Molecular Engineering of Porous Fe‐N‐C Catalyst with Sulfur Incorporation for Boosting CO2 Reduction and Zn‐CO2 Battery.

Transition metal‐nitrogen‐carbon (M‐N‐C) catalysts have emerged as promising candidates for electrocatalytic CO2 reduction reaction (CO2RR) due to their uniform active sites and high atomic utilization rate. However, poor efficiency at low overpotentials and unclear reaction mechanisms limit the application of M‐N‐C catalysts. In this study, Fe‐N‐C catalysts are developed by incorporating S atoms onto ordered hierarchical porous carbon substrates with a molecular iron thiophenoporphyrin. The well‐prepared FeSNC catalyst exhibits superior CO2RR activity and stability, attributes to an optimized electronic environment, and enhances the adsorption of reaction intermediates. It displays the highest CO selectivity of 94.0% at −0.58 V (versus the reversible hydrogen electrode (RHE)) and achieves the highest partial current density of 13.64 mA cm−2 at −0.88 V. Furthermore, when employed as the cathode in a Zn‐CO2 battery, FeSNC achieves a high‐power density of 1.19 mW cm−2 and stable charge–discharge cycles. Density functional theory calculations demonstrate that the incorporation of S atoms into the hierarchical porous carbon substrate led to the iron center becoming more electron‐rich, consequently improving the adsorption of the crucial reaction intermediate *COOH. This study underscores the significance of hierarchical porous structures and heteroatom doping for advancing electrocatalytic CO2RR and energy storage technologies. [ABSTRACT FROM AUTHOR]