Evaluation of synergistic adsorption approach for terbinafine removal by cotton shell powder immobilized zerovalent copper: Adsorption kinetics and DFT simulation

Abstract

Cotton shell powder (CS), nano zerovalent copper (nZVC) and cotton shell powder immobilized zerovalent copper (ZVC@CS) were evaluated for their adsorption efficiencies towards terbinafine hydrochloride (TBH), an antifungal drug. The nZVC and ZVC@CS synthesized via one pot redox precipitation method were characterized by FTIR, XRD, BET, FESEM and TGA analysis. The TGA and AAS analysis confirmed the loading of nearly 10% of nZVC on cotton shell powder in ZVC@CS. The effect of operational parameters (pH, adsorbent dose, initial drug concentration, time, etc.) determining the extent of terbinafine hydrochloride adsorption on ZVC@CS were investigated to ascertain the optimal experimental conditions to achieve maximum adsorption efficiencies. To investigate the adsorption behavior of TBH on ZVC@CS, the experimental data were fitted for five different adsorption models viz. Langmuir, Freundlich, Temkin, Redlich-Peterson and Hill isotherms. The TBH adsorption data was best fit with Hill isotherm model indicating cooperative sorption of TBH molecules on ZVC@CS surface. Among the five kinetic equations namely the pseudo-first-order (PFO), the pseudo-second-order (PSO), Elovich model, the intraparticle diffusion model, and Boyd kinetic model used to estimate the adsorption mechanism, the PFO kinetic model give best fit with a good correlation for the physisorption of TBH on ZVC@CS composite. The mechanism of the adsorption process was observed to be complex, consisting of both surface adsorption and pore diffusion. However, the Boyd plot confirms external mass transport as the rate limiting step for the adsorption of TBH on ZVC@CS. The synergistic adsorption of TBH on ZVC@CS was hypothesized, and the idea was supported by structure optimization results from DFT studies. The ZVC@CS exhibits equilibrium TBH adsorption efficiency (qmax) of 285.3 mg.g?1, significantly higher than adsorbents used in literature for the TBH removal. It is suggested that ZVC@CS may serve as sustainