Influence of Cluster–Support Interactions on Reactivity of Size-Selected Nb _x O _y Clusters
journal, April 2015

In situ FTIR spectroscopic studies of electrooxidation of ethanol on Pd electrode in alkaline media
journal, November 2010

Ethanol Steam Reforming in a Microchannel Reactor
journal, January 2007

High Activity of Ce1−xNixO2−y for H2 Production through Ethanol Steam Reforming: Tuning Catalytic Performance through Metal-Oxide Interactions
journal, November 2010

Ethanol Activation on Closed-Packed Surfaces
journal, December 2014

C ₂ N-graphene supported single-atom catalysts for CO ₂ electrochemical reduction reaction: mechanistic insight and catalyst screening
journal, January 2018

Nanocatalysts for Electrocatalytic Oxidation of Ethanol
journal, April 2019

Intrinsic composition and electronic effects of multicomponent platinum nanocatalysts with high activity and selectivity for ethanol oxidation reaction
journal, January 2018