PTSA-mediated interfacial catalytic polymerization of crystalline dense covalent organic framework membranes for enhanced desalination

Construction of covalent organic frameworks (COF) membranes for desalination applications was challenging, mainly due to the poor crystallinity and large intrinsic pore size of COFs. Herein, the p-toluenesulfonic acid (PTSA)-mediated interfacial catalytic polymerization (ICP) strategy was proposed to fabricate COF membranes with high crystallinity and sub-nano pores on the polysulfone substrate to enhance desalination and selectivity performance. The proposed PTSA-mediated ICP strategy facilitated the amorphous-to-crystalline transformation and regulated the stacking behavior of COF crystals. Via PTSA meditated ICP process, a ribbon-like crystal structure was observed on the membrane surface. The amorphous COF layers with a thickness of 122-412 nm transformed into crystalline COF layers with a thickness of approximately 245-390 nm, while the pore radius of the COF membranes decreased from 0.65-1.25 nm to 0.17-0.25 nm due to the multilayer stacking of COF crystals on the membrane surface. Meanwhile, the crystalline degree of these COF membranes increased from 21.45% to 73.95% with increasing PTSA concentration and ICP time. The optimal TpPa3%-15 membrane had a water permeability of approximately 3.74 L-1 m-2 h-1 bar- 1 and substantial enhancement of Na2SO4 rejection from 19.7% to 90.4%. The 30-day duration of the cross-flow operation measurement demonstrated excellent stability and robust selectivity of SO42- and Cl- for the optimal TpPa3%-15 membrane. In addition, the optimal membrane exhibited excellent desalination performance for divalent ions in petrochemical wastewater and shale gas produced water than that of pristine membrane, rendering their applicability for industrial wastewater desalination. The mechanisms analysis verified that PTSA induced disorder multilayer stacking of crystalline COF crystals on the substrate surface, resulting in reduced pore sizes and increased desalination of the COF membranes. As the traditional IP process, this work proposed that PTSA mediated ICP process was a facile, scalable and time-saving approach for the construction of highly crystalline COF membranes with sub-nanometer pores to achieve enhanced desalination performance.