To solve serious energy and environmental crises caused by rapid industrial development, the formation of heterostructured photocatalysts is a promising approach for efficient and scalable H 2 production from water splitting. In this study, a strategy for the synthesis of triphenylphosphine-based covalent organic framework (P-COF-1)/covalent triazine framework (CTF) 2D−2D heterojunctions via intermolecular π−π interactions has been reported. The experimental results show that the H 2 production rate of the 5% P-COF-1/CTF heterojunction exhibits 14,100 μmol h −1 g −1 , which is 2.5−2.6 times as much as that of pure CTF and the mechanical mixture (5% P-COF-1 + CTF). Based on the results of characterization and theoretical calculations, a possible mechanism to well explain the enhanced photocatalytic performance of the Type II heterojunction system has been proposed. The present work provides an idea to construct highly efficient and stable COF/CTF all-organic heterojunctions, and this strategy broadens the application range of COF/CTF-based heterojunction materials easily by adjusting the composition and structure of COF materials.

The synthesis of phosphine‐based functional covalent organic frameworks (COFs) has attracted great attention recently. Herein, we present two examples of triphenylphosphine‐based COFs (termed P‐COFs) with well‐defined crystalline structures, high specific surface areas, and good thermal stability. Furthermore, rhodium catalysts with these P‐COFs as support material show high turnover frequency for the hydroformylation of olefins, as well as excellent recycling performance. This work not only extends the phosphine‐based COF family, but also demonstrates their application in immobilizing homogeneous metal‐based (e.g., Rh‐phosphine) catalysts for application in heterogeneous catalysis.

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The introduction of donor–acceptor (D–A) motifs into organic semiconductors has been considered as one of the effective strategies to regulate photocatalytic activity. Herein, D–A-type benzodithiophene-based covalent triazine framework materials (BDT-CTFs) have been reported. It has been shown that the valence band and conduction band positions, band gaps, and electron–hole separation efficiency can be adjusted by altering the D/A ratio in the BDT-CTF photocatalytic materials. It has been revealed that the high electron–hole separation, migration efficiency, and low electron–hole recombination rates, as well as the special D–A pore structures are the main reasons for the higher photocatalytic hydrogen evolution reaction (HER) activities of BDT-CTF-1 materials. This work revealed the structure–activity relationship in BDT-based CTFs with different D–A ratios, providing a strategy to develop organic photocatalysts with high performance.