Precise Modulation of Carbon Activity Sites in Metal‐Free Covalent Organic Frameworks for Enhanced Oxygen Reduction Electrocatalysis

Abstract Metal‐free carbon‐based materials have gained recognition as potential electrocatalysts for the oxygen reduction reaction (ORR) in new environmentally‐friendly electrochemical energy conversion technologies. The presence of effective active centers is crucial for achieving productive ORR. In this study, we present the synthesis of two metal‐free dibenzo[a,c]phenazine‐based covalent organic frameworks (DBP‐COFs), specifically JUC‐650 and JUC‐651, which serve as ORR electrocatalysts. Among them, JUC‐650 demonstrates exceptional catalytic performance for ORR in alkaline electrolytes, exhibiting an onset potential of 0.90 V versus RHE and a half‐wave potential of 0.72 V versus RHE. Consequently, JUC‐650 stands out as one of the most outstanding metal‐free COF‐based ORR electrocatalysts report to date. Experimental investigations and density functional theory calculations confirm that modulation of the frameworks' electronic configuration allows for the reduction of adsorption energy at the Schiff‐base carbon active sites, leading to more efficient ORR processes. Moreover, the DBP‐COFs can be assembled as excellent air cathode catalysts for zinc‐air batteries (ZAB), rivaling the performance of commercial Pt/C. This study provides valuable insights for the development of efficient metal‐free organoelectrocatalysts through precise regulation of active site strategies.