Density functional theory study of carbon dioxide electrochemical reduction on the Fe(100) surface

Nicole J. Bernstein, Sneha A. Akhade, Michael John Janik

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

Carbon dioxide electroreduction offers the possibility of producing hydrocarbon fuels using energy from renewable sources. Herein, we use density functional theory to analyze the feasibility of CO2 electroreduction on a Fe(100) surface. Experimentally, iron is nonselective for hydrocarbon formation. A simplistic analysis of low-coverage reaction intermediate energies for the paths to produce CH4 and CH3OH from CO2 suggests Fe(100) could be more active than Cu(111), currently the only metallic catalyst to show selectivity towards hydrocarbon formation. We consider a series of impediments to CO2 electroreduction on Fe(100) including O*/OH* (* denotes surface bound species) blockage of active surface sites; competitive adsorption effects of H*, CO* and C*; and iron carbide formation. Our results indicate that under CO 2 electroreduction conditions, Fe(100) is predicted to be covered in C* or CO* species, blocking any C-H bond formation. Further, bulk Fe is predicted to be unstable relative to FeCx formation at potentials relevant to CO2 electroreduction conditions. This journal is

Original languageEnglish (US)
Pages (from-to)13708-13717
Number of pages10
JournalPhysical Chemistry Chemical Physics
Volume16
Issue number27
DOIs
StatePublished - Jul 21 2014

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Carbon Monoxide
Hydrocarbons
Carbon Dioxide
Density functional theory
carbon dioxide
density functional theory
Reaction intermediates
Catalyst selectivity
hydrocarbons
hydrocarbon fuels
Iron
iron
reaction intermediates
Adsorption
Catalysts
carbides
selectivity
catalysts
adsorption
energy

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

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Density functional theory study of carbon dioxide electrochemical reduction on the Fe(100) surface. / Bernstein, Nicole J.; Akhade, Sneha A.; Janik, Michael John.

In: Physical Chemistry Chemical Physics, Vol. 16, No. 27, 21.07.2014, p. 13708-13717.

Research output: Contribution to journalArticle

TY - JOUR

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AU - Bernstein, Nicole J.

AU - Akhade, Sneha A.

AU - Janik, Michael John

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N2 - Carbon dioxide electroreduction offers the possibility of producing hydrocarbon fuels using energy from renewable sources. Herein, we use density functional theory to analyze the feasibility of CO2 electroreduction on a Fe(100) surface. Experimentally, iron is nonselective for hydrocarbon formation. A simplistic analysis of low-coverage reaction intermediate energies for the paths to produce CH4 and CH3OH from CO2 suggests Fe(100) could be more active than Cu(111), currently the only metallic catalyst to show selectivity towards hydrocarbon formation. We consider a series of impediments to CO2 electroreduction on Fe(100) including O*/OH* (* denotes surface bound species) blockage of active surface sites; competitive adsorption effects of H*, CO* and C*; and iron carbide formation. Our results indicate that under CO 2 electroreduction conditions, Fe(100) is predicted to be covered in C* or CO* species, blocking any C-H bond formation. Further, bulk Fe is predicted to be unstable relative to FeCx formation at potentials relevant to CO2 electroreduction conditions. This journal is

AB - Carbon dioxide electroreduction offers the possibility of producing hydrocarbon fuels using energy from renewable sources. Herein, we use density functional theory to analyze the feasibility of CO2 electroreduction on a Fe(100) surface. Experimentally, iron is nonselective for hydrocarbon formation. A simplistic analysis of low-coverage reaction intermediate energies for the paths to produce CH4 and CH3OH from CO2 suggests Fe(100) could be more active than Cu(111), currently the only metallic catalyst to show selectivity towards hydrocarbon formation. We consider a series of impediments to CO2 electroreduction on Fe(100) including O*/OH* (* denotes surface bound species) blockage of active surface sites; competitive adsorption effects of H*, CO* and C*; and iron carbide formation. Our results indicate that under CO 2 electroreduction conditions, Fe(100) is predicted to be covered in C* or CO* species, blocking any C-H bond formation. Further, bulk Fe is predicted to be unstable relative to FeCx formation at potentials relevant to CO2 electroreduction conditions. This journal is

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