ABSTRACT
Finely tuning the pore structure of traditional nanofiltration (NF) membranes is challenging but highly effective for achieving efficient separations. Herein, we propose a concept of using macrocyclic amines (1,4,7-triazacyclononane, 3A; 1,4,7,10-tetraazacyclododecane, 4A1; and 1,4,8,11-tetraazacyclotetradecane, 4A2) with different intra-annular apertures to finely modulate the pore structure of microporous membranes via interfacial polymerization (IP). The boost in the intracavity size of the building blocks results in heightened steric hindrance of these amine monomers, leading to a controlled increase in membrane pore size, as demonstrated by both film characterizations and multiscale simulations. In conjunction with the increased intracavity size, the water permeability follows an augmented trend of 3A-TMC, 4A1-TMC, and 4A2-TMC (TMC: trimesoyl chloride) while exhibiting increased molecular weight cut-offs due to larger free-volume elements and stronger pore interconnectivity. Our proposed macrocyclic amine design strategy provides a guideline for finely regulated microporous membranes with high potential in NF-related applications.
ABSTRACT
Microporous organic nanotubes (MONs) hold considerable promise for designing molecular-sieving membranes because of their high microporosity, customizable chemical functionalities, and favorable polymer affinity. Herein, we report the use of MONs derived from covalent organic frameworks to engineer 15-nm-thick microporous membranes via interfacial polymerization (IP). The incorporation of a highly porous and interpenetrated MON layer on the membrane before the IP reaction leads to the formation of polyamide membranes with Turing structure, enhanced microporosity, and reduced thickness. The MON-modified membranes achieve a remarkable water permeability of 41.7 L m-2 h-1 bar-1 and high retention of boron (78.0%) and phosphorus (96.8%) at alkaline conditions (pH 10), surpassing those of reported nanofiltration membranes. Molecular simulations reveal that introducing the MONs not only reduces the amine molecule diffusion toward the organic phase boundary but also increases membrane porosity and the density of water molecules around the membrane pores. This MON-regulated IP strategy provides guidelines for creating high-permeability membranes for precise nanofiltration.
ABSTRACT
Covalent organic frameworks (COFs) have evinced a potential solution that promises for fast and efficient molecular separation due to the presence of orderly arranged pores and regulable pore apertures. Herein, the synthesized COF (TPB-DMTP-COF) with the pore aperture matching the pore size of the nanofiltration (NF) membrane was utilized to modulate the physicochemical characters of the polyamide (PA) membranes. It is demonstrated that COFs with superior polymer affinity and hydrophilicity not only circumvent the nonselective interfacial cavities but also improve the hydrophilicity of the resultant thin-film nanocomposite (TFN) membranes. Furthermore, the predeposited COF layer is able to slow down the diffusion rate toward the reaction boundary through hydrogen bonding, which is consistent with the results of molecular dynamic (MD) and dissipative particle dynamic (DPD) simulations. In this context, COF-modulated TFN membranes show a roughened and thickened surface with bubble-shaped structures in contrast to the nodular structure of original polyamide membranes. Combined with the introduced in-plane pores of COFs, the resultant TFN membranes display a significantly elevated water permeance of 35.7 L m2 h-1 bar-1, almost 4-fold that of unmodified polyamide membranes. Furthermore, the selectivity coefficient of Cl-/SO42- for COF-modulated TFN membranes achieves a high value of 84 mainly related to the enhanced charge density, far exceeding the traditional NF membranes. This work is considered to provide a guideline of exploring hydrophilic COFs as an interlayer for constructing highly permeable membranes with precise ion-sieving ability.