文献类型：期刊文献

英文题名：From photocorrosion to photoactivity: sulfite-gated self-etching of BiVO4 into a black Bi-O phase

作者：Hu, Hangyu[1,2];Han, Yang[1,2];Bao, Zhemeng[1,2];Zhuang, Weijie[1,2];Jia, Yaohua[1,2];Yang, Kai[1,2];Kan, Miao[1,2];Zhang, Jinlong[1,2]

机构：[1]East China Univ Sci & Technol, Sch Chem & Mol Engn, State Key Lab Green Chem Engn & Ind Catalysis, 130 Meilong Rd, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Shanghai Engn Res Ctr Multimedia Environm Catalysi, 130 Meilong Rd, Shanghai 200237, Peoples R China

年份：2026

外文期刊名：NANOSCALE

收录：;EI(收录号：20261920664078);WOS:【SCI-EXPANDED(收录号:WOS:001757289600001)】；

基金：M. K. thanks for the support from the National Natural Science Foundation of China (22302067 and 22461142136), the Innovation Program of Shanghai Municipal Education Commission (2021-01-07-00-02-E00106), the Science and Technology Commission of Shanghai Municipality (22230780200 and 20DZ2250400) and the Fundamental Research Funds for the Central Universities (222201717003).

语种：英文

外文关键词：Bismuth compounds - Black holes - Corrosion - Engineering research - Etching - Negative ions - Oxygen vacancies

摘要：Photocorrosion has long been viewed as the primary failure mode limiting BiVO4 photoanodes. Herein, we redefine it as a programmable pathway for activation. We demonstrate that sulfite anions, beyond acting as hole scavengers, can precisely gate a light-driven self-etching/reconstruction. This converts a 1 cm2 BiVO4 photoanode into a black Bi-O phase under 5-sun illumination. Mechanistic studies reveal that sulfite oxidation generates transient Bi-O motifs, which, in concert with cleavage of the V-O framework, lead to an oxygen-vacancy-rich Bi-O network. The reconstructed black phase exhibits a spectrum-wide absorption uplift and a measurable photothermal response under high-flux excitation, consistent with enhanced non-radiative dissipation and potential plasmon-related contributions from minor Bi0 species. After a 12-hour in situ reconstruction, the resulting nanoporous, disordered network delivers a stable photocurrent density of over similar to 12 mA cm-2 at 1.4 V vs. RHE under 5-sun illumination. This work establishes photocorrosion not as a problem to be solved, but as an anion-directed engineering tool, opening a general avenue of "corrosion engineering" or designing high-performance oxide photoelectrodes.