Three-Dimensional Covalent Organic Frameworks with Ultra-Large Pores for Highly Efficient Photocatalysis.

Benefiting from their unique structural merits, three-dimensional (3D) large-pore COF materials demonstrate high surface areas and interconnected large channels, which makes these materials promising in practical applications. Unfortunately, functionalization strategies and application research are still absent in these structures. To this end, a series of functional 3D stp -topologized COFs are designed based on porphyrin or metalloporphyrin moieties, named JUC-640-M (M = Co, Ni, or H). Interestingly, JUC-640-H exhibits a record-breaking low crystal density (0.106 cm 3 g -1 ) among all crystalline materials, along with the largest interconnected pore size (4.6 nm) in 3D COFs, high surface area (2204 m 2 g -1 ), and abundant exposed porphyrin moieties (0.845 mmol g -1 ). Inspired by the unique structural characteristics and photoelectrical performance, JUC-640-Co is utilized for the photoreduction of CO 2 to CO and demonstrates a high CO production rate (15.1 mmol g -1 h -1 ), selectivity (94.4%), and stability. It should be noted that the CO production rate of JUC-640-Co has exceeded those of all reported COF-based materials. This work not only produces a series of novel 3D COFs with large channels but also provides a new guidance for the functionalization and applications of COFs.