A first principles analysis of the electro-oxidation of CO over Pt(1 1 1)

Michael J. Janik, Matthew Neurock

Research output: Contribution to journalArticle

48 Citations (Scopus)

Abstract

First principle density functional theoretical calculations carried out within a constant potential half-cell formalism were used to model the electro-oxidation of CO over Pt(1 1 1). The method involves tuning the potential by the addition or removal of electrons from the system. The free energy for different adsorbed species within the double-layer is analyzed over a range of different potentials to establish the lowest energy states and the reaction energies that connect these states. The potentials are calculated based on a novel double-reference approach [J.S. Filhol, M. Neurock, Angew. Chem. Int. Ed. 45 (2006) 402] discussed earlier. The potential-dependent reaction energies are reported for the elementary steps of water activation in the presence of co-adsorbed CO and CO oxidation over the model Pt(1 1 1) surface. The potential-dependent activation barriers are computed for the key elementary steps in CO oxidation to develop a detailed reaction energy profile as a function of electrode potential. The results suggest that the coupling of co-adsorbed CO and OH controls the rate. Water activation, however, is necessary to supply a critical coverage of the surface OH oxidant.

Original languageEnglish (US)
Pages (from-to)5517-5528
Number of pages12
JournalElectrochimica Acta
Volume52
Issue number18
DOIs
StatePublished - May 10 2007

Fingerprint

Electrooxidation
Carbon Monoxide
Chemical activation
Oxidation
Oxidants
Electron energy levels
Free energy
Density functional theory
Water
Tuning
Electrodes
Electrons

All Science Journal Classification (ASJC) codes

  • Chemical Engineering(all)
  • Electrochemistry

Cite this

@article{2c080bedc4874f3bb2aff37e423ed5f0,
title = "A first principles analysis of the electro-oxidation of CO over Pt(1 1 1)",
abstract = "First principle density functional theoretical calculations carried out within a constant potential half-cell formalism were used to model the electro-oxidation of CO over Pt(1 1 1). The method involves tuning the potential by the addition or removal of electrons from the system. The free energy for different adsorbed species within the double-layer is analyzed over a range of different potentials to establish the lowest energy states and the reaction energies that connect these states. The potentials are calculated based on a novel double-reference approach [J.S. Filhol, M. Neurock, Angew. Chem. Int. Ed. 45 (2006) 402] discussed earlier. The potential-dependent reaction energies are reported for the elementary steps of water activation in the presence of co-adsorbed CO and CO oxidation over the model Pt(1 1 1) surface. The potential-dependent activation barriers are computed for the key elementary steps in CO oxidation to develop a detailed reaction energy profile as a function of electrode potential. The results suggest that the coupling of co-adsorbed CO and OH controls the rate. Water activation, however, is necessary to supply a critical coverage of the surface OH oxidant.",
author = "Janik, {Michael J.} and Matthew Neurock",
year = "2007",
month = "5",
day = "10",
doi = "10.1016/j.electacta.2007.01.060",
language = "English (US)",
volume = "52",
pages = "5517--5528",
journal = "Electrochimica Acta",
issn = "0013-4686",
publisher = "Elsevier Limited",
number = "18",

}

A first principles analysis of the electro-oxidation of CO over Pt(1 1 1). / Janik, Michael J.; Neurock, Matthew.

In: Electrochimica Acta, Vol. 52, No. 18, 10.05.2007, p. 5517-5528.

Research output: Contribution to journalArticle

TY - JOUR

T1 - A first principles analysis of the electro-oxidation of CO over Pt(1 1 1)

AU - Janik, Michael J.

AU - Neurock, Matthew

PY - 2007/5/10

Y1 - 2007/5/10

N2 - First principle density functional theoretical calculations carried out within a constant potential half-cell formalism were used to model the electro-oxidation of CO over Pt(1 1 1). The method involves tuning the potential by the addition or removal of electrons from the system. The free energy for different adsorbed species within the double-layer is analyzed over a range of different potentials to establish the lowest energy states and the reaction energies that connect these states. The potentials are calculated based on a novel double-reference approach [J.S. Filhol, M. Neurock, Angew. Chem. Int. Ed. 45 (2006) 402] discussed earlier. The potential-dependent reaction energies are reported for the elementary steps of water activation in the presence of co-adsorbed CO and CO oxidation over the model Pt(1 1 1) surface. The potential-dependent activation barriers are computed for the key elementary steps in CO oxidation to develop a detailed reaction energy profile as a function of electrode potential. The results suggest that the coupling of co-adsorbed CO and OH controls the rate. Water activation, however, is necessary to supply a critical coverage of the surface OH oxidant.

AB - First principle density functional theoretical calculations carried out within a constant potential half-cell formalism were used to model the electro-oxidation of CO over Pt(1 1 1). The method involves tuning the potential by the addition or removal of electrons from the system. The free energy for different adsorbed species within the double-layer is analyzed over a range of different potentials to establish the lowest energy states and the reaction energies that connect these states. The potentials are calculated based on a novel double-reference approach [J.S. Filhol, M. Neurock, Angew. Chem. Int. Ed. 45 (2006) 402] discussed earlier. The potential-dependent reaction energies are reported for the elementary steps of water activation in the presence of co-adsorbed CO and CO oxidation over the model Pt(1 1 1) surface. The potential-dependent activation barriers are computed for the key elementary steps in CO oxidation to develop a detailed reaction energy profile as a function of electrode potential. The results suggest that the coupling of co-adsorbed CO and OH controls the rate. Water activation, however, is necessary to supply a critical coverage of the surface OH oxidant.

UR - http://www.scopus.com/inward/record.url?scp=34247154901&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=34247154901&partnerID=8YFLogxK

U2 - 10.1016/j.electacta.2007.01.060

DO - 10.1016/j.electacta.2007.01.060

M3 - Article

AN - SCOPUS:34247154901

VL - 52

SP - 5517

EP - 5528

JO - Electrochimica Acta

JF - Electrochimica Acta

SN - 0013-4686

IS - 18

ER -