p-Block Single-Atom Anchored MoS2 Monolayer for Efficient Electroreduction of CO2 to Formate via Strong p–sp Interaction

The electrocatalytic reduction of CO2 (CO2RR) to high market value HCOOH is highly attractive and challenging in chemistry. p-Block metals (Sn, Bi, In, Pb, and Sb) are promising candidates to trigger CO2 reduction to formate due to their specific stabilization of the HCOO* intermediate, while the high overpotential and low selectivity have now limited its practical application. Herein, we rationally designed a series of p-block single atom anchored MoS2 monolayer catalysts for efficient electroreduction of CO2 to formate by DFT methods. The systematic thermal evaluation demonstrates that single In, Sn, Sb, Tl, Pb, and Bi atoms could be atomically dispersed on 1T-MoS2 with high stability and could potentially be synthesized in the experiment. We reveal that the catalytic CO2RR activity of a p-block metal is highly correlated with the degree of charge transfer between the metal and the substrate, with the higher charge distribution on the metal induced by a stronger interaction with the HCOO intermediate. Among the six concept SACs, single Sb- and Bi-atom-supported 1T-MoS2 are identified as the most promising CO2RR catalysts to produce HCOOH, offering excellent energy efficiency and selectivity against the hydrogen evolution reaction.