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

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• 作者：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
• 刊名：Chemical Reviews
• 出版年：2016
• 出版时间：March 9, 2016
• 年：2016
• 卷：116
• 期：5
• 页码：2886-2936
• 全文大小：2458K
• 年卷期：Mohammad Mahdi Najafpour received his Ph.D. in Inorganic Chemistry from Sharif University of Technology, Tehran, Iran, in 2009. Mahdi is a recipient of several awards and fellowships, notably the gold medal of the National Chemistry Olympiad in 2004. In addition, he ranked 1st in the Khwarizmi Youth Festival in 2010, and he was selected for the TWAS young affiliateship (2014). Mahdi also received the Al-Biruni award by the Academy of Sciences of Iran (2015), and he was selected to be among the best researchers in Iran by the Ministry of Science of Iran (2015). Currently, he is a faculty member in Chemistry in the Institute for Advanced Studies in Basic Sciences (IASBS) (Zanjan, Iran). As a nanobioinorganic chemist, Mahdi believes that with learning strategies from natural systems, design of modern catalysts for all reactions using only Earth abundant, low cost, and environmentally friendly metal ions is possible. Mahdi and his research group explore transition-metal compounds as water-oxidizing catalysts for artificial photosynthesis. He is the author of over 160 publications in these and other areas.
  Gernot Renger (1937–2013) obtained his doctoral degree, in 1970, in the research group of Professor Horst Witt at the Max-Volmer-Laboratory at the Technical Universtity (TU) in Berlin, Germany. His thesis project, which remained his scientific passion throughout his career, concerned the mechanism of photosynthetic water oxidation, which back then was basically a black box that he studied by light-induced oxygen evolution. After his habilitation in 1977, he soon became full professor of Physical Chemistry, in 1980, at the TU in Berlin, where he worked beyond his retirement (2003) until the evening before his unexpected death on January 12, 2013. His scientific work covered nearly all areas of the primary processes in photosynthesis. He made tremendous contributions, especially regarding the elucidation of the kinetics and thermodynamics of photosynthetic water oxidation. Gernot Renger has authored more than 400 scientific publications. We miss him and his thought-provoking questions and congenial friendship at international meetings.
  Małgorzata Hołyńska received her Ph.D. degree from Wrocław University (Poland) in 2009. Subsequently, she completed a one-year postdoctoral research stay as an Alexander von Humboldt fellow in the group of Prof. Dr. Stefanie Dehnen at Philipps-University Marburg (Germany). Since then she continues her independent academic career as a junior research group leader (habilitation in 2014) at the same university. Her research interests include the chemistry of polynuclear metal complexes with oxime/Schiff-base ligands as new magnetic materials and for biological/catalytic applications, in particular as gene transfer agents and as precursors of new water-oxidation catalysts.
  Atefeh Nemati Moghaddam received her B.Sc. in Chemistry from the University of Tabriz in 2008. In 2012, she joined Dr. Najafpour’s research group as a M.Sc. student at the Institute for Advanced Studies in Basic Sciences. Her major research interest is water oxidation by Mn-based catalysts, and she has had 10 publications in the field. Atefeh also received an award for her research presentation on a “mathematical model for manganese oxide-coated clay as catalysts for water oxidation” at the international conference on Photosynthesis Research for Sustainability held in Baku, Azerbaijan in 2013.
  Eva-Mari Aro is an Academy Professor working in the Department of Biochemistry, University of Turku. She has published over 250 peer-reviewed scientific papers, mostly on biophysics, biochemistry, and molecular biology of the photosynthetic apparatus. Aro has chaired the Academy of Finland Center of Excellence (AFCoE) “Integrative photosynthesis, bioactive compound and biohydrogen research” (2008–2013) and is currently chairing the AFCoE “Molecular biology of primary producers” 2014–2019. Aro is a partner and coordinator of several EU and Nordic research networks, and also a partner of an Australian CoE on Plant Energy Biology. Between 2004–2010 she served as president and past president of the International Society of Photosynthesis Research. Aro was vice chair of the Finnish Academy of Science and Letters 2012–2014 and is currently chair 2014–2016. She has many research- and science policy-related international duties of trust. She serves on the Science Advisory Boards of the Max Planck Institute (Golm) and the Dutch Government Program “BioSolarCells”.
  Robert Carpentier is Professor at Universite du Québec a Trois-Rivières, Québec, Canada. He obtained his Ph.D. in biochemistry from Laval University (1983, Québec). He is editor of the Journal of Photochemistry and Photobiology B: Biology, associate editor of Photosynthesis Research, and was the chair of the XIIIth International Congress on Photosynthesis (Montreal, 2004). His research interests concern the influence of environmental stresses on electron transport pathways in Photosystems I and II, and energy dissipation in photosynthesis.
