Interstitial Oxygen Acts as Electronic Buffer Stabilizing High‐Entropy Alloys for Trifunctional Electrocatalysis

Abstract Understanding the effect of elements’ oxygen affinity is essential for comprehending high‐entropy alloys’ (HEAs) complete properties. However, the origin of HEAs' oxygen‐containing structure and stability remains poorly understood, primarily due to their diverse components, hindering synthesis and analysis. Herein, the O‐doping HEAs (HEA‐O) have demonstrated outstanding performance and stability in electrolyzed water and Zinc–air batteries which can be reassembled after being stable for more than 1600 h when the zinc consumption is over. The experiment and DFT simulation demonstrate that Cr with strong oxygen affinity can introduce more oxygen into the system of HEAs. Consequently, interstitial oxygens act as electronic buffers making the binding energy of other metal elements move to a higher level. Additionally, O‐doping lowers the d‐band center promoting electrochemical activity and increasing vacancy formation energies of metal active sites leading to super stability. The study provides significant insights into the design and comprehension of interstitial oxygen‐doped HEAs.