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ChemSusChem. 2018 Sep 21;11(18):3315-3322. doi: 10.1002/cssc.201801066. Epub 2018 Aug 1.

Immobilization of a Full Photosystem in the Large-Pore MIL-101 Metal-Organic Framework for CO2 reduction.

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Laboratoire de Chimie des Processus Biologiques (LCPB), Collège de France, PSL Research University, CNRS, Sorbonne Universités, 11 Marcelin Berthelot, 75231, Paris Cedex 05, France.
Univ. Lyon, Université Claude Bernard Lyon 1, CNRS, IRCELYON-UMR 5256, 2 Avenue Albert Einstein, 69626, Villeurbanne Cedex, France.


A molecular catalyst [Cp*Rh(4,4'-bpydc)]2+ and a molecular photosensitizer [Ru(bpy)2 (4,4'-bpydc)]2+ (bpydc=bipyridinedicarboxylic acid) were co-immobilized into the highly porous metal-organic framework MIL-101-NH2 (Al) upon easy postsynthetic impregnation. The Rh-Ru@MIL-101-NH2 composite allows the reduction of CO2 under visible light, while exhibiting remarkable selectivity with the exclusive production of formate. This Rh-Ru@MIL-101-NH2 solid represents the first example of MOFs functionalized with both a catalyst and a photosensitizer in a noncovalent fashion. Thanks to the coconfinement of the catalyst and photosensitizer into the cavity's nanospace, the MOF pores are used as nanoreactors and enable molecular catalysis in a heterogeneous manner.


carbon dioxide; heterogeneous catalysis; metal-organic frameworks; nanoreactors; photocatalysis


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