For mimicry of natural photosynthesis, particulate-based Z-scheme overall water splitting (ZOWS) free of external bias is intriguing for hydrogen production, but it commonly confronts low efficiency with the huge challenge of charge transfer and separation. Here we report an assembly of unprecedentedly efficient ZOWS system with apparent quantum efficiency (AQE) of 10.3% at 420 nm using [Fe(CN)₆]³⁻/[Fe(CN)₆]⁴⁻ as redox mediator. The breakthrough of AQE is mainly ascribed to an effective cocatalyst strategy that significantly promotes charge transfer and surface catalysis. Meanwhile, the metallic Au cocatalyst is first revealed to favor electron transfer from BiVO₄ to [Fe(CN)₆]³⁻ shuttle ions, and site-selective deposition of Au and CoO_x dual cocatalysts on the corresponding electron-rich {010} and hole-rich {110} facets of BiVO₄ is crucial for promotion of water oxidation. This work highlights the importance of the cocatalyst strategy as well as site-selective deposition in accelerating charge separation and surface catalysis of artificial photocatalyst for enhanced solar-to-chemical energy conversion.

对于模拟自然光合作用，无外部偏压的基于颗粒的Z方案总水分解法（ZOWS）令人着迷，但它通常面临效率低下以及电荷转移和分离的巨大挑战。在这里，我们报告了一个空前有效的ZOWS系统的组装，该系统使用[Fe（CN）₆ ] ³⁻ / [Fe（CN）₆ ] ⁴⁻作为氧化还原介体，在420 nm处的表观量子效率（AQE）为10.3％。AQE的突破主要归功于有效促进了电荷转移和表面催化的助催化剂策略。同时，首先发现金属金助催化剂有利于电子从BiVO ₄转移到[Fe（CN）₆ ]^3- Bi离子，BiVO ₄的相应富电子{010}和富空穴{110}面上的Au和CoO _x双助催化剂的位置选择性沉积对于促进水氧化至关重要。这项工作强调了助催化剂策略以及位点选择性沉积在加速人工光催化剂的电荷分离和表面催化以增强太阳能到化学能转化方面的重要性。