A silk-like hydrogen-bonded organic framework functionalized membrane with intrinsic catalytic activity for nonmetallic reduction of 4-nitrophenol

A hydrogen-bonded organic framework based on the self-assembly of 4,4′,4′',4′''-(pyrene-1,3,6,8-tetrayl) tetraaniline was prepared for the functional coating on the membrane and show an intrinsic metal-free catalytic activity for 4-nitrophenol reduction. • HOF-PyTTA is synthesized for the first time based on the self-assembly of PyTTA. • The HOF-PyTTA exhibits metal-free catalytic activity for 4-NP reduction into 4-AP. • HOF-PyTTA was applied for the functional coating on membrane of different materials. • A catalytic column for 4-NP was fabricated using HOF-PyTTA/glass fiber membrane. Investigating the hydrogen-bonded organic frameworks (HOFs) with intrinsic functions has been a great challenge for the development of HOF materials. In this paper, an efficient way of obtaining a HOF with intrinsic catalytic activity is presented. A microporous HOF-PyTTA was self-assembled by using 4,4′,4′',4′''-(pyrene-1,3,6,8-tetrayl) tetraaniline (PyTTA) as an organic monomer. The monomer has a pyrene ring with a conjugated structure, which is conducive to the construction of large-area π-π interactions, therefore improving the stability of the HOF structure. The amino-functional group of the monomer serves as the active site which enables the HOF-PyTTA, which acts as a non-metallic catalyst to catalyze the conversion of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP). The permanent pore structure of the HOF-PyTTA was confirmed by X-ray single-crystal diffraction and CO 2 isotherm adsorption experiments. To broaden the application of HOF-PyTTA, we propose growing HOF-PyTTA on the filter membranes of diverse materials and making a catalytic column by filling the HOF-PyTTA/glass fiber membrane into the syringe. After pouring the mixture of 4-NP and NaBH 4 into the catalytic column, 4-NP was converted into 4-AP with a high rate of conversion. This work develops a simple, robust, and flexible HOF with intrinsic catalytic reduction activity for 4-NP, and broadens the application of HOF for functional modification and catalytic application.