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

Abstract 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.