CO2 thermoreduction to methanol on the MoS2 supported single Co atom catalyst: A DFT study

Abstract Single-atom catalysts have attracted wide attention due to the maximum usage of single atom and the great potential to achieve high activity and selectivity for CO2 reduction reaction (CO2RR). CO2RR on the MoS2 supported single cobalt atom (Co/MoS2) monolayer is performed by using the first-principles simulation, and it is found that cobalt atom prefers to dispersedly anchor on MoS2 support as single atom. According to the transition state calculation for the various possible reaction pathways together with the reaction rate constants calculation, the preferable CO2RR pathway is the reverse water gas conversion (RWGS) and CO hydrogenation pathway with the rate-limiting step of CO hydrogenation into formyl (HCO). The entire reaction pathway can be summarized as *CO2 → *CO → *CHO → *CH2O → *CH2OH and *CH3O → CH3OH. The electronic structures analysis indicates that Co adatom induced gap states play an important role for CO2 activation and reduction. Therefore, the single cobalt atom supported on MoS2 monolayer is an efficient single atom catalyst for CO2 activation and conversion, and the current work may shed light on the development of single atom catalysts to CO2 reduction.