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In situ quantitative analysis of electrochemical oxide film development on metal surfaces using ambient pressure X-ray photoelectron spectroscopy : Industrial alloys

Larsson, Alfred LU ; Simonov, Konstantin LU ; Eidhagen, Josefin ; Grespi, Andrea LU ; Yue, Xiaoqi ; Tang, Huajie ; Delblanc, Anna ; Scardamaglia, Mattia LU ; Shavorskiy, Andrey LU and Pan, Jinshan , et al. (2023) In Applied Surface Science 611.
Abstract

Ambient Pressure X-ray Photoelectron Spectroscopy combined with an electrochemical setup is used to study, in situ, the electrochemical oxide growth on an industrial Ni-Cr-Mo alloy. The native oxide film was characterized in vacuum and in water vapor at 17 mbar, and was found to be 11.4 Å thick and rich in Cr3+. In 0.1 M NaCl electrolyte, anodic growth of the oxide film at potentials up to 700 mV vs Ag/AgCl nearly doubled the thickness of the oxide film. Moreover, a transformation of the oxide composition occurred, as the oxide became enriched in Mo6+ with a chemical fingerprint more like that of pure MoO3. Both thermodynamics and kinetics of the oxidation of the alloying elements dictate the oxide film... (More)

Ambient Pressure X-ray Photoelectron Spectroscopy combined with an electrochemical setup is used to study, in situ, the electrochemical oxide growth on an industrial Ni-Cr-Mo alloy. The native oxide film was characterized in vacuum and in water vapor at 17 mbar, and was found to be 11.4 Å thick and rich in Cr3+. In 0.1 M NaCl electrolyte, anodic growth of the oxide film at potentials up to 700 mV vs Ag/AgCl nearly doubled the thickness of the oxide film. Moreover, a transformation of the oxide composition occurred, as the oxide became enriched in Mo6+ with a chemical fingerprint more like that of pure MoO3. Both thermodynamics and kinetics of the oxidation of the alloying elements dictate the oxide film growth and composition. Furthermore, we develop the quantitative analysis of oxide composition and thickness to take into account the attenuation through the liquid water and the water vapor atmosphere. Finally, we discuss the differences between ex situ, UHV, in situ, and operando measurements. Our approach is robust, fast, simple, and suitable for systematically probing metal surfaces after aqueous exposure and electrochemical polarization, which promises wide applications for studies of solid–liquid interfaces in corrosion, batteries, fuel cells, and electrocatalysis.

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publishing date
type
Contribution to journal
publication status
published
subject
in
Applied Surface Science
volume
611
article number
155714
publisher
Elsevier
external identifiers
  • scopus:85142169021
ISSN
0169-4332
DOI
10.1016/j.apsusc.2022.155714
language
English
LU publication?
yes
id
1701a700-bad2-4e77-a946-ffc2c48ff2e8
date added to LUP
2023-02-08 15:44:03
date last changed
2023-11-17 05:50:54
@article{1701a700-bad2-4e77-a946-ffc2c48ff2e8,
  abstract     = {{<p>Ambient Pressure X-ray Photoelectron Spectroscopy combined with an electrochemical setup is used to study, in situ, the electrochemical oxide growth on an industrial Ni-Cr-Mo alloy. The native oxide film was characterized in vacuum and in water vapor at 17 mbar, and was found to be 11.4 Å thick and rich in Cr<sup>3+</sup>. In 0.1 M NaCl electrolyte, anodic growth of the oxide film at potentials up to 700 mV vs Ag/AgCl nearly doubled the thickness of the oxide film. Moreover, a transformation of the oxide composition occurred, as the oxide became enriched in Mo<sup>6+</sup> with a chemical fingerprint more like that of pure MoO<sub>3</sub>. Both thermodynamics and kinetics of the oxidation of the alloying elements dictate the oxide film growth and composition. Furthermore, we develop the quantitative analysis of oxide composition and thickness to take into account the attenuation through the liquid water and the water vapor atmosphere. Finally, we discuss the differences between ex situ, UHV, in situ, and operando measurements. Our approach is robust, fast, simple, and suitable for systematically probing metal surfaces after aqueous exposure and electrochemical polarization, which promises wide applications for studies of solid–liquid interfaces in corrosion, batteries, fuel cells, and electrocatalysis.</p>}},
  author       = {{Larsson, Alfred and Simonov, Konstantin and Eidhagen, Josefin and Grespi, Andrea and Yue, Xiaoqi and Tang, Huajie and Delblanc, Anna and Scardamaglia, Mattia and Shavorskiy, Andrey and Pan, Jinshan and Lundgren, Edvin}},
  issn         = {{0169-4332}},
  language     = {{eng}},
  publisher    = {{Elsevier}},
  series       = {{Applied Surface Science}},
  title        = {{In situ quantitative analysis of electrochemical oxide film development on metal surfaces using ambient pressure X-ray photoelectron spectroscopy : Industrial alloys}},
  url          = {{http://dx.doi.org/10.1016/j.apsusc.2022.155714}},
  doi          = {{10.1016/j.apsusc.2022.155714}},
  volume       = {{611}},
  year         = {{2023}},
}