Two-Dimensional Cobaltporphyrin-based Cobalt–Organic Framework as an Efficient Photocatalyst for CO2 Reduction Reaction: A Computational Study

The improvement of the photocatalytic performance of cobaltporphyrin as CO2 reduction catalysts by chemical modification has become a current research hotspot. Here, we contrastively investigate the catalytic performance of the two-dimensional (2D) cobaltporphyrin-based organic frameworks linked with phenyl, CoO-cluster, ZnO-cluster, and ZrO-cluster as CO2 reduction photocatalysts (abbreviated as CoP, Co-PMOF, Zn-PMOF, and Zr-PMOF, respectively) using density functional theory (DFT) computations. The computational results demonstrate that the 2D Co-PMOF exhibits superior catalytic activity than other MOFs in direct reduction of CO2 without introducing any cocatalysts, in which CH4 is final product with the lowest limiting potential of 0.39 V among all the reported data. The superior photocatalytic performance should be ascribed to highly accessible active sites on the double sides and the collaborative contribution from CoO-cluster and cobaltporphyrin during CO2 reduction. Therefore, our work may pave the way to extend the potential applications of 2D porphyrin-based MOFs toward photocatalytic CO2 reduction.