A novel two-dimensional cobaltporphyrin-based organic framework as a promising electrocatalyst for CO₂ reduction reaction: a computational study

The electrocatalytic CO2 reduction reaction (CO2RR) offers a fascinating approach to converting CO2 into valuable chemical feedstocks. Up to now, the development of highly efficient electrocatalysts has been a significant bottleneck in this field. In this study, employing density functional theory (DFT) calculations, we design a range of stable two-dimensional (2D) metalloporphyrin organic frameworks (TM-PMOFs, TM = Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, and Ag, respectively) built by copper clusters and metalloporphyrin (TM-TCPP), whose CO2RR performance is studied in detail. Among them, the 2D cobaltporphyrin-based organic framework (Co-PMOF) is identified to be the best CO2RR electrocatalyst on account of its low limiting potential (-0.53 V), whose enhanced electrocatalytic performance can be attributed to the presence of numerous active sites on both sides of its 2D framework, as well as the synergistic effect between copper clusters and cobaltporphyrins in facilitating CO2 reduction. These findings provide valuable insights and encourage further experimental research on metallic 2D PMOF materials for CO2 electrochemical reduction.