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

Artificial photosynthesis of H2O2 from H2O and O2 by visible light is a promising approach, but the efficiency is still unsatisfactory because of the inefficient O2 adsorption and proton supply. Here, terphenyl functionalized covalent triazine polymer (CTP‐TD) is prepared for efficient H2O2 production. Experimental and theoretical results show that terphenyl structure can promote O2 adsorption by regulating the oxygen evolution (O2→1O2) and improve proton supply by accelerating water oxidation. The terphenyl structure significantly promotes the singlet oxygen (1O2) production via the intersystem crossing (ISC) process. The electrophilic 1O2 is more easily adsorbed on the catalyst surface than O2. 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 H2O2 generation from the perspective of reactant supply. [ABSTRACT FROM AUTHOR]