Photochemical water splitting is the ideal target reaction in artificial photosynthesis [1,2], potentially able to provide long-term solutions to solar energy conversion and storage. While the reduction of water to hydrogen is of obvious interest as the fuel generating reaction, the kinetic bottleneck towards water splitting is represented by the oxidation of water to molecular oxygen, a complex process involving four-electron abstraction from two water molecules, with formation of a new O–O bond, and release of four protons [3,4]. This is why most of the attention in the area is focusing on the development of efficient water oxidation catalysts (WOCs). Among molecular WOCs, those featuring a reactive set of four transition metals can leverage an extraordinary interplay of electronic and structural properties [5]. These are of particular interest, owing to their close structural, and possibly functional, relationship to the oxygen evolving complex of natural photosynthesis. In the presentation, special attention will be given to two classes of tetrametallic molecular WOCs: (i) M4O4 cubane-type structures stabilized by simple organic ligands [6], and (ii) systems in which a tetranuclear metal core is stabilized by coordination of fully inorganic polyoxometalate (POM) ligands [7,8].
Tetrametallic Molecular Catalysts for Photochemical Water Oxidation
NATALI, Mirco;SCANDOLA, Franco
2014
Abstract
Photochemical water splitting is the ideal target reaction in artificial photosynthesis [1,2], potentially able to provide long-term solutions to solar energy conversion and storage. While the reduction of water to hydrogen is of obvious interest as the fuel generating reaction, the kinetic bottleneck towards water splitting is represented by the oxidation of water to molecular oxygen, a complex process involving four-electron abstraction from two water molecules, with formation of a new O–O bond, and release of four protons [3,4]. This is why most of the attention in the area is focusing on the development of efficient water oxidation catalysts (WOCs). Among molecular WOCs, those featuring a reactive set of four transition metals can leverage an extraordinary interplay of electronic and structural properties [5]. These are of particular interest, owing to their close structural, and possibly functional, relationship to the oxygen evolving complex of natural photosynthesis. In the presentation, special attention will be given to two classes of tetrametallic molecular WOCs: (i) M4O4 cubane-type structures stabilized by simple organic ligands [6], and (ii) systems in which a tetranuclear metal core is stabilized by coordination of fully inorganic polyoxometalate (POM) ligands [7,8].I documenti in SFERA sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
