Nanofiltration Membranes Containing a Metal-Polyphenol Network Layer: Using Casting Solution pH as a Tool to Tailor the Separation Performance

Thin-film composite (TFC) membranes containing metal-polyphenol network (MPN) selective layers were fabricated using a supramolecular self-assembly between tannic acid (TA) and ferric ion (Fe3+). The TA-Fe3+ thin film was coated on a porous polyacrylonitrile support using aqueous solutions of TA and FeCl3 via a layer-by-layer deposition technique. The pH of the TA solution was used as a tool to alter the membrane characteristics. The surface porosity and water contact angle of the fabricated membranes gradually decreased as the pH of TA casting solutions was increased from 3 to 8.5 for both single-layered and double-layered TA-Fe3+ TFC membranes. This allowed us to tune the water permeance and the retentions of water-soluble neutral and anionic molecules by the MPN membranes by varying the pH of the casting solution. It has been shown that the water permeance decreased from 184 to 156 L<middle dot>m-2<middle dot>h-1<middle dot>bar-1 for single TA-Fe3+ layer coated membranes when the pH was increased from 3 to 8.5, while it declined from 51 to 17 for the double TA-Fe3+ layer. Anionic solutes in aqueous solutions were highly retained compared to neutral components as the TFC membranes had a negative surface charge. Retentions of 95 and 90% were achieved for naphthol green B and orange II dyes by a double-layered M4 membrane fabricated at pH 8.5, while only 13% retention was found for the neutral riboflavin. The neutral dye riboflavin permeated 30.8 times higher than the anionic dye naphthol green B during a mixed dye filtration test through the TFC membrane prepared by using a TA solution of pH 8.5. To the best of our knowledge, this is the highest selectivity of a neutral/anionic dye pair so far reported for a TFC membrane having an MPN selective layer. Moreover, fouling tests have demonstrated that the MPN separation layers exhibit robust stability and adequate antifouling performance with a flux recovery ratio as high as 82%.