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论文类型：期刊论文

发表时间：2018-01-01

发表刊物：Dalton Transactions

卷号：47

期号：41

页面范围：14381-14387

ISSN号：14779226

摘要：Resolving the questions, namely, the selection of Mn by nature to build the oxygen-evolving complex (OEC) and the presence of a cubic Mn3CaO4 structure in OEC coupled with an additional dangling Mn (Mn4) via μ-O atom are not only important to uncover the secret of water oxidation in nature, but also essential to achieve a blueprint for developing advanced water-oxidation catalysts for artificial photosynthesis. Based on the important experimental results reported so far in the literature and on our own findings, we propose a new hypothesis for the water oxidation mechanism in OEC. In this new hypothesis, we propose for the first time, a complete catalytic cycle involving a charge-rearrangement-induced MnVII-dioxo species on the dangling Mn4 during the S3  ?S4 transition. Moreover, the O-O bond is formed within this MnVII-dioxo site, which is totally different from that discussed in other existing proposals. © 2018 The Royal Society of Chemistry.