Oxidative modification is a facile method to improve the desalination performance of thin-film composite membranes. In this study, we comparatively investigated the modification mechanisms induced by sulfate radical (SO4• -) and hydroxyl radical (HO•) for polyamide reverse osmosis (RO) membrane. The SO4• -- and HO•-based membrane modifications were manipulated by simply adjusting the pH of the thermal-activated persulfate solution. Although both of them improved the water permeability of the RO membrane under certain conditions, the SO4• --modified membrane notably prevailed over the HO•-modified one due to higher permeability, more consistent salt rejection rates over wide pH and salinity ranges, and better stability when exposed to high doses of chlorine. The differences of the membranes modified by the two radical species probably can be related to their distinct surface properties in terms of morphology, hydrophilicity, surface charge, and chemical composition. Further identification of the transformation products of a model polyamide monomer using high-resolution mass spectrometry demonstrated that SO4• - initiated polymerization reactions and produced hydroquinone/benzoquinone and polyaromatic structures; whereas the amide group of the monomer was degraded by HO•, generating hydroxyl, carboxyl, and nitro groups. The results will enlighten effective ways for practical modification of polyamide RO membranes to improve desalination performances and the development of sustainable oxidation-combined membrane processes.
Keywords: chlorine resistance; desalination; fouling resistance; hydroxyl radical; oxidative modification; polyamide RO membrane; sulfate radical.