Theory‐Guided Experimental Design of Covalent Triazine Frameworks for Efficient Photocatalytic Hydrogen Production

Abstract The high crystalline covalent triazine framework‐1 (CTF‐1), composed of alternating triazine and phenylene, has emerged as an efficient photocatalyst for solar‐driven hydrogen evolution reaction (HER). However, it is of great challenge to further improve photocatalytic HER performance via increasing crystallinity due to its near‐perfect crystallization. Herein, an alternative strategy of scaffold functionalization is employed to optimize the energy band structure of crystalline CTF‐1 for boosting hydrogen‐evolving activity. Guided by the computational predictions, versatile CTF‐based polymer photocatalysts are prepared with different functional groups (OH, NH2, COOH) using binary polymerization for practical hydrogen production. Experiment evidence verifies that the introduction of a limited number of electron‐donating groups is sufficient to maintain high crystallinity in CTF, modulate the band structure, broaden visible light absorption, and consequently enhance its photophysical properties. Notably, the functionalization with OH exhibits the most positive effect on CTF‐1, delivering a photocatalytic activity with a hydrogen‐producing rate exceeding 100 µmol h−1.