Chitosan–Silica Hybrid Composites for Removal of Sulfonated Azo Dyes from Aqueous Solutions

In this study, the influence of the chitosan immobilization method on the properties of final hybrid materials was performed. Chitosan was immobilized on the surface of mesoporous (ChS2) and fumed silica (ChS3) by physical adsorption and the sol–gel method (ChS1). It was found that physical immobilization of chitosan allows to obtain hybrid composites (ChS) with a homogeneous distribution of polymer on the surface, relatively wide pores, and specific surface area of about 170 m²/g, pH_PZC = 5.7 for ChS3 and 356 m²/g and pH_PZC = 6.0 for ChS2. The microporous chitosan–silica material with a specific surface area of 600 m²/g and a more negatively charged surface (pH_PZC = 4.2) was obtained by the sol–gel reaction. The mechanisms of azo dye adsorption were studied, and the correlation with the composite structure was distinguished. The generalized Langmuir equation and its special cases, that is, Langmuir–Freundlich and Langmuir equations, were applied for the analysis of adsorption isotherm data. The adsorption study showed that physically adsorbed chitosan (ChS1 and ChS2) on a silica surface has a higher sorption capacity, for example, 0.48 mmol/g for the acid red 88 (AR88) dye (ChS2) and 0.23 mmol/g for the acid orange 8 (AO8) dye (ChS1), compared to the composite obtained by the sol-gel method [ChS1, 0.05 mmol/g for the AO8 dye]. For a deeper understanding of the behavior of immobilized chitosan in the adsorption processes, various kinetic equations were applied: first-order, second-order, mixed 1,2-order (MOE), multiexponential, and fractal-like MOE as well as intraparticle and pore diffusion model equations. In the case of AO8 dye, the adsorption rates were differentiated for three composites: for ChS3, 50% of the dye was removed from the solution after merely 5 min and almost 90% after 80 min. The slowest adsorption process controlled by the diffusion rate of dye molecules into the internal space of the pore structure was found for ChS1 (225 min halftime). In the case of ChS2, the rates for various dyes change in the following order: acid orange (AO7) > orange G (OG) > acid red 1 (AR1) > AR88 > AO8 (halftimes: 10.5 < 15.7 < 23.7 < 34.9 < 42.9 min)