3D qtz‐Topology COFs With Bicarbazole‐Centered Nodes for High‐Performance Adsorption of C ₆ VOCs

ABSTRACT The periodic structure featuring ordered open nanopores and high porosity endows covalent organic frameworks (COFs), especially three‐dimensional (3D) COFs, with remarkable potential for various applications. However, the precise construction of highly crystalline and functionalized 3D COFs remains a major challenge, due to the limited availability of suitable 3D building blocks and the inherent complexity of synthesis. Herein, by selecting a unique 3D precursor containing a bicarbazole motif, we successfully synthesized two 3D COFs (3D‐BCZ‐COF‐1 and 3D‐BCZ‐COF‐2) featuring threefold interpenetrated qtz topology. Notably, both COFs exhibit inherent porosity, high crystallinity, and large BET surface areas (2073 m ² g ⁻¹ for 3D‐BCZ‐COF‐1, 1989 m ² g ⁻¹ for 3D‐BCZ‐COF‐2). Benefiting from their excellent crystallinity and bicarbazole‐derived pore environments, both COFs demonstrate highly efficient adsorption of C ₆ volatile organic compounds (VOCs). In particular, 3D‐BCZ‐COF‐1 achieves adsorption capacities of 910.2 mg g ⁻¹ for benzene, 796.2 mg g ⁻¹ for cyclohexane, and 684.0 mg g ⁻¹ for n‐hexane, outperforming most reported porous materials. This work indicates that the precise fabrication of highly crystalline 3D COFs with functional units offers a promising platform for addressing VOCs challenges.