Re-visiting the O/Cu(111) system - when metastable surface oxides could become an issue!

Norina A. Richter, Chang Eun Kim, Catherine Stampfl, Aloysius Soon

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

Surface oxidation processes are crucial for the functionality of Cu-based catalytic systems used for methanol synthesis, partial oxidation of methanol or the water-gas shift reaction. We assess the stability and population of the "8"-structure, a oxide phase, on the Cu(111) surface. This structure has been observed in X-ray photoelectron spectroscopy and low-energy electron diffraction experiments as a Cu(111) surface reconstruction that can be induced by a hyperthermal oxygen molecular beam. Using density-functional theory calculations in combination with ab initio atomistic thermodynamics and Boltzmann statistical mechanics, we find that the proposed oxide superstructure is indeed metastable and that the population of the "8"-structure is competitive with the known "29" and "44" oxide film structures on Cu(111). We show that the configuration of O and Cu atoms in the first and second layers of the "8"-structure closely resembles the arrangement of atoms in the first two layers of Cu2O(110), where the atoms in the "8"-structure are more constricted. Cu2O(110) has been suggested in the literature as the most active low index facet for reactions such as water splitting under light illumination. If the "8"-structure were to form during a catalytic process, it is therefore likely to be one of the reactive phases.

Original languageEnglish
Pages (from-to)26735-26740
Number of pages6
JournalPhysical Chemistry Chemical Physics
Volume16
Issue number48
DOIs
Publication statusPublished - 2014 Nov 19

Fingerprint

Oxides
Atoms
Methanol
oxides
methyl alcohol
atoms
Oxidation
oxidation
water splitting
Statistical mechanics
Water gas shift
Molecular beams
Surface reconstruction
Low energy electron diffraction
statistical mechanics
molecular beams
Oxide films
Density functional theory
oxide films
flat surfaces

All Science Journal Classification (ASJC) codes

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

Cite this

Richter, Norina A. ; Kim, Chang Eun ; Stampfl, Catherine ; Soon, Aloysius. / Re-visiting the O/Cu(111) system - when metastable surface oxides could become an issue!. In: Physical Chemistry Chemical Physics. 2014 ; Vol. 16, No. 48. pp. 26735-26740.
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Re-visiting the O/Cu(111) system - when metastable surface oxides could become an issue! / Richter, Norina A.; Kim, Chang Eun; Stampfl, Catherine; Soon, Aloysius.

In: Physical Chemistry Chemical Physics, Vol. 16, No. 48, 19.11.2014, p. 26735-26740.

Research output: Contribution to journalArticle

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AB - Surface oxidation processes are crucial for the functionality of Cu-based catalytic systems used for methanol synthesis, partial oxidation of methanol or the water-gas shift reaction. We assess the stability and population of the "8"-structure, a oxide phase, on the Cu(111) surface. This structure has been observed in X-ray photoelectron spectroscopy and low-energy electron diffraction experiments as a Cu(111) surface reconstruction that can be induced by a hyperthermal oxygen molecular beam. Using density-functional theory calculations in combination with ab initio atomistic thermodynamics and Boltzmann statistical mechanics, we find that the proposed oxide superstructure is indeed metastable and that the population of the "8"-structure is competitive with the known "29" and "44" oxide film structures on Cu(111). We show that the configuration of O and Cu atoms in the first and second layers of the "8"-structure closely resembles the arrangement of atoms in the first two layers of Cu2O(110), where the atoms in the "8"-structure are more constricted. Cu2O(110) has been suggested in the literature as the most active low index facet for reactions such as water splitting under light illumination. If the "8"-structure were to form during a catalytic process, it is therefore likely to be one of the reactive phases.

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