Mesoporous N,S‐Dual‐Doped Carbon Nanoreactors via Entropy‐Driven Interface Self‐Assembly for Efficient H ₂ O ₂ Electrosynthesis

ABSTRACT The electrochemical two‐electron oxygen reduction reaction (2e − ORR) offers a sustainable route for H 2 O 2 production. Rational catalyst design is essential for achieving efficient H 2 O 2 electrosynthesis, in which porous heteroatom‐doped carbon‐based materials hold tremendous potential. Nevertheless, the simultaneous realization of homogenized heteroatom doping and a precisely engineered porous structure in the carbon skeleton remains a significant challenge. Herein, we propose an entropy‐driven interface self‐assembly strategy to fabricate mesoporous N,S‐dual‐doped carbon‐based nanoreactors with tunable geometries. The optimal sample shows exceptional performance in a flow cell, achieving H 2 O 2 production rate of 17.38 mol gcat −1 h −1 at −0.2 V versus reversible hydrogen electrode (RHE) with > 90% selectivity. DFT calculations and finite element analysis simulations reveal that the N,S‐dual‐doping configuration optimizes the *OOH adsorption energy, while the well‑defined mesoporous structure accelerates mass transport and promotes the enrichment of surface O 2 concentration. This work provides a general principle for synergizing heteroatom doping and nanostructural engineering toward high‐performance electrocatalysts for sustainable synthesis.