Polyamide thin film nanocomposite with in-situ co-constructed COFs for organic solvent nanofiltration

Organic solvent nanofiltration (OSN) is a novel membrane technology, it has great potential for organic solvent separation and purification due to its advantages of low energy consumption and mild operating conditions. High-performance OSN membranes are essential for OSN technology. Herein, we adopted a straightforward one-step in-situ co-polymerization procedure for the fabrication of a thin film nanocomposite (TFN) OSN membrane having a COFs-polyamide selective layer via doping the COFs reaction monomers, p-phenylenediamine (Pa) and 1,3,5-triformylphloroglucinol (Tp), into the aqueous m-phenylenediamine (MPD) solution and organic trimesoyl chloride (TMC) solution, respectively, during the interfacial polymerization (IP) process. With the ultra-low concentrations used in both MPD and COFs reactive monomers, the optimal TFN OSN membrane, TFN-100-75, achieves an ethanol permeance of 65.7 L m−2 h−1 MPa−1 and an Rhodamine B (RDB, 479 Da) rejection of 99.0%. Meanwhile, this OSN membrane has an ultra-smooth surface, corresponding to a roughness of only 2.9 ± 0.3 nm. Also, this membrane has larger porosity, average pore size, and surface pore density compared with the COFs-free thin-film composite (TFC) membrane. Besides, the TFN-100-75 membrane has a pure methanol and ethanol permeance of 184.3 and 105 L m−2 h−1 MPa−1, respectively, and a molecular weight cut-off (MWCO) of about 362 Da. The TFN-100-75 membrane achieved an rifampicin rejection of above 99% during the separation of rifampicin/ethanol solutions with different concentration as well as the continuous concentration experiment, demonstrating its potential in pharmaceutical separation and purification. During a long-time variable temperature immersion test in pure N,N-dimethylformamide (DMF) at 25 °C for 32 days and then at 80 °C for 24 days, the TFN-100-75 membrane demonstrates superior solvent resistance, where the RDB rejection decreased only by 2%, from 99.0% to 97.0%. The TFN OSN membrane fabricated by the simple process in this work shows better separation performance than most OSN membranes reported in literatures, and has bright prospects for industrial organic solvents treatment.