Carbonate ions induce highly performed electrocatalytic water oxidation by cobalt oxyhydroxide nanoparticles
Carbonate ions induce highly performed electrocatalytic water oxidation by cobalt oxyhydroxide nanoparticles
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碳酸根离子通过羟基氧化钴纳米颗粒诱导高性能电催化水氧化
DOI：
10.1002/cssc.201601494
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发表时间：
2017
期刊：
影响因子：
--
通讯作者：
M. Yagi
中科院分区：
文献类型：
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作者：
K. Aiso;R. Takeuchi;T. Masaki;D. Chandra;K. Saito;T. Yui;M. Yagi
放氧复合体(OEC)的合成模型不仅可以更好地了解光合作用中水氧化的机理和辅助因素的作用，还可以作为水氧化催化剂实现人工光合作用，有望成为一种很有前途的太阳能燃料生产系统。然而，尽管多相OEC模型的活性中心的组成和结构已经引起了人们的广泛关注，但对光合作用OEC氧化水分所必需的辅因子的研究还很少。CoO(OH)纳米粒子对电催化水氧化的高活性是由Co32−辅因子诱导的。根据质子协同氧原子转移机理，提出了CO32-−离子作为O-−-O键形成的质子受体的可能性。O-−-O键的形成是由于配位在CoIV中心的相邻−离子对质子的有效接受而加速的，这与米氏动力学和电催化中观察到的显著的H/D同位素效应相一致。
Synthetic models of oxygen evolving complex (OEC) are used not only to gain better understanding of the mechanism and the roles of cofactors for water oxidation in photosynthesis, but also as water oxidation catalysts to realize artificial photosynthesis, which is anticipated as a promising solar fuel production system. However, although much attention has been paid to the composition and structure of active sites for development of heterogeneous OEC models, the cofactors, which are essential for water oxidation by the photosynthetic OEC, remain little studied. The high activity of CoO(OH) nanoparticles for electrocatalytic water oxidation is shown to be induced by a CO32−cofactor. The possibility of CO32−ions acting as proton acceptors for O−O bond formation based on the proton‐concerted oxygen atom transfer mechanism is proposed. The O−O bond formation is supposed to be accelerated due to effective proton acceptance by adjacent CO32−ions coordinated on the CoIVcenter in the intermediate, which is consistent with Michaelis–Menten‐type kinetics and the significant H/D isotope effect observed in electrocatalysis.