Mechanism of Anodic Dissolution of Tungsten in Sulfate–Fluoride Solutions

IF 2.6 3区 材料科学 Q3 MATERIALS SCIENCE, MULTIDISCIPLINARY Metals Pub Date : 2024-09-02 DOI:10.3390/met14091004
Martin Bojinov, Yoanna Penkova, Iva Betova, Vasil Karastoyanov
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Abstract

Thin passive films on tungsten play an important role during the surface levelling of the metal for various applications and during the initial stages of electrochemical synthesis of thick, nanoporous layers that perform well as photo-absorbers and photo-catalysts for light-assisted water splitting. In the present work, the passivation of tungsten featuring metal dissolution and thin oxide film formation is studied by a combination of in situ electrochemical (voltammetry and impedance spectroscopy) and spectro-electrochemical methods coupled with ex situ surface oxide characterization by XPS. Voltametric and impedance data are successfully reproduced by a kinetic model featuring oxide growth and dissolution coupled with the recombination of point defects, as well as a multistep tungsten dissolution reaction at the oxide/electrolyte interface. The model is in good agreement with the spectro-electrochemical data on soluble oxidation products and the surface chemical composition of the passive oxide.
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钨在硫酸盐-氟化物溶液中的阳极溶解机理
钨上的钝化薄膜在各种应用的金属表面钝化过程中,以及在电化学合成厚纳米多孔层的初始阶段发挥着重要作用,这些纳米多孔层可作为光吸收剂和光催化剂用于光助水分离。在本研究中,结合原位电化学(伏安法和阻抗光谱法)和光谱电化学方法以及 XPS 原位表面氧化物表征法,对以金属溶解和氧化薄膜形成为特征的钨钝化进行了研究。一个动力学模型成功地再现了伏安法和阻抗数据,该模型的特点是氧化物的生长和溶解与点缺陷的再结合,以及氧化物/电解质界面上的多步钨溶解反应。该模型与可溶性氧化产物的光谱电化学数据以及被动氧化物的表面化学成分十分吻合。
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来源期刊
Metals
Metals MATERIALS SCIENCE, MULTIDISCIPLINARY-METALLURGY & METALLURGICAL ENGINEERING
CiteScore
4.90
自引率
13.80%
发文量
1832
审稿时长
1.5 months
期刊介绍: Metals (ISSN 2075-4701) is an open access journal of related scientific research and technology development. It publishes reviews, regular research papers (articles) and short communications. Our aim is to encourage scientists to publish their experimental and theoretical results in as much detail as possible. Therefore, there is no restriction on the length of the papers. The full experimental details must be provided so that the results can be reproduced. Metals provides a forum for publishing papers which advance the in-depth understanding of the relationship between the structure, the properties or the functions of all kinds of metals.
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