Constructing Integrative Catalytic Pairs in Carbon Nanohorns for Enhanced Neutral H 2 O 2 Electrosynthesis

ABSTRACT Electrosynthesis of hydrogen peroxide (H 2 O 2 ) via the two‐electron oxygen reduction reaction (2e − ORR) offers a sustainable and decentralized alternative to the anthraquinone process. However, conventional solo‐active‐site catalysts are intrinsically limited by scaling relationships, imposing a trade‐off between activity and selectivity. Here, we construct integrative catalytic pairs (ICPs) comprising topological and chemical defects on carbon nanohorns (CNHs). Defect engineering on this conical CNH framework enables a coupling of pentagonal carbocycles with spatial adjacent oxygen functional groups to form ICPs, which deliver a remarkable partial current density of 513 mA cm −2 and over 80% Faradaic efficiency for H 2 O 2 electrosynthesis in neutral media. Control experiments and theoretical calculations reveal that these ICPs modulate the local electronic structure of each active site, enabling cascade reactions, tunable reactant‐adsorption modes, and efficient 2e − ORR. This work establishes a topological‐chemical strategy for constructing ICPs that break scaling relationships and guide the rational design of high‐efficiency carbon catalysts for H 2 O 2 electrosynthesis.