Tailoring the catalytic activity and selectivity on CO2 to C1 products by the synergistic effect of reactive molecules: A DFT study

The conversion of CO2 to CO is one of the crucial pathways in the carbon dioxide reduction reaction (CO2RR). Iron and nitrogen co-doped carbon matrix (FeN4) is a promising catalyst for converting CO2to CO with excellent activity and selectivity. However, the reactive mechanism of CO2RR on the FeN4 catalyst is not fully unveiled. For example, it is still evasive that the obtained C1 product is methanol and/or methane instead of CO in some cases. Herein, DFT calculation is conducted to unravel the effect from both solvent molecules and intermediates as axial groups on the selectivity of C1 products in CO2RR using FeN4 catalyts. Calculation results demonstrate that the FeN4(H), FeN4(OH), FeN4(COOH), and FeN4(CO) configurations are not only beneficial to the removal of CO, but also effectively suppress the hydrogen evolution reaction, whereas the FeN4, FeN4(CO2) and FeN4(H2O) configurations are inclined to produce CH3OH and/or CH4. The mechanism studied in this work provides an inspiration of optimizing the selectivity of C1 products in CO2RR from the perspective of regulating solvent molecules and intermediates as axial groups on FeN4.