Theory Study on Catalytic Hydrogenation Transformation of CO 2 to Formic Acid Over B, N, Si Doped Modified Holey Graphyne Supported Single Atom Fe

Abstract Conversion of CO 2 to formic acid based on efficient catalysts is a promising strategy for reducing CO 2 content. In this work, density functional theory (DFT) calculations were employed to construct models of Fe‐X‐Holey graphyne (X = C, B, N, Si) catalysts, and the reaction mechanisms of carbon dioxide hydrogenation to formic acid over these four catalysts were investigated. The results showed that all the above four catalysts were able to activate H 2 with varying degrees and provided reaction sites for H 2 cleavage, leading to the generation of Fe‐H hydrides. The energy barriers for the process of CO 2 protonation to produce HCOO* intermediates were lower on Fe‐H metal hydrides. Doping of B, N, and Si atoms introduced new reaction sites and lowered the reaction barriers, of which the doping of B atoms was the most effective.