Thiamine-Functionalized Maleated Chitosan: A Novel Bio-Based Adsorbent for Efficient Uptake of Methylene Blue from...

A new type of bio-based adsorbents thiamine-functionalized maleated chitosan (CSMA@TA) was prepared and tested to help the effective removal of methylene blue (MB) in water systems. Successful functionalization was confirmed using structural and surface analysis by FTIR, SEM, XRD, TGA, BET and XPS that revealed a mesoporous structure with a surface area of 50.61 m²/g, pore volume of 0.062 cm³/g and an average pore diameter of 2.65 nm, as well as incorporation of active sites containing nitrogen and sulfur. The best fit of the Langmuir model (R² ≈ 0.986; RMSE less than 1.0) demonstrated that the adsorption capacity of CSMA@TA was highly dependent on operation parameters, with an optimum adsorption capacity of about 230 mg/g and a removal efficiency of more than 93.4% under an initial MB concentration of 25 mg/L. Kinetic studies followed the pseudo-second-order model (R² ≈ 0.986), indicating that the uptake was dominated by chemisorption. Analysis of intraparticle diffusion indicated that the adsorption process involved three stages: diffusion in the boundary layer (k1d = 17.95 mg/g·min^-1/2), which controlled the first stage; gradual diffusion in the pore diffusion; and stabilization of the equilibrium. The thermodynamic parameters indicated the presence of strong adsorbate-adsorbent interactions and interfacial structuring. ∆G° values ranged between -24.85 and -23.56 kJ/mol, ∆H° = -44.08 kJ/mol, and ∆S° = -64.65 J/molK indicated strong adsorbate-adsorbent interactions and interfacial structuring. The adsorbent also exhibited good reusability, retaining more than 90% of its initial efficiency after five cycles, making it stable. The enhanced performance of CSMA@TA is due to the synergistic effect of carboxyl groups and heteroaromatic thiamine moieties, which enable electrostatic attraction, hydrogen bonding, and π-π interactions. These findings support the claim that CSMA@TA is a high-efficiency, sustainable, and reusable adsorbent with strong potential for practical wastewater treatment applications.