Atomically Correlated Phosphorus–Sulfur Sites in Carbon Nitride for Efficient Hydrogen Peroxide Production

ABSTRACT Photocatalytic oxygen reduction offers a sustainable route to hydrogen peroxide (H 2 O 2 ) production; however, rapid charge‐carrier recombination and sluggish oxygen‐reduction reaction (ORR) kinetics remain the primary bottlenecks. Herein, an atomically correlated phosphorus–sulfur co‐doped graphitic carbon nitride (g‐C 3 N 4 ), referred to as P‐S:gCN, is demonstrated to enable efficient H 2 O 2 photogeneration in O 2 ‐saturated water without sacrificial agents. Introducing atomically correlated P‐S sites within the heptazine framework creates an asymmetric charge distribution that suppresses trap‐mediated recombination and promotes efficient charge separation. These coupled heteroatom sites also enhance oxygen adsorption and activation on the catalytic surface, directing the reaction through the selective 2e − ORR pathway to increase H 2 O 2 generation. Under visible‐light irradiation, P‐S:gCN achieves an apparent quantum yield of 6.80% at 420 nm and a solar‐to‐chemical conversion efficiency of 0.49% in pure water. Combined experimental and theoretical evidence reveals that atomically correlated P‐S sites regulate charge transport, suppress recombination, and promote selective 2e − ORR more effectively than isolated dopants. This atomically correlated dual‐site engineering opens avenues for tuning charge transport, electronic structure, and the stability of reaction intermediates in metal‐free photocatalytic systems.