Covalent organic frameworks (COFs) with two-dimensional (2D) structure are regarded as potential photocatalysts for light-induced hydrogen evolution due to their excellent visible light response performance, designable structure, and suitable energy bands for water reduction and oxidation. To investigate how linkages in the COF framework affect the holistic visible-light photocatalytic hydrogen production (PHP), herein, three tunable COF platforms with the same triazine benzene as the knot and phenyl as the linker, but with different linkages were constructed. The structure, photoelectrochemical properties and bandgap structure of these COFs were systematically discussed. The results showed that the dianhydride substituted imide-COF (PMDA-COF) possesses a sustainable and stable PHP rate of 435.6 μmol·g⁻¹·h⁻¹ under visible light irradiation, which is much higher than that hydrogen bond containing imine-COF (DHTA-COF, 56.2 μmol·g⁻¹·h⁻¹) and imine-COF (TPAL-COF, 6.8 μmol·g⁻¹·h⁻¹). In addition, PMDA-COF has excellent photo-generated charge separation capabilities, energy difference exists between PMDA and TAPT. Among them, D-A molecular heterojunction plays a crucial role., which helps not only to modify the electronic band structure but also to separate the reduction and oxidation sites. Our research is instructive for the further design of COF-based photocatalysts for H₂ evolution.

具有二维（2D）结构的共价有机骨架（COFs）由于其优异的可见光响应性能、可设计的结构以及适合水还原和氧化的能带，被认为是光诱导析氢的潜在光催化剂。为了研究 COF 框架中的连接如何影响整体可见光光催化制氢 (PHP)，本文构建了三个可调的 COF 平台，其具有相同的三嗪苯作为结和苯基作为连接体，但具有不同的连接。系统地讨论了这些COFs的结构、光电化学性能和带隙结构。结果表明，二酐取代酰亚胺-COF（PMDA-COF）具有435.6 μmol·g ^-1 ·h的可持续稳定的PHP速率^-1在可见光照射下，远高于含氢键的亚胺-COF（DHTA-COF，56.2 μmol·g ^-1 ·h ^-1）和亚胺-COF（TPAL-COF，6.8 μmol·g ^-1 ·h ^-1 )。此外，PMDA-COF 具有优异的光生电荷分离能力，PMDA 和 TAPT 之间存在能量差异。其中，DA分子异质结起着至关重要的作用，它不仅有助于改变电子能带结构，还有助于分离还原位点和氧化位点。我们的研究对于进一步设计用于 H ₂析出的基于 COF 的光催化剂具有指导意义。