MOF-Templated Sulfurization of Atomically Dispersed Manganese Catalysts Facilitating Electroreduction of CO2 to CO

To reach a carbon-neutral future, electrochemical CO2 reduction reaction (eCO(2)RR) has proven to be a strong candidate for the next-generation energy system. Among potential materials, single-atom catalysts (SACs) serve as a model to study the mechanism behind the reduction of CO(2)to CO, given their well-defined active metal centers and structural simplicity. Moreover, using metal-organic frameworks (MOFs) as supports to anchor and stabilize central metal atoms, the common concern, metal aggregation, for SACs can be addressed well. Furthermore, with their turnability and designability, MOF-derived SACs can also extend the scope of research on SACs for the eCO(2)RR. Herein, we synthesize sulfurized MOF-derived Mn SACs to study effects of the S dopant on the eCO(2)RR. Using complementary characterization techniques, the metal moiety of the sulfurized MOF-derived Mn SACs (Mn-SA/SNC) is identified as MnN3S1. Compared with its non-sulfur-modified counterpart (Mn-SA/NC), the Mn-SA/SNC provides uniformly superior activity to produce CO. Specifically, a nearly 30% enhancement of Faradaic efficiency (F.E.) in CO production is observed, and the highest F.E. of approximately 70% is identified at -0.45 V. Through operando spectroscopic characterization, the probing results reveal that the overall enhancement of CO production on the Mn-SA/SNC is possibly caused by the S atom in the local MnN3S1 moiety, as the sulfur atom may induce the formation of S-O bonding to stabilize the critical intermediate, *COOH, for CO2-to-CO. Our results provide novel design insights into the field of SACs for the eCO(2)RR.