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

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 mu mol h-1. In order to promote photocatalytic hydrogen evolution reaction in covalent triazine frameworks (CTFs), it is imperative to functionalize highly crystalline CTFs. Guided by theoretical predictions and calculations, modifications are applied to CTF-1 using functional groups with varying electronic effects. The improved photocatalytic activity is witnessed by the incorporation of electron-donating groups. Experimental findings indicate that chemical modification optimizes the valence band position, broadens visible light absorption, and accelerates the charge carrier dynamics. image