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