Synergistic d‐Band Center Tailoring in Zn–Cu Dual‐Atom Catalysts for Enhanced Polysulfide Conversion in Na–S Batteries

ABSTRACT Room‐temperature sodium‐sulfur (RT Na–S) batteries have garnered considerable interest due to their low cost and high energy density. However, their practical application is impeded by the dissolution and shuttle effect of sodium polysulfides. In this work, we design a novel Zn‐Cu dual‐atom catalyst supported on g‐C 3 N 4 , which demonstrates superior catalytic activity and anchoring capability of the sulfur cathode through modulation of the electronic structure and adsorption configuration at the active sites. The catalyst is constructed by first fabricating single‐atom Zn sites, followed by the reduction and anchoring of adjacent Cu atoms via photogenerated electrons, leading to the formation of stable heteronuclear Zn‐Cu dual‐atom sites. Theoretical simulations reveal that the introduction of Cu induces notable splitting of the Zn d‐orbitals, upshifts the d‐band center, and strengthens coupling with the p‐orbitals of polysulfides. Moreover, the dual‐atom site offers multiple adsorption geometries, synergistically promoting both chemical anchoring and conversion kinetics of polysulfides. Therefore, the designed ZnCu dual‐atom‐based cathode exhibits long cycle stability and rate capability. This study provides new perspectives for the rational design of dual‐atom catalysts to suppress shuttle effects and accelerate reaction kinetics in RT Na–S batteries.