  Hiroshi Nishihara received his B.Sc. degree in 1977, M.Sc. in 1979, and D.Sc. in 1982 from the University of Tokyo. He was appointed research associate of the Department of Chemistry, Faculty of Science and Technology at Keio University in 1982, and he was promoted Lecturer in 1990, and Associate Professor in 1992. Since 1996, he has been a Professor of the Department of Chemistry, School of Science at the University of Tokyo. He also worked as a visiting research associate of the Department of Chemistry at the University of North Carolina at Chapel Hill (1987–1989), and as a researcher of PRESTO, JRDC (1992–1996). His research has been focused on the creation of new electro- and photofunctional materials comprising both transition metals and p-conjugated chains, and invention of unidirectional electron-transfer systems utilizing molecular layer interfaces.
  Julian J. Eaton-Rye is a Professor in the Department of Biochemistry at the University of Otago, New Zealand. He received his Ph.D. from the University of Illinois in 1987, where he worked with Govindjee on the role of bicarbonate in the regulation of electron transfer through Photosystem II. Before joining the Biochemistry Department at Otago University in 1994, he was a postdoctoral researcher focusing on various aspects of Photosystem II protein biochemistry with Professor Norio Murata at the National Institute of Basic Biology in Okazaki, Japan; with Professor Wim Vermaas at Arizona State University; and with Dr. Geoffrey Hind at Brookhaven National Laboratory. His current research interests include structure–function relationships of Photosystem II proteins as well as the role of additional protein factors in the assembly of Photosystem II.
  Jian-Ren Shen is a Professor and the Director of the Photosynthesis Research Center, Graduate School of Natural Science and Technology, Okayama University in Japan. He received his bachelor’s degree in Biology from Zhejiang Agricultural University (now Zhejiang University) in China in 1982 and gained his Ph.D. in Biochemistry from the University of Tokyo in 1990. He subsequently spent 13 years in RIKEN (The Institute of Physical and Chemical Research) in Japan with the group of Yorinao Inoue studying the structure and function of Photosystem II, and moved to Okayama University as a Professor in 2003, where he is continuing studies on the mechanism of photosynthetic water oxidation based on structural analysis of Photosystem II. In collaboration with his colleagues, he solved the structure of Photosystem II at 1.9 Å in 2011, which was selected as one of the “Breakthroughs of the Year 2011” by the journal Science. His research interests include the structure and function of Photosystem II, the water-oxidizing complex, catalytic conversion of solar energy, and high-resolution crystal structural analysis of membrane proteins and their complexes.
  Suleyman I. Allakhverdiev is the Head of the Controlled Photobiosynthesis Laboratory at the Institute of Plant Physiology of the Russian Academy of Sciences (RAS), Moscow; Chief Research Scientist at the Institute of Basic Biological Problems RAS, Pushchino, Moscow Region; Professor at M.V. Lomonosov Moscow State University, Moscow, Russia; and Invited-Adjunct Professor at the Department of New Biology, Daegu Gyeongbuk Institute of Science & Technology (DGIST), Daegu, Republic of Korea. He is originally from Chaykend (Karagoyunly/Dilichanderesi), Armenia, and he obtained both his B.S. and M.S. in Physics from the Department of Physics, Azerbaijan State University, Baku. He obtained his Dr. Sci. degree (highest/top degree in science) in Plant Physiology and Photobiochemistry from the Institute of Plant Physiology, RAS (2002, Moscow), and Ph.D. in Physics and Mathematics (Biophysics), from the Institute of Biophysics, USSR (1984, Pushchino). His Ph.D. advisors were Academician Alexander A. Krasnovsky and Dr. Sci. Vyacheslav V. Klimov. He worked for many years (1990–2007) as a visiting scientist at the National Institute for Basic Biology (with Prof. Norio Murata), Okazaki, Japan, and in the Department de Chimie-Biologie, Université du Québec at Trois Rivières (with Prof. Robert Carpentier), Québec, Canada (1988–1990). He has been a guest editor of many (more than 30) special issues in international peer-reviewed journals. At present, he is a member of the Editorial Board of more than 15 international journals. Besides being editor-in-chief of SOAJ NanoPhotoBioSciences, associate editor of the International Journal of Hydrogen Energy, section editor of BBA Bioenergetics, he also acts as a referee for major international journals and grant proposals. He has authored (or coauthored) more than 350 research papers and 7 books. He has organized several (more than 10) international conferences on photosynthesis. His research interests include the structure and function of Photosystem II, the Photosystem II water-oxidizing complex, artificial photosynthesis, hydrogen photoproduction, catalytic conversion of solar energy, plants under environmental stress, and photoreceptor signaling.
• ISSN：1520-6890

文摘

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 O<sub>2sub> 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.