With diverse selectivity, higher permeance, and good antifouling property, loose polyamide nanofiltration (NF) membranes can be potentially deployed in various bioseparation applications. However, the loose NF membrane with a low crosslinking degree generally suffers from the alkali-induced pore swelling during chemical cleaning, resulting in degradation of separation performance with time. In this work, we conceive a novel strategy to tailor the separating layer through alkaline post-etching following the interfacial polymerization process, where piperazine and tannic acid (TA) were used as water-phase monomers, and trimesoyl chloride (TMC) and ferric acetylacetonate were employed as organic monomers in n-hexane. Thereinto, the polyester network formed by TA and TMC was selectively etched by alkaline treatment, thus obtaining a loose NF membrane, whose structure and performance could be facilely tailored by controlling the TA ratio and the etching pH. As a result, the well-designed loose NF membrane exhibited higher flux, better selectivity, and more stable separation performance in a long-term filtration of diluted cane molasses. Interestingly, the obtained loose NF membrane showed excellent antiswelling ability during alkaline cleaning because of network locking induced by Fe3+ chelation, decrease in the carboxyl proportion (more hydroxyl generation due to the ester bond hydrolysis), and enhanced interface interaction between the separation layer and the sublayer attributed to catechol adhesion effect. Therefore, such a "selective-etching-induced reinforcing" strategy could endow the polyamide NF membrane with both loose and antiswelling separation layer in a reliable and scalable way, which provides a new perspective for preparing highly selective and stable NF membrane for resource recovery.
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