Synergistic Conversion of Hydrogen Peroxide and Benzaldehyde in Air by Silver Single‐Atom Modified Thiophene‐Functionalized g‐C 3 N 4

Abstract This study reports the synthesis of silver single‐atom‐loaded thiophene‐conjugated carbon nitride (Ag@T─C 3 N 4 ), a material with high carrier concentration and efficient carrier separation. Under visible light, Ag@T─C 3 N 4 catalyzes hydrogen peroxide (H 2 O 2 ) production and benzyl alcohol oxidation to benzaldehyde, achieving production rates of 4729.82 µmol·g −1 ·h −1 for H 2 O 2 and 19.71 mmol·g −1 ·h −1 for benzaldehyde. The synergy between thiophene conjugation and silver atoms extends visible light absorption and accelerates the 2‐electron oxygen reduction reaction (ORR), enhancing H 2 O 2 yield. Photogenerated holes oxidize benzyl alcohol to benzaldehyde, while the biphasic benzaldehyde‐water system enables spontaneous product separation. In situ Raman spectroscopy, rotating disk electrode testing, EPR, GC‐MS, and DFT calculations highlight the critical role of thiophene‐silver synergy in optimizing reaction pathways, enhancing catalyst‐intermediate interactions, and reducing Gibbs free energy, improving H 2 O 2 and benzaldehyde synthesis. This study provides new insights for designing carbon nitride‐based photocatalysts and offers a strategy for co‐producing value‐added chemicals.