A Computation‐guided Design of Highly Defined and Dense Bimetallic Active Sites on a Two‐dimensional Conductive Metal‐organic Framework for Efficient H2O2 Electrosynthesis

Abstract Electrochemical synthesis of hydrogen peroxide (H 2 O 2 ) via the two‐electron oxygen reduction reaction (2e − ‐ORR) provides an alternative method to the energy‐intensive anthraquinone method. Metal macrocycles with precise coordination are widely used for 2e − ‐ORR electrocatalysis, but they have to be commonly loaded on conductive substrates, thus exposing a large number of 2e − ‐ORR‐inactive sites that result in poor H 2 O 2 production rate and efficiency. Herein, guided by first‐principle predictions, a substrate‐free and two‐dimensional conductive metal–organic framework (Ni‐TCPP(Co)), composed of CoN 4 sites in porphine(Co) centers and Ni 2 O 8 nodes, is designed as a multi‐site catalyst for H 2 O 2 electrosynthesis. The approperiate distance between the CoN 4 and Ni 2 O 8 sites in Ni‐TCPP(Co) weakens the electron transfer between them, thus ensuring their inherent activities and creating high‐density active sites. Meanwhile, the intrinsic electronic conductivity and porosity of Ni‐TCPP(Co) further facilitate rapid reaction kinetics. Therefore, outstanding 2e − ‐ORR electrocatalytic performance has been achieved in both alkaline and neutral electrolytes (>90 %/85 % H 2 O 2 selectivity within 0–0.8 V vs. RHE and >18.2/18.0 mol g −1 h −1 H 2 O 2 yield under alkaline/neutral conditions), with confirmed feasibility for water purification and disinfection applications. This strategy thus provides a new avenue for designing catalysts with precise coordination and high‐density active sites, promoting high‐efficiency electrosynthesis of H 2 O 2 and beyond.