Effective biosorption of Cu(II) using hybrid biocomposite based on N-maleated chitosan/calcium alginate/titania: Equilibrium sorption, kinetic and thermodynamic studies.

In this research work, a hybrid biocomposite based on N-maleated chitosan, amino-thiocarbamate functionalised calcium alginate and anhydrous Titania nanoparticles (NMC-MCA-TiO2) was fabricated. The study involves the one pot facile synthesis of N-maleated chitosan and amino-thiocarbamate functionalised alginate under moderate conditions. Sorbent was conditioned in the form of hydrogel beads and characterized through FT-IR and SEM analysis. Newly grafted functional groups could act as potential chelating sites for enhanced Cu(II) sorption. Modified biopolymers were organo-functionalised which provided excellent support for immobilization of Titania nanoparticles (TiO2) as inorganic filler. Kinetic data illustrated the manifestation of intrinsic chemisorption instead of simple bulk/film diffusion. Equilibrium sorption data fitted well with Freundlich adsorption model (R2 ≈ 0.99) which designated the heterogeneous nature of sorbent. Maximum sorption capacity of biosorbent was found 192 mg/g at 298 K and pH = 6.0. Standard Gibbs free energy change ∆Go (-21.53, -21.97, and - 22.42 kJ/mol), standard enthalpy change ∆Ho (5.12 kJ/mol) and standard entropy change ∆So (0.09 kJ/mol K-1) values suggested that the sorption process to be spontaneous and endothermic. The sorbent 3NMC-MCA-TiO2 could be competitive candidate for economical and rapid adsorptive removal of Cu(II) from dilute contaminated liquids.

Synthesis of hybrid biosorbent based on 1,2-cyclohexylenedinitrilotetraacetic acid modified crosslinked chitosan and organo-functionalized calcium alginate for adsorptive removal of Cu(II).

The present study is based on the synthesis of a novel hybrid biosorbent using 1,2-cyclohexylenedinitrilotetraacetic acid modified crosslinked chitosan and amino-thiocarbamate moiety functionalized sodium alginate (CDTA-CS/TSC-CA). The fabricated sorbent was employed to investigate the efficient recovery of Cu(II) from aqueous media. CDTA-CS/TSC-CA was characterized using Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscopy (SEM). Analysis confirmed the successful modification of both biopolymers and subsequent loading of Cu(II) ions. CDTA-CS/TSC-CA was casted in the form of hydrogel beads having different CDTA-CS to TSC-CA mass ratios i.e., 10.0-40.0% by mass. The hydrogel beads 4CDTA-CS/TSC-CA with CDTA-CS/TSC-CA mass ratio of 40.0% was found most effective for copper sorption. Equilibrium sorption results showed that initial concentration of copper, medium pH, contact time, sorbent dosage and temperature influenced the sorption capacity (qe). Rate of sorption data was interpreted using different kinetic models and found best fitted with pseudo second order rate expression (R2 ≈ 0.99), illustrating that the rate determining step includes the electron density transfer from sorbent coordination sites to central copper ions. Crank's RIDE equation and Elovich chemisorption model (ECM) revealed the presence of two sorption phases, initially rapid sorption followed by comparatively a slow uptake. Equilibrium sorption data was well depicted by Langmuir model and maximum monolayer adsorption capacity (qm) was computed as 276.53 mg·g-1 at 298 K. Standard Gibbs free energy change, ∆G° (-19.99, -20.18 and -20.36 kJ/ mol), standard enthalpy change, ∆H° (-8.95 kJmol) and standard entropy change, ∆S° (0.04 kJ/mol K-1) values suggested that the adsorption process is spontaneous and exothermic. Hence, 4CDTA-CS/TSC-CA was found efficient biosorbent for copper removal from its dilute effluents.