Two-Dimensional Porphyrin-Based Covalent Organic Framework with Enlarged Inter-layer Spacing for Tunable Photocatalytic CO2 Reduction

Two-dimensional (2D) porphyrin-based covalent organic frameworks (COFs) are one of the most promising candidates for photocatalytic carbon dioxide reduction reaction (CO₂RR), which however still suffer from the hindered mass transfer during the catalysis procedure associated with the close packing of 2D COF layers due to the strong axial π-π stacking. Herein, condensation between the porphyrinic aldehydes p-MPor-CHO (M = H₂, Co, and Ni) and 3,8-diamino-6-phenyl-phenanthridine (DPP) affords new porphyrin-based 2D COF architecture MPor-DPP-COFs (M = H₂, Co, and Ni). The bulky phenyl substituent at the phenanthridine periphery of the linking unit reduces the axial π-π stacking, providing an enlarged inter-layer spacing of 6.0 Å according to high-resolution transmission electron microscopy. This, in combination with the large surface area (1021 m² g^-1) revealed by nitrogen sorption measurements at 77 K for CoPor-DPP-COF possessing electroactive Co ions, endows it with excellent photocatalytic activity for CO₂RR with a CO generation rate of 10 200 μmol g^-1 h^-1 and a CO selectivity up to 82%. This work affords new ideas for achieving efficient photocatalytic CO₂RR upon fine-tuning the inter-layer spacing of 2D COFs.