Hydrated Manganese(II) Phosphate (Mn3(PO4)2•3H2O) as a Water Oxidation Catalyst
Hydrated Manganese(II) Phosphate (Mn3(PO4)2•3H2O) as a Water Oxidation Catalyst
复制标题
DOI：
10.1021/ja5026529
复制
发表时间：
2014-05-21
影响因子：
15
通讯作者：
Nam, Ki Tae
中科院分区：
文献类型：
--
作者：
Jin, Kyoungsuk;Park, Jimin;Nam, Ki Tae
水氧化催化剂的开发在实现水裂解系统中一直是一个苛刻的挑战。生物Mn 4CaO 5簇的不对称几何结构和柔性连接是光系统II功能的重要性质，这些性质可应用于新型无机水氧化催化剂的设计。我们发现了一种新的晶体结构，Mn-3（PO 4）（2）中心点3 H（2）O，它在室温下在水溶液中自发沉淀，并在中性条件下表现出高的催化性能。磷酸盐多面体的存在导致Mn-3（PO 4）（2）中心点3 H（2）O中Mn的几何结构不规则。计算分析表明，Mn-3（PO 4）（2）中心点3 H（2）O的结构柔性可以稳定Jahn-Teller畸变的Mn（III），从而促进Mn（II）的氧化.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。
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, Mn-3(PO4)(2)center dot 3H(2)O, 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 Mn-3(PO4)(2)center dot 3H(2)O. Computational analysis indicated that the structural flexibility in Mn-3(PO4)(2)center dot 3H(2)O 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.