Mechanistic study of the competition between carbon dioxide reduction and hydrogen evolution reaction and selectivity tuning via loading single-atom catalysts on graphitic carbon nitride

In the context of catalytic CO2 reduction (CO2RR), the interference of the inherent hydrogen evolution reaction (HER) and the possible selectivity towards CO have posed a significant challenge to the generation of formic acid. To address this hurdle, in this work, we have investigated the impact of different single-atom metal catalysts on tuning selectivity by employing density functional theory (DFT) calculations to scrutinize the reaction pathways. Single-atom catalysts supported on carbon-based systems have proven to be pivotal in altering both the activity and selectivity of the CO2RR. In this study, a series of single-atom-metal-loaded g-C3N4 monolayers (MCN, M = Ni, Cu, Zn, Ga, Cd, In, Sn, Pb, Ag, Au, Bi, Pd and Pt) were systematically examined. Through detailed DFT calculations, we explored their influence on reaction selectivity between the *COOH and *OCHO intermediates. Notably, NiCN favors the reaction via the *OCHO route, with a significantly lower rate-determining potential of 0.36 eV, which is approximately 73.5% lower than that of the CN system (1.36 eV). Most importantly, the Ni single-atom catalyst with lower coordination significantly enhances CO2 adsorption, promoting CO2RR over HER. Overall, this study, guided by DFT calculations, provides a theoretical prediction of how the selection of single-atom metal catalysts can effectively modulate the reaction pathway, thereby offering a potential solution for achieving high product selectivity in CO2RR.