A Fully Noble Metal-Free Photosystem Based on Cobalt-Polyoxometalates Immobilized in a Porphyrinic Metal-Organic Framework for Water Oxidation.

Authors :: Paille G
Gomez-Mingot M
Roch-Marchal C
Lassalle-Kaiser B
Mialane P
Fontecave M
Mellot-Draznieks C
Dolbecq A
Source :: Journal of the American Chemical Society [J Am Chem Soc] 2018 Mar 14; Vol. 140 (10), pp. 3613-3618. Date of Electronic Publication: 2018 Feb 02.
Publication Year :: 2018
Abstract: The sandwich-type polyoxometalate (POM) [(PW <subscript>9</subscript> O <subscript>34</subscript> ) <subscript>2</subscript> Co <subscript>4</subscript> (H <subscript>2</subscript> O) <subscript>2</subscript> ] <superscript>10-</superscript> was immobilized in the hexagonal channels of the Zr(IV) porphyrinic MOF-545 hybrid framework. The resulting composite was fully characterized by a panel of physicochemical techniques. Calculations allowed identifying the localization of the POM in the vicinity of the Zr <subscript>6</subscript> clusters and porphyrin linkers constituting the MOF. The material exhibits a high photocatalytic activity and good stability for visible-light-driven water oxidation. It thus represents a rare example of an all-in-one fully noble metal-free supramolecular heterogeneous photocatalytic system, with the catalyst and the photosensitizer within the same porous solid material.

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