Rational design of isostructural 2D porphyrin-based covalent organic frameworks for tunable photocatalytic hydrogen evolution.

Covalent organic frameworks have recently gained increasing attention in photocatalytic hydrogen generation from water. However, their structure-property-activity relationship, which should be beneficial for the structural design, is still far-away explored. Herein, we report the designed synthesis of four isostructural porphyrinic two-dimensional covalent organic frameworks (MPor-DETH-COF, M = H2, Co, Ni, Zn) and their photocatalytic activity in hydrogen generation. Our results clearly show that all four covalent organic frameworks adopt AA stacking structures, with high crystallinity and large surface area. Interestingly, the incorporation of different transition metals into the porphyrin rings can rationally tune the photocatalytic hydrogen evolution rate of corresponding covalent organic frameworks, with the order of CoPor-DETH-COF < H2Por-DETH-COF < NiPor-DETH-COF < ZnPor-DETH-COF. Based on the detailed experiments and calculations, this tunable performance can be mainly explained by their tailored charge-carrier dynamics via molecular engineering. This study not only represents a simple and effective way for efficient tuning of the photocatalytic hydrogen evolution activities of covalent organic frameworks at molecular level, but also provides valuable insight on the structure design of covalent organic frameworks for better photocatalysis.