Though bismuth vanadate (BiVO) exhibits a promising potential as a semiconductor photoanode toward photoelectrochemical (PEC) water oxidation, its PEC performance is still limited by the poor charge carrier transport and sluggish oxygen evolution kinetics. Herein, the polyaniline (PANI) and cobalt coordinated-phthalocyanines (CoTcPc) were introduced onto the BiVO semiconductor substrate, constructing the integrated CoTcPc/nPANI/BiVO (n = 30, 60 and 90, n represents the deposition time for PANI with the unit of s) composite photoanodes. It is demonstrated that the PEC water oxidation activity of BiVO is significantly boosted by the incorporation of PANI and CoTcPc, stemming from the improved electron/hole transfer, enhanced charge separation efficiency, and accelerated carrier mobility and water oxidation kinetics. CoTcPc/60PANI/BiVO composite photoanode with the optimized compositions exhibits an enhanced photocurrent density of 4.03 mA/cm at 1.23 V vs. RHE under illumination, ranking among the best records reported recently. Furthermore, the roles of electrodeposition time to generate PANI are also distinguished through experimental studies. These results reveal the crucial role of engineering the hole transfer layer to optimize the semiconductor photoanodes toward efficient PEC water oxidation.

中文翻译：

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空穴传输聚苯胺层与钴酞菁助催化剂的耦合促进钒酸铋光阳极的光电化学水氧化

尽管钒酸铋（BiVO）作为半导体光阳极在光电化学（PEC）水氧化方面表现出巨大的潜力，但其PEC性能仍然受到载流子传输差和析氧动力学缓慢的限制。本文将聚苯胺（PANI）和钴配位酞菁（CoTcPc）引入到 BiVO 半导体衬底上，构建集成的 CoTcPc/nPANI/BiVO（n = 30、60 和 90，n 代表 PANI 的沉积时间，单位为s)复合光电阳极。结果表明，PANI 和 CoTcPc 的掺入显着提高了 BiVO 的 PEC 水氧化活性，这是由于改善了电子/空穴传输、增强了电荷分离效率、加速了载流子迁移率和水氧化动力学。具有优化成分的 CoTcPc/60PANI/BiVO 复合光电阳极在 1.23 V 光照下与 RHE 相比表现出 4.03 mA/cm 的增强光电流密度，跻身最近报道的最佳记录之列。此外，通过实验研究还区分了电沉积时间对生成PANI的作用。这些结果揭示了设计空穴传输层以优化半导体光电阳极以实现高效 PEC 水氧化的关键作用。