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Thickness and Chemistry of Electrochemically Formed Oxide Films on Au(111) Probed with Ambient Pressure X-ray Photoelectron Spectroscopy

Ti, Auden LU orcid ; Grespi, Andrea LU orcid ; Larsson, Alfred LU orcid ; Küst, Ulrike LU orcid ; Paoletti, Niccolo ; Scardamaglia, Mattia LU ; Shavorskiy, Andrey LU ; Lira, Estephania LU orcid ; Merte, Lindsay and Lundgren, Edvin LU (2026) In ACS Electrochemistry 2(8). p.1855-1864
Abstract

The increasing demand for advances in efficient electrochemical (EC) energy conversion requires a fundamental understanding of the EC interface, which is challenging to study in situ. High-resolution ambient-pressure X-ray photoelectron spectroscopy, in combination with an EC cell, has been used in a dip-and-pull approach to study the EC oxidation of a Au(111) model electrode during oxidation and water electrolysis conditions. The behavior of Au(111) in 0.05 M H2SO4 was studied in a controlled gaseous environment of ∼13 mbar of water vapor after fully withdrawing the sample from the electrolyte at increasing anodic potential steps. Above 1.5 VRHE, a thin 2D Au(OH)3 film of ≈ 5 Å is observed... (More)

The increasing demand for advances in efficient electrochemical (EC) energy conversion requires a fundamental understanding of the EC interface, which is challenging to study in situ. High-resolution ambient-pressure X-ray photoelectron spectroscopy, in combination with an EC cell, has been used in a dip-and-pull approach to study the EC oxidation of a Au(111) model electrode during oxidation and water electrolysis conditions. The behavior of Au(111) in 0.05 M H2SO4 was studied in a controlled gaseous environment of ∼13 mbar of water vapor after fully withdrawing the sample from the electrolyte at increasing anodic potential steps. Above 1.5 VRHE, a thin 2D Au(OH)3 film of ≈ 5 Å is observed and exhibits a stable thickness until the onset of the oxygen evolution reaction (OER, ≈ 1.8 VRHE). From the onset of OER, a thicker bulk-like 3D Au(OH)3/Au2O3 mixture rapidly grows to a thickness of ≈ 21 Å at 2.02 VRHE. The initial 2D film exhibits self-limited kinetics, typically described by the Cabrera–Mott model and the point-defect model. The subsequent rapid growth of thicker bulk-like 3D islands suggests a disruption of the passive state coupled with the onset of OER. These results highlight surface passivation, which inhibits further oxidation due to surface oxidation, and provide quantitative and detailed insights into changes in the surface chemical composition of Au(111) under anodic polarization.

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organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
ambient pressure, electrochemical oxidation, electrochemistry, interface chemistry, surface science, synchrotrons, X-ray photoelectron spectroscopy
in
ACS Electrochemistry
volume
2
issue
8
pages
10 pages
publisher
The American Chemical Society (ACS)
external identifiers
  • scopus:105047396665
ISSN
2997-0571
DOI
10.1021/acselectrochem.6c00113
language
English
LU publication?
yes
id
254620ec-03f9-450d-aa9c-ae5cb1a23f73
date added to LUP
2026-09-03 15:10:57
date last changed
2026-09-03 15:11:36
@article{254620ec-03f9-450d-aa9c-ae5cb1a23f73,
  abstract     = {{<p>The increasing demand for advances in efficient electrochemical (EC) energy conversion requires a fundamental understanding of the EC interface, which is challenging to study in situ. High-resolution ambient-pressure X-ray photoelectron spectroscopy, in combination with an EC cell, has been used in a dip-and-pull approach to study the EC oxidation of a Au(111) model electrode during oxidation and water electrolysis conditions. The behavior of Au(111) in 0.05 M H<sub>2</sub>SO<sub>4</sub> was studied in a controlled gaseous environment of ∼13 mbar of water vapor after fully withdrawing the sample from the electrolyte at increasing anodic potential steps. Above 1.5 V<sub>RHE</sub>, a thin 2D Au(OH)<sub>3</sub> film of ≈ 5 Å is observed and exhibits a stable thickness until the onset of the oxygen evolution reaction (OER, ≈ 1.8 V<sub>RHE</sub>). From the onset of OER, a thicker bulk-like 3D Au(OH)<sub>3</sub>/Au<sub>2</sub>O<sub>3</sub> mixture rapidly grows to a thickness of ≈ 21 Å at 2.02 V<sub>RHE</sub>. The initial 2D film exhibits self-limited kinetics, typically described by the Cabrera–Mott model and the point-defect model. The subsequent rapid growth of thicker bulk-like 3D islands suggests a disruption of the passive state coupled with the onset of OER. These results highlight surface passivation, which inhibits further oxidation due to surface oxidation, and provide quantitative and detailed insights into changes in the surface chemical composition of Au(111) under anodic polarization.</p>}},
  author       = {{Ti, Auden and Grespi, Andrea and Larsson, Alfred and Küst, Ulrike and Paoletti, Niccolo and Scardamaglia, Mattia and Shavorskiy, Andrey and Lira, Estephania and Merte, Lindsay and Lundgren, Edvin}},
  issn         = {{2997-0571}},
  keywords     = {{ambient pressure; electrochemical oxidation; electrochemistry; interface chemistry; surface science; synchrotrons; X-ray photoelectron spectroscopy}},
  language     = {{eng}},
  month        = {{08}},
  number       = {{8}},
  pages        = {{1855--1864}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{ACS Electrochemistry}},
  title        = {{Thickness and Chemistry of Electrochemically Formed Oxide Films on Au(111) Probed with Ambient Pressure X-ray Photoelectron Spectroscopy}},
  url          = {{http://dx.doi.org/10.1021/acselectrochem.6c00113}},
  doi          = {{10.1021/acselectrochem.6c00113}},
  volume       = {{2}},
  year         = {{2026}},
}