Defect-Engineered MoS ₂ to Anchor Fe Clusters for CO ₂ Hydrogenation to Methanol

MoS 2 has been recognized as an effective catalyst for the hydrogenation of CO 2 to methanol, where sulfur vacancies (S v ) serve as the active sites. However, its catalytic performance depends not only on the vacancy location (in-plane versus edge) but also on its precise configuration. In-plane adjacent double S v function as the active sites for methanol formation, whereas in-plane separated single vacancies remain inactive due to the insufficient assembly of metal centers. In this study, we employed an etching-before-loading strategy to synthesize Fe/MoS 2 -e catalysts that build defect–metal interfaces between Fe clusters and the MoS 2 basal plane, thereby activating basal-plane single S v . Compared to Fe clusters supported on pristine MoS 2, Fe clusters anchored at defect sites not only facilitated the generation of adjacent S v during H 2 pretreatment but also led to the formation of a distinct type of active site with single S v . This architecture effectively activates CO 2 into CO and modulates the adsorption strength of the key intermediate CO*, both of which contribute to a stable methanol yield of 170.8 mg·g cat. –1 ·h –1 and a high methanol selectivity (78.9%). This work provides a strategy for engineering defect-metal interfaces to enhance the catalytic performance in CO 2 conversion and other thermochemical processes.