A Universal Electronic Structure Modulation Strategy: Is Strong Adsorption Always Correlated with High Catalysis?

Abstract Unveiling the inherent link between polysulfide adsorption and catalytic activity is key to achieving optimal performance in Lithium‐sulfur (Li‐S) batteries. Current research on the sulfur reaction process mainly relies on the strong adsorption of catalysts to confine lithium polysulfides (LiPSs) to the cathode side, effectively suppressing the shuttle effect of polysulfides. However, is strong adsorption always correlated with high catalysis? The inherent relationship between adsorption and catalytic activity remains unclear, limiting the in‐depth exploration and rational design of catalysts. Herein, the correlation between “d‐band center‐adsorption strength‐catalytic activity” in porous carbon nanofiber catalysts embedded with different transition metals (M‐PCNF‐3, M = Fe, Co, Ni, Cu) is systematically investigated, combining the d‐band center theory and the Sabatier principle. Theoretical calculations and experimental analysis results indicate that Co‐PCNF‐3 electrocatalyst with appropriate d‐band center positions exhibits moderate adsorption capability and the highest catalytic conversion activity for LiPSs, validating the Sabatier relationship in Li‐S battery electrocatalysts. These findings provide indispensable guidelines for the rational design of more durable cathode catalysts for Li‐S batteries.