A serendipity of nanofiltration membrane modification using a simple approach: Limited sulfonamidation, remarkable improvements

• Published in: Separation and purification technology 2023-10, Vol.322, p.124329, Article 124329
• Main Authors: Wang, Zhiqiang, Gao, Yawei, Zhang, Jinsong, Peng, Zanguo, Wang, Xiao-mao, Liu, Shuming, Huang, Xia
• Format: Article
• Language: English
• Subjects: Nanofiltration membrane; Rejection selectivity; Secondary interfacial polymerization; Sulfuryl chloride; Surface modification
• ISSN: 1383-5866; 1873-3794
• DOI: 10.1016/j.seppur.2023.124329

[Display omitted] •Sulfuryl chloride (SC) was used for NF membrane surface modification and mechanism study.•SC behaved alike small and reactive diacyl chlorides in tuning pore size and surface charge.•SC was incorporated with a low percentage but endowed the membrane with substantial effects.•SC could elevate the crosslinking degree of the top segment of nascent membrane.•The effect of secondary amidation on membrane after heat curing would be restricted. Surface modification via secondary interfacial polymerization (IP) is a promising technology for the enhancement of nanofiltration (NF) membrane performance such as rejection selectivity. In this study, sulfuryl chloride (SC), containing sulfur element, was employed to introduce sulfonic groups into the active layer of membranes, with a main purpose of investigating the secondary IP mechanisms as well as the variation of membrane structural and physicochemical properties. Moreover, the SC-modified membranes would be endowed with favorable performance. Results showed that SC in a hexane environment behaved similarly with small and reactive diacyl dichloride in enhancing membrane surface negative charge density and contracting membrane pores. Membrane surface characterization showed that the sulfur element had a low concentration with an S/N ratio less than 0.04. This indicated that, on the one hand, the residual amine groups in the nascent active layer for secondary IP were quite limited, and on the other hand, the improvement of membrane performance was remarkably affected by the introduced sulfonyl groups. Consequently, SC in the hexane environment could further enhance the crosslinking degree of the active layer. In addition, SC modification could increase the membrane surface hydrophilicity and narrow the pore size distribution. The SC-modified membranes would be suitable for advanced treatment of drinking water. An optimized membrane with SC modification had a molecular weight cutoff of ∼350 Da and a surface zeta potential of ∼−55.8 mV, and could effectively reject five negatively charged per- and polyfluoroalkyl substances (with molecular weight ranging from 214 to 414 Da) by over 80% while with a low rejection of MgCl2 below 30%..