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

Mohammad Mahdi Najafpour, Gernot Renger, Małgorzata Hołyńska, Atefeh Nemati Moghaddam, Eva Mari Aro, Robert Carpentier, Hiroshi Nishihara, Julian J. Eaton-Rye, Jian Ren Shen, Suleyman I. Allakhverdiev

Research output: Contribution to journalReview article

294 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)2886-2936
Number of pages51
JournalChemical Reviews
Volume116
Issue number5
DOIs
Publication statusPublished - Mar 9 2016

ASJC Scopus subject areas

  • Chemistry(all)

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    Najafpour, M. M., Renger, G., Hołyńska, M., Moghaddam, A. N., Aro, E. M., Carpentier, R., Nishihara, H., Eaton-Rye, J. J., Shen, J. R., & Allakhverdiev, S. I. (2016). Manganese Compounds as Water-Oxidizing Catalysts: From the Natural Water-Oxidizing Complex to Nanosized Manganese Oxide Structures. Chemical Reviews, 116(5), 2886-2936. https://doi.org/10.1021/acs.chemrev.5b00340