Activating molecular catalysts at the surface of metal oxides can be a promising strategy to overcome the sluggish interfacial kinetics and enhance the efficiencies for photo(electro)chemical (PEC) water oxidation. However, the physical association between inorganic semiconductors for PEC process and organometallic molecular catalysts for surface catalytic reactions generally remains a challenging problem. In the present work, Kläui-type organometallic precursor [Cp*Ir{P(O)(OH)₂}₃]Na was first synthesized and subsequently successfully anchored onto BiVO₄ nanopyramids grown on transparent conducting substrates through various procedures. Treating the resulting hybrid heteronanostructure with IO₄^– induces a strong synergism between iridium atoms and BiVO₄ nanocrystals that exhibits a 5.5 times enhancement in photocurrent density at 1.23 V vs reversible hydrogen electrode (RHE) for PEC water oxidation. This simple approach provides an effective alternative pathway for molecular catalysts anchoring on inorganic semiconductors for efficient renewable energy utilization.

中文翻译：

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在金属氧化物表面活化Kläui型有机金属前驱物以增强太阳能氧化能力

在金属氧化物表面活化分子催化剂可能是克服缓慢的界面动力学并提高光（电）化（PEC）水氧化效率的有前途的策略。然而，用于PEC工艺的无机半导体与用于表面催化反应的有机金属分子催化剂之间的物理缔合通常仍然是一个具有挑战性的问题。在本工作中，首先合成了Kläui型有机金属前体[Cp * Ir {P（O）（OH）₂ } ₃ ] Na，随后通过各种方法成功地将其锚定在透明导电基板上生长的BiVO ₄纳米金字塔上。使用IO ₄处理所得的杂化异质结构^–诱导铱原子与BiVO ₄纳米晶体之间的强协同作用，与PEC水氧化的可逆氢电极（RHE）相比，在1.23 V时光电流密度提高了5.5倍。这种简单的方法为分子催化剂锚定在无机半导体上提供了有效的替代途径，以有效地利用可再生能源。