Despite recent efforts to improve BiVO₄ semiconductor photoanodes, the electron‐hole recombination in BiVO₄ photoanodes is still a critical problem in efficient photoelectrochemical water oxidation. In this work, a dual modification of BiVO₄ photoanodes is performed utilising the polyoxometalate compound H₃PW₁₂O₄₀ (PW₁₂), acting as electron shuttle (electron capture and transfer), and nickel (II) phthalocyanine tetrasulfonic acid (NiTsPc), acting as hole extractor (accelerating hole transport). As for the photoelectrochemical water oxidation, the BiVO₄/PW₁₂/NiTsPc photoanode displays a 5.4‐fold improvement in photocurrent density at 1.23 V (vs. RHE) as compared to the pristine BiVO₄ photoanode, under illumination of simulated solar light. Furthermore, we demonstrate that the recombination of electron‐hole pairs could be remarkably suppressed in the dual modified BiVO₄ photoanode, by means of the electrochemical impedance spectroscopy measurements together with hydrogen peroxide as the hole scavenger. Additionally, the energy band distributions among PW₁₂, BiVO₄, and NiTsPc allow the photoelectron to transfer from BiVO₄ to PW₁₂ and the hole from BiVO₄ to NiTsPc, which is responsible for the improved photoactivity of BiVO₄. This work provides a new insight into effectively improving BiVO₄ photoanode by rational design of dual modification.

中文翻译：

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三元复合光阳极BiVO4 / PW12 / NiTsPc的合理设计，以改善光电化学水氧化性能

尽管最近努力改善BiVO ₄半导体光阳极，在BiVO的电子-空穴重组₄光阳极仍然在有效的光电化学水氧化的关键问题。在这项工作中，利用多金属氧酸盐化合物H ₃ PW ₁₂ O ₄₀（PW ₁₂）（充当电子穿梭（电子捕获和转移））和镍酞菁四磺酸镍（IITsPc）对BiVO _4光阳极进行了双重修饰。，充当空穴提取器（加速空穴传输）。至于光电化学水氧化，BiVO ₄ / PW ₁₂与原始BiVO ₄光电阳极相比，在模拟太阳光下，/ NiTsPc光电阳极在1.23 V（vs. RHE）下的光电流密度提高了5.4倍。此外，我们证明，通过电化学阻抗谱测量和过氧化氢作为空穴清除剂，可以在双重修饰的BiVO ₄光电阳极中显着抑制电子-空穴对的重组。另外，PW之间的能带分布₁₂，BiVO ₄，和NiTsPc允许光电子从BiVO转移₄到PW ₁₂从BiVO和空穴₄NiTsPc，这有助于BiVO _4的光活性的提高。这项工作为通过合理的双重修饰设计有效改善BiVO ₄光电阳极提供了新的见解。