A computational study on CO2 electrochemical reduction on two dimensional metal-1,2,3,4,5,6,7,8,9,10,11,12-perthiolated coronene frameworks

Abstract

The electrochemical CO₂ reduction reaction (CO₂RR) is a valid strategy for the conversion of CO₂ into valuable fuels and chemical products, thereby alleviating the energy crisis and environmental problems. In this work, the reaction mechanism of the CO₂RR has been studied on the two dimensional MOFs TM–PTC (TM = Sc–Zn, Y–Mo, and Ru–Ag; PTC = 1,2,3,4,5,6,7,8,9,10,11,12-perthiolated coronene) by using the density functional method. Our results showed that for the studied catalysts, the main products are CH₄ and HCOOH. Mo–PTC has the best catalytic activity for the CO₂RR in producing CH₄. Axial oxygen modified TM–PTC, i.e., TM–O–PTC shows different catalytic behavior compared with those without axial oxygen in producing CH₄. The inactive catalyst Nb–PTC for CH₄ becomes active after modification with an axial oxygen ligand. Zn–PTC and Mn–PTC are the promising catalysts for the CO₂RR in producing HCOOH. The solvent effect plays an important role in both the reaction mechanism and catalytic activity. We hope that this work can provide a new avenue for the development of 2D MOF type CO₂RR electrocatalysts.