School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, P. R. China.
Tianjin Key Laboratory of Membrane Science and Desalination Technology, State Key Laboratory of Chemical Engineering, Tianjin University, Tianjin 300072, P. R. China.
Environ Sci Technol. 2024 Mar 19;58(11):5174-5185. doi: 10.1021/acs.est.3c10195. Epub 2024 Mar 7.
Nanofiltration (NF) has the potential to achieve precise ion-ion separation at the subnanometer scale, which is necessary for resource recovery and a circular water economy. Fabricating NF membranes for selective ion separation is highly desirable but represents a substantial technical challenge. Dipole-dipole interaction is a mechanism of intermolecular attractions between polar molecules with a dipole moment due to uneven charge distribution, but such an interaction has not been leveraged to tune membrane structure and selectivity. Herein, we propose a novel strategy to achieve tunable surface charge of polyamide membrane by introducing polar solvent with a large dipole moment during interfacial polymerization, in which the dipole-dipole interaction with acyl chloride groups of trimesoyl chloride (TMC) can successfully intervene in the amidation reaction to alter the density of surface carboxyl groups in the polyamide selective layer. As a result, the prepared positively charged (PEI-TMC)-NH and negatively charged (PEI-TMC)-COOH composite membranes, which show similarly high water permeance, demonstrate highly selective separations of cations and anions in engineering applications, respectively. Our findings, for the first time, confirm that solvent-induced dipole-dipole interactions are able to alter the charge type and density of polyamide membranes and achieve tunable surface charge for selective and efficient ion separation.
纳滤 (NF) 具有在亚纳米尺度实现精确离子-离子分离的潜力,这对于资源回收和循环水经济是必要的。制造用于选择性离子分离的 NF 膜是非常理想的,但代表了一个重大的技术挑战。偶极-偶极相互作用是由于电荷分布不均匀而在具有偶极矩的极性分子之间产生分子间吸引力的一种机制,但这种相互作用尚未被利用来调节膜结构和选择性。在此,我们提出了一种在界面聚合过程中引入具有大偶极矩的极性溶剂来实现聚酰胺膜可调表面电荷的新策略,其中与均苯三甲酰氯 (TMC) 的酰氯基团的偶极-偶极相互作用可以成功地干预酰胺化反应,从而改变聚酰胺选择层中表面羧基的密度。结果,所制备的带正电的 (PEI-TMC)-NH 和带负电的 (PEI-TMC)-COOH 复合膜,其水通量相似,分别在工程应用中表现出对阳离子和阴离子的高度选择性分离。我们的研究结果首次证实,溶剂诱导的偶极-偶极相互作用能够改变聚酰胺膜的电荷类型和密度,并实现选择性和高效离子分离的可调表面电荷。