Industrial H ₂ O ₂ Electrosynthesis in Neutral Saltwater Over Polythiophene‐Modulated Edge‐Nickel Sites in Conductive Metal‐Organic‐Framework

ABSTRACT Electrochemical hydrogen peroxide (H 2 O 2 ) synthesis in neutral saltwater holds promise for medical sterilization and marine remediation, but is limited by the scarcity of catalysts combining high selectivity and industrial‐current capability. Here, we report a polythiophene‐modulated strategy to activate the edge‐nickel sites in the conductive metal‐organic framework (Ni‐HHTP) for efficient H 2 O 2 electrosynthesis via two‐electron oxygen reduction reaction (2e − ORR). The polythiophene with sufficient oxygen‐containing species in situ coordinated with the edge Ni‐sites in Ni‐HHTP to form a penta‐coordinated Ni‐O 5 configuration, thus tailoring the electronic structure of nickel centers and optimizing the 2e − ORR activity and selectivity. Meanwhile, Ni‐HHTP possesses a well‐defined porous architecture, in which polythiophene is incorporated and significantly enhances its electronic conductivity, favoring rapid reaction kinetics. Thus, the resulting catalyst achieves over 90% H 2 O 2 selectivity in simulated seawater (3.6 wt.% NaCl), and operates stably at an industrial current density of 250 mA cm −2 . When integrated into a solar‐driven system, there is still an average Faradaic efficiency of ∼100% for H 2 O 2 electrosynthesis, as well as a solar‐to‐H 2 O 2 conversion efficiency of 12.8%. This work demonstrates the precise activation of metal sites in conductive metal‐organic frameworks via polymer modulation, offering a practical avenue for industrial‐scale H 2 O 2 electrosynthesis under neutral conditions.