Thermodynamics‐Guided Design of Carbon Catalysts for Efficient on‐Site Hydrogen Peroxide Electrosynthesis

ABSTRACT Carbon catalysts featuring basal etheric C─O─C structures are promising for 2e‐ORR, with etheric carbon (C etheric ) serves as the active sites, but their controlled synthesis remains challenging. Here, we propose a thermodynamics‐guided methodology for predicting the formation probability of carbon active sites. Based on this framework, cobalt (Co) atoms are employed as coordination‐induced structural directors to experimentally realize the targeted sites. Statistical thermodynamic and DFT analyses reveal that Co incorporation thermodynamically promotes the formation of C─O─C moieties in CoC 3 O 1 and CoC 2 O 2 configurations, while maintaining favorable 2e‐ORR activity and selectivity. Guided by these insights, a Co‐induced etheric carbon catalyst (C─O─C(Co)) was successfully synthesized, which features the coexistence of CoC 3 O 1 and CoC 2 O 2 configurations and exhibits a 1.5‐fold increase in C etheric active site density compared to Co‐free catalysts. The C─O─C(Co) catalyst delivers outstanding 2e‐ORR performance, achieving a 0.68 V onset potential and ∼95% H 2 O 2 selectivity across a broad potential range. Practical applicability was validated through integration into PEMFC‐type devices, where the system could simultaneously generate electrical power and electrosynthesize H 2 O 2 . This work presents a thermodynamics‐guided, metal‐directed approach for rational design of carbon active sites, offering a predictive framework for functional carbon materials.