Manganese Compounds as Water-Oxidizing Catalysts: From the Natural Water-Oxidizing Complex to Nanosized Manganese Oxide Structures

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Department of Chemistry, and Centre of Climate Change and Global Warming, Institute for Advanced Studies in Basic Sciences (IASBS), Zanjan 45195-1159, Iran
§ Institute of Chemistry, Max-Volmer-Laboratory of Biophysical Chemistry, Technical University Berlin, Straße des 17. Juni 135, D-10623 Berlin, Germany
Fachbereich Chemie und Wissenschaftliches Zentrum für Materialwissenschaften (WZMW), Philipps-Universität Marburg, Hans-Meerwein-Straße, D-35032 Marburg, Germany
Department of Biochemistry and Food Chemistry, University of Turku, 20014 Turku, Finland
# Groupe de Recherche en Biologie Végétale (GRBV), Université du Québec à Trois-Rivières, C.P. 500, Trois-Rivières, Québec G9A 5H7, Canada
Department of Chemistry, School of Science, The University of Tokyo, 7-3-1, Hongo, Bunkyo-Ku, Tokyo 113-0033, Japan
Department of Biochemistry, University of Otago, P.O. Box 56, Dunedin 9054, New Zealand
Photosynthesis Research Center, Graduate School of Natural Science and Technology, Faculty of Science, Okayama University, Okayama 700-8530, Japan
Photosynthesis Research Center, Key Laboratory of Photobiology, Institute of Botany, Chinese Academy of Sciences, Beijing 100093, China
Controlled Photobiosynthesis Laboratory, Institute of Plant Physiology, Russian Academy of Sciences, Botanicheskaya Street 35, Moscow 127276, Russia
Institute of Basic Biological Problems, Russian Academy of Sciences, Pushchino, Moscow Region 142290, Russia
Department of Plant Physiology, Faculty of Biology, M.V. Lomonosov Moscow State University, Leninskie Gory 1-12, Moscow 119991, Russia
Cite this: Chem. Rev. 2016, 116, 5, 2886–2936
Publication Date (Web):January 26, 2016
Copyright © 2016 American Chemical Society
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All cyanobacteria, algae, and plants use a similar water-oxidizing catalyst for water oxidation. This catalyst is housed in Photosystem II, a membrane-protein complex that functions as a light-driven water oxidase in oxygenic photosynthesis. Water oxidation is also an important reaction in artificial photosynthesis because it has the potential to provide cheap electrons from water for hydrogen production or for the reduction of carbon dioxide on an industrial scale. The water-oxidizing complex of Photosystem II is a Mn–Ca cluster that oxidizes water with a low overpotential and high turnover frequency number of up to 25–90 molecules of O2 released per second. In this Review, we discuss the atomic structure of the Mn–Ca cluster of the Photosystem II water-oxidizing complex from the viewpoint that the underlying mechanism can be informative when designing artificial water-oxidizing catalysts. This is followed by consideration of functional Mn-based model complexes for water oxidation and the issue of Mn complexes decomposing to Mn oxide. We then provide a detailed assessment of the chemistry of Mn oxides by considering how their bulk and nanoscale properties contribute to their effectiveness as water-oxidizing catalysts.

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