Hydrophobic Modification of Alginate Nanofibrous Membrane by Group IV Elements Ion Crosslinking

Hydrophobic nanofiber membranes derived from the biopolymer alginate were fabricated by electrospinning followed by metal ion crosslinking, and their potential as oil-water separation membranes was primarily investigated. Sodium alginate (SA) was co-electrospun with polyethylene glycol and subsequently crosslinked using calcium chloride and group IV metal ions (zirconium or titanium). Metal ion crosslinking changed the surface wettability of the nanofiber membranes, as confirmed by water contact angle measurements. Both zirconium- and titanium-crosslinked SA nanofiber membranes exhibited effective gravity-driven oil-water separation with complete water blocking. Although hydrophobic modification reduced direct water affinity, the resulting membranes retained residual adsorption capability toward methylene blue, indicating the presence of accessible internal polar sites. The adsorption behavior varied depending on the crosslinking ion. In addition, titanium-crosslinked membranes showed an auxiliary UV-assisted dye removal contribution under irradiation, arising from photoactive Ti species. These findings demonstrate that metal ion crosslinking provides a practical route for tuning the functional properties of alginate nanofiber membranes, with oil-water separation as the primary application and dye adsorption/photocatalysis as secondary functionalities.