Terphenyl Functionalized Covalent Triazine Polymer as Metal‐Free Photocatalyst for Superior Hydrogen Peroxide Production

Abstract Artificial photosynthesis of H 2 O 2 from H 2 O and O 2 by visible light is a promising approach, but the efficiency is still unsatisfactory because of the inefficient O 2 adsorption and proton supply. Here, terphenyl functionalized covalent triazine polymer (CTP‐TD) is prepared for efficient H 2 O 2 production. Experimental and theoretical results show that terphenyl structure can promote O 2 adsorption by regulating the oxygen evolution (O 2 → 1 O 2 ) and improve proton supply by accelerating water oxidation. The terphenyl structure significantly promotes the singlet oxygen ( 1 O 2 ) production via the intersystem crossing (ISC) process. The electrophilic 1 O 2 is more easily adsorbed on the catalyst surface than O 2 . Simultaneously, the accumulated holes at the terphenyl structure lower water oxidation energy barriers and accelerate the water dehydrogenation process. This work provides a valuable reference and new inspiration for the polymer design of efficient H 2 O 2 generation from the perspective of reactant supply.