Development of Blended Biopolymer-Based Photocatalytic Hydrogel Beads for Adsorption and Photodegradation of Dyes.

Blended biopolymer-based photocatalytic hydrogel beads were synthesized by dissolving the biopolymers in 1-ethyl-3-methylimidazolium acetate ([Emim][Ac]), adding TiO, and reconstituting the beads with ethanol. The incorporation of modifying biopolymer significantly enhanced the adsorption capacity of the cellulose/TiO beads. Cellulose/carrageenan/TiO beads exhibited a 7.0-fold increase in adsorption capacity for methylene blue (MB). In contrast, cellulose/chitosan/TiO beads showed a 4.8-fold increase in adsorption capacity for methyl orange (MO) compared with cellulose/TiO beads. In addition, cellulose/TiO microbeads were prepared through the sol-gel transition of the [Emim][Ac]-in-oil emulsion to enhance photodegradation activity. These microbeads displayed a 4.6-fold higher adsorption capacity and 2.8-fold higher photodegradation activity for MB than the millimeter-sized beads. Furthermore, they exhibited superior dye removal efficiencies for various dyes such as Congo red, MO, MB, crystal violet, and rhodamine B, surpassing the performance of larger beads. To expand the industrial applicability of the microbeads, biopolymer/TiO magnetic microbeads were developed by incorporating FeO. These magnetic microbeads outperformed millimeter-sized beads regarding the efficiency and time required for MB removal from aqueous solutions. Furthermore, the physicochemical properties of magnetic microbeads can be easily controlled by adjusting the type of biopolymer modifier, the TiO and magnetic particle content, and the ratio of each component based on the target molecule. Therefore, biopolymer-based photocatalytic magnetic microbeads have great potential not only in environmental fields but also in biomedical fields.