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投稿者: Yuma Morimoto

Article

Molecular Water Oxidation Mechanisms Followed by Transition Metals: State of the Art

† Departament de Química, Universitat Autònoma de Barcelona, Cerdanyola del Vallès, 08193 Barcelona,Spain
‡ Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans, 16, 43007 Tarragona, Spain
Acc. Chem. Res., Article ASAP
DOI: 10.1021/ar400169p
Publication Date (Web): December 11, 2013
Copyright © 2013 American Chemical Society
Biography
Xavier Sala was born in Sant Feliu de Guíxols in 1979 and received a Ph.D. in Chemistry from UdG in 2007. After postdoctoral research with P. W. N. M. van Leeuwen and A. Llobet at ICIQ, he is currently Lecturer at UAB, where he leads the SelOxCat research group.
Biography
Somnath Maji received his Ph.D. in 2009 from I.I.T. Bombay, India, under the supervision of G. K. Lahiri. Henceforth he is a postdoctoral researcher in Antoni Llobet’s group at ICIQ, Tarragona, Spain. Currently he is working on all aspects of ruthenium complexes that catalyze water oxidation.
Biography
Roger Bofill, born in Catalonia (Spain) in 1973, obtained the degree and Ph.D. in Chemistry at the UAB. He was a postdoctoral researcher at the universities of Sussex and Nottingham (UK) during 2001–2004, and he is currently Lecturer at the UAB, working on selective oxidation catalysis.
Biography
Jordi García-Antón was born in Cubelles (Barcelona, Spain) in 1976. He received his Ph.D. in Chemistry in 2003 from the UAB. After a postdoctoral stay at the LCC–CNRS in Toulouse (France) in the group of Bruno Chaudret, he joined the UAB as a Lecturer in chemistry.
Biography
Lluis Escriche was born in Manresa, Spain, in 1957. He received B.S. and Ph.D. degrees in chemistry from the UAB, and since 1990, he has been associate professor of Inorganic Chemistry at this university.
Biography
Antoni Llobet received a Ph.D. from UAB. Then he was a Post-Fellow at the University of North Carolina with T.J. Meyer and at Texas A&M University with D.T. Sawyer and A.E. Martell. He is currently a Professor of Chemistry at UAB and Group Leader at ICIQ.

Abstract

Abstract Image
One clean alternative to fossil fuels would be to split water using sunlight. However, to achieve this goal, researchers still need to fully understand and control several key chemical reactions. One of them is the catalytic oxidation of water to molecular oxygen, which also occurs at the oxygen evolving center of photosystem II in green plants and algae. Despite its importance for biology and renewable energy, the mechanism of this reaction is not fully understood.
Transition metal water oxidation catalysts in homogeneous media offer a superb platform for researchers to investigate and extract the crucial information to describe the different steps involved in this complex reaction accurately. The mechanistic information extracted at a molecular level allows researchers to understand both the factors that govern this reaction and the ones that derail the system to cause decomposition. As a result, rugged and efficient water oxidation catalysts with potential technological applications can be developed.
In this Account, we discuss the current mechanistic understanding of the water oxidation reaction catalyzed by transition metals in the homogeneous phase, based on work developed in our laboratories and complemented by research from other groups. Rather than reviewing all of the catalysts described to date, we focus systematically on the several key elements and their rationale from molecules studied in homogeneous media. We organize these catalysts based on how the crucial oxygen–oxygen bond step takes place, whether via a water nucleophilic attack or via the interaction of two M–O units, rather than based on the nuclearity of the water oxidation catalysts. Furthermore we have used DFT methodology to characterize key intermediates and transition states. The combination of both theory and experiments has allowed us to get a complete view of the water oxidation cycle for the different catalysts studied. Finally, we also describe the various deactivation pathways for these catalysts.
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