Department of Materials Science and Engineering and ‡Research Institute of Advanced Materials (RIAM), Seoul National University , Seoul 151-744, Korea.
J Am Chem Soc. 2014 May 21;136(20):7435-43. doi: 10.1021/ja5026529. Epub 2014 May 7.
The development of a water oxidation catalyst has been a demanding challenge in realizing water splitting systems. The asymmetric geometry and flexible ligation of the biological Mn4CaO5 cluster are important properties for the function of photosystem II, and these properties can be applied to the design of new inorganic water oxidation catalysts. We identified a new crystal structure, Mn3(PO4)2·3H2O, that precipitates spontaneously in aqueous solution at room temperature and demonstrated its high catalytic performance under neutral conditions. The bulky phosphate polyhedron induces a less-ordered Mn geometry in Mn3(PO4)2·3H2O. Computational analysis indicated that the structural flexibility in Mn3(PO4)2·3H2O could stabilize the Jahn-Teller-distorted Mn(III) and thus facilitate Mn(II) oxidation. This study provides valuable insights into the interplay between atomic structure and catalytic activity.
开发水氧化催化剂一直是实现水分解系统的一个艰巨挑战。生物 Mn4CaO5 簇的不对称几何形状和灵活的配位是光合作用 II 功能的重要特性,这些特性可应用于新型无机水氧化催化剂的设计。我们鉴定出一种新的晶体结构 Mn3(PO4)2·3H2O,它可在室温下于水溶液中自发沉淀,并在中性条件下表现出高催化性能。大体积的磷酸盐多面体在 Mn3(PO4)2·3H2O 中诱导出较无序的 Mn 几何形状。计算分析表明,Mn3(PO4)2·3H2O 中的结构灵活性可以稳定 Jahn-Teller 扭曲的 Mn(III),从而促进 Mn(II)氧化。这项研究为原子结构和催化活性之间的相互作用提供了有价值的见解。