Reaction Pathways for Water Oxidation to Molecular Oxygen Mediated by Model Cobalt Oxide Dimer and Cubane Catalysts
Reaction Pathways for Water Oxidation to Molecular Oxygen Mediated by Model Cobalt Oxide Dimer and Cubane Catalysts
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DOI：
10.1021/jp511805x
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发表时间：
2015-05-21
影响因子：
3.7
通讯作者：
Aikens, Christine M.
中科院分区：
文献类型：
--
作者：
Fernando, Amendra;Aikens, Christine M.
用混合密度泛函理论方法研究了模型氧化钴二聚体和立方烷配合物上的水氧化反应。对这些模型化合物的电子结构和能量学进行了深入研究。二聚体催化剂上的热力学最低能量途径是通过溶剂水分子对Co(V)-O自由基部分的亲核攻击进行的。立方烷催化剂上最低的能量途径是Co(V)-O自由基氧基与桥式氧位的偶联。发现模型体系对配体的位置和氢键环境非常敏感，从而导致不同的异构体能量。
Hybrid density functional theory calculations have been employed to investigate the water oxidation reaction on model cobalt oxide dimer and cubane complexes. Electronic structure and energetics of these model compounds were thoroughly investigated. The thermodynamically lowest energy pathway on the dimer catalyst proceeds through a nucleophilic attack of a solvent water molecule to Co(V)-O radical moiety. The lowest energy pathway on the cubane catalyst involves a geminal coupling of Co(V)-O radical oxo group with bridging oxo sites. Model systems were found to be very sensitive to the positions of ligands and to the hydrogen-bonding environment leading to different isomer energies.