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Improving WO3/SnO2 photoanode stability by inhibiting hydroxyl radicals with cobalt ions in strong acid

通过钴离子抑制羟基自由基提高WO3/SnO2光阳极在 强酸中的稳定性

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Abstract

Photoelectrochemical (PEC) water splitting in acid is promising, but its development has been hindered by the lack of stable photoanodes and effective nonprecious cocatalysts. WO3 is one of the few acid-stable semiconductors, but its fast performance decay under illumination remains elusive and unsolved. Herein, we present that the fast photo-current decreases of both WO3 and WO3/SnO2 photoanodes were caused by the hydroxyl radicals (OH}·) generated at the electrode/electrolyte interfaces, and we solved this issue by introducing cobalt (Co2+) ions into the electrolyte at pH 0.3, allowing for the efficient oxidation of H2O to O2 rather than to detrimental OH· radicals, with the Faradaic efficiency toward oxygen evolution increasing from 40% to 95% and the photocurrent density increasing from 0.6 to 0.8 mA cm−2 and being stable for 25 h at 1.2 V (reversible hydrogen electrode). Importantly, the scavenging of OH· radicals by vitamin C demonstrated the same photocurrent stability as the introduction of Co2+ ions, further implying the crucial inhibiting role of Co2+ ions. In-situ ultraviolet-visible and Raman spectroscopy indicated the trapping of surface holes by the oxidation of Co2+ to Co3+, and electron paramagnetic resonance revealed the role of Co2+ ions in the inhibition of OH· radicals. This study provides an ideal model for combining a homogeneous redox-active Co2+/Co3+ couple with a photoanode for water oxidation in strong acid.

摘要

酸性环境中光电化学水分解具有广阔的应用前景, 但由于缺乏 稳定的光阳极以及有效的非贵金属助催化剂, 其发展受到了极大的阻 碍. WO3是能够在酸性环境下稳定的半导体之一, 但其在光照下的快速 性能衰减仍然是一个悬而未决的问题. 本研究提出WO3和WO3/SnO2光 阳极光电流的快速下降是因为电极/电解质界面上产生的羟基自由基 (OH·)导致的. 我们发现在pH为0.3的电解质中引入钴(Co2+)离子可以有 效解决这个问题. Co2+的存在可以促进H2O高效氧化为O2, 而不是产生 不利的OH·自由基. 最终在Co2+存在条件下, 可以将光电分解水的法拉 第效率从40%提高到95%, 将光电流密度从0.6提高到0.8 mA cm−2, 并在 1.2 V (可逆氢电极)下稳定25 h. 重要的是, 在利用维生素C淬灭OH·自 由基以后, 其光电流稳定性表现出与引入Co2+离子时一致, 进一步表明 Co2+离子对于OH·的关键抑制作用. 此外, 原位紫外-可见光谱和拉曼光 谱表明Co2+会捕获表面空穴并被氧化为Co3+. 电子顺磁共振也进一步 揭示了Co2+离子对OH·自由基的抑制作用. 本研究为均相的Co2+/Co3+ 氧化还原物种与光阳极结合用于强酸中的水氧化提供了参考.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (22072013).

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Authors and Affiliations

  1. Molecular Electrochemistry Laboratory, Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu, 610054, China

    Xiaobing Shi  (石小兵), Qianbao Wu  (吴千宝) & Chunhua Cui  (崔春华)

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  1. Xiaobing Shi  (石小兵)
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  2. Qianbao Wu  (吴千宝)
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  3. Chunhua Cui  (崔春华)
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Contributions

Cui C conceived this study and led the project. Shi X conducted the experiment and analyzed the data; Wu Q performed the EPR measurement and optimized the graphs; Cui C and Shi X wrote the paper. All authors contributed to the general discussion.

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Correspondence to Chunhua Cui  (崔春华).

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Conflict of interest

The authors declare that they have no conflict of interest.

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Supporting data are available in the online version of the paper.

Xiaobing Shi received his master’s degree from the School of Chemistry and Chemical Engineering, Guangxi University in 2019. He is now a PhD candidate under the supervision of Prof. Chunhua Cui at the University of Electronic Science and Technology of China. His research focuses on the synthesis and in-situ spectrum of semiconductor for photoelectrocatalytic water splitting.

Chunhua Cui is currently a professor at the Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China. He received his PhD degree from the University of Science and Technology of China in 2011. He joined the University of Electronic Science and Technology of China in 2017. His research interest includes synthetic chemistry, electrocatalytic conversion of small molecules, and in-situ electrochemical spectroscopy.

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Shi, X., Wu, Q. & Cui, C. Improving WO3/SnO2 photoanode stability by inhibiting hydroxyl radicals with cobalt ions in strong acid. Sci. China Mater. 66, 614–622 (2023). https://doi.org/10.1007/s40843-022-2188-5

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