Porphyrin-based Bi-MOFs with Enriched Surface Bi Active Sites for Boosting Photocatalytic CO2 Reduction.

The inherent challenges in using metal-organic frameworks (MOFs) for photocatalytic CO2 reduction are the combination of wide-range light harvesting, efficient charge separation and transfer as well as highly exposed catalytic active sites for CO2 activation and reduction. We present here a promising solution to satisfy these requirements together by modulating the crystal facet and surface atomic structure of a porphyrin-based bismuth-MOF (Bi-PMOF). The series of structural and photo-electronic characterizations together with photocatalytic CO2 reduction experiment collectively establish that the enriched Bi active sites on the (010) surface prefer to promote efficient charge separation and transfer as well as the activation and reduction of CO2 . Specifically, the Bi-PMOFs-120-F with enriched surface Bi active sites exhibits optimal photocatalytic CO2 reduction performance to CO (28.61 µmol h-1 g-1 ) and CH4 (8.81 µmol h-1 g-1 ). This work provides new insights to synthesize highly efficient main group p-block metal Bi-MOF photocatalysts for CO2 reduction through a facet-regulation strategy and sheds light on the surface structure-activity relationships of the MOFs.