Issue 41, 2018

Why nature chose the Mn4CaO5 cluster as water-splitting catalyst in photosystem II: a new hypothesis for the mechanism of O–O bond formation

Abstract

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.

Graphical abstract: Why nature chose the Mn4CaO5 cluster as water-splitting catalyst in photosystem II: a new hypothesis for the mechanism of O–O bond formation

Article information

Article type
Perspective
Submitted
13 may 2018
Accepted
06 avq 2018
First published
21 avq 2018
This article is Open Access
Creative Commons BY-NC license

Dalton Trans., 2018,47, 14381-14387

Why nature chose the Mn4CaO5 cluster as water-splitting catalyst in photosystem II: a new hypothesis for the mechanism of O–O bond formation

B. Zhang and L. Sun, Dalton Trans., 2018, 47, 14381 DOI: 10.1039/C8DT01931B

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