Steric Hindrance‐ and Work Function‐Promoted High Performance for Electrochemical CO Methanation on Antisite Defects of MoS2 and WS2.

CO methanation from electrochemical CO reduction reaction (CORR) is significant for sustainable environment and energy, but electrocatalysts with excellent selectivity and activity are still lacking. Selectivity is sensitive to the structure of active sites, and activity can be tailored by work function. Moreover, intrinsic active sites usually possess relatively high concentration compared to artificial ones. Here, antisite defects MoS2 and WS2, intrinsic atomic defects of MoS2 and WS2 with a transition metal atom substituting a S2 column, were investigated for CORR by density functional theory calculations. The steric hindrance from the special bowl structure of MoS2 and WS2 ensured good selectivity towards CO methanation. Coordination environment variation of the active sites, the under‐coordinated Mo or W atoms, effectively lowered the work function, making MoS2 and WS2 highly active for CO methanation with the required potential of −0.47 and −0.49 V vs. reversible hydrogen electrode, respectively. Moreover, high concentration of active sites and minimal structural deformation during the catalytic process of MoS2 and WS2 enhanced their attraction for future commercial application. [ABSTRACT FROM AUTHOR]