High Entropy Alloys Enable Durable and Efficient Lithium‐Mediated CO2 Redox Reactions

Abstract Designing electrocatalysts with high activity and durability for multistep reduction and oxidation reactions is challenging. High‐entropy alloys (HEAs) are intriguing due to their tunable geometric and electronic structure through entropy effects. However, understanding the origin of their exceptional performance and identifying active centers is hindered by the diverse microenvironment in HEAs. Herein, NiFeCoCuRu HEAs designed with an average diameter of 2.17 nm, featuring different adsorption capacities for various reactants and intermediates in Li‐mediated CO 2 redox reactions, are introduced. The electronegativity‐dependent nature of NiFeCoCuRu HEAs induces significant charge redistribution, shifting the d ‐band center closer to Fermi level and forming highly active clusters of Ru, Co, and Ni for Li‐based compounds adsorptions. This lowers energy barriers and simultaneously stabilizes *LiCO 2 and LiCO 3 +CO intermediates, enhancing the efficiency of both CO 2 reduction and Li 2 CO 3 decomposition over extended periods. This work provides insights into specific active site interactions with intermediates, highlighting the potential of HEAs as promising catalysts for intricate CO 2 redox reactions.