Chen Yang, Xu Boran, Yao Ruoqing, Chen Changhui, Zhang Chunxi
Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing, China.
University of Chinese Academy of Sciences, Beijing, China.
Front Plant Sci. 2022 Jul 7;13:929532. doi: 10.3389/fpls.2022.929532. eCollection 2022.
The oxygen-evolving center (OEC) in photosystem II (PSII) of oxygenic photosynthetic organisms is a unique heterometallic-oxide MnCaO-cluster that catalyzes water splitting into electrons, protons, and molecular oxygen through a five-state cycle (S, = 0 ~ 4). It serves as the blueprint for the developing of the man-made water-splitting catalysts to generate solar fuel in artificial photosynthesis. Understanding the structure-function relationship of this natural catalyst is a great challenge and a long-standing issue, which is severely restricted by the lack of a precise chemical model for this heterometallic-oxide cluster. However, it is a great challenge for chemists to precisely mimic the OEC in a laboratory. Recently, significant advances have been achieved and a series of artificial MnXO-clusters (X = Ca/Y/Gd) have been reported, which closely mimic both the geometric structure and the electronic structure, as well as the redox property of the OEC. These new advances provide a structurally well-defined molecular platform to study the structure-function relationship of the OEC and shed new light on the design of efficient catalysts for the water-splitting reaction in artificial photosynthesis.
产氧光合生物的光系统II（PSII）中的析氧中心（OEC）是一种独特的异金属氧化物MnCaO簇，它通过五态循环（S₀至S₄）催化水分解为电子、质子和分子氧。它为人工光合作用中开发用于生成太阳能燃料的人造水分解催化剂提供了蓝图。理解这种天然催化剂的结构-功能关系是一项巨大挑战和长期存在的问题，这受到该异金属氧化物簇缺乏精确化学模型的严重限制。然而，化学家在实验室中精确模拟OEC是一项巨大挑战。最近，已取得重大进展，报道了一系列人工MnXO簇（X = Ca/Y/Gd），它们紧密模拟了OEC的几何结构、电子结构以及氧化还原性质。这些新进展提供了一个结构明确的分子平台，用于研究OEC的结构-功能关系，并为人工光合作用中水分解反应的高效催化剂设计提供了新线索。
