Kondo Mio, Tatewaki Hayato, Masaoka Shigeyuki
Division of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan.
Chem Soc Rev. 2021 Jun 21;50(12):6790-6831. doi: 10.1039/d0cs01442g.
The four-electron oxidation of water (2H2O → O2 + 4H+ + 4e-) is considered the main bottleneck in artificial photosynthesis. In nature, this reaction is catalysed by a Mn4CaO5 cluster embedded in the oxygen-evolving complex of photosystem II. Ruthenium-based complexes have been successful artificial molecular catalysts for mimicking this reaction. However, for practical and large-scale applications in the future, molecular catalysts that contain earth-abundant first-row transition metal ions are preferred owing to their high natural abundance, low risk of depletion, and low costs. In this review, the frontier of water oxidation reactions mediated by first-row transition metal complexes is described. Special attention is paid towards the design of molecular structures of the catalysts and their reaction mechanisms, and these factors are expected to serve as guiding principles for creating efficient and robust molecular catalysts for water oxidation using ubiquitous elements.
水的四电子氧化反应（2H₂O → O₂ + 4H⁺ + 4e⁻）被认为是人工光合作用的主要瓶颈。在自然界中，该反应由嵌入光系统II放氧复合体中的Mn₄CaO₅簇催化。钌基配合物已成为模拟该反应的成功人工分子催化剂。然而，对于未来的实际大规模应用而言，含有储量丰富的第一排过渡金属离子的分子催化剂更受青睐，因为它们具有天然丰度高、耗尽风险低和成本低的特点。在这篇综述中，描述了由第一排过渡金属配合物介导的水氧化反应的前沿进展。特别关注了催化剂分子结构的设计及其反应机制，并且这些因素有望作为使用常见元素创建高效且稳定的水氧化分子催化剂的指导原则。
