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Highly Efficient Binuclear Ruthenium Catalyst for Water Oxidation
Author(s) -
Sander Anett C.,
Maji Somnath,
Francàs Laia,
Böhnisch Torben,
Dechert Sebastian,
Llobet Antoni,
Meyer Franc
Publication year - 2015
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.201403344
Subject(s) - catalysis , ruthenium , chemistry , redox , carboxylate , water splitting , molecule , ligand (biochemistry) , catalytic oxidation , photochemistry , inorganic chemistry , organic chemistry , photocatalysis , biochemistry , receptor
Water splitting is one of the key steps in the conversion of sunlight into a usable renewable energy carrier such as dihydrogen or more complex chemical fuels. Developing rugged and highly efficient catalysts for the oxidative part of water splitting, the water oxidation reaction generating dioxygen, is a major challenge in the field. Herein, we introduce a new, and rationally designed, pyrazolate‐based diruthenium complex with the highest activity in water oxidation catalysis for binuclear systems reported to date. Single‐crystal X‐ray diffraction showed favorable preorganization of the metal ions, well suited for binding two water molecules at a distance adequate for OO bond formation; redox titrations as well as spectroelectrochemistry allowed characterization of the system in several oxidation states. Low oxidation potentials reflect the trianionic character of the elaborate compartmental pyrazolate ligand furnished with peripheral carboxylate groups. Water oxidation has been mediated both by a chemical oxidant (Ce IV )—by means of manometry and a Clark electrode for monitoring the dioxygen production—and electrochemically with impressive activities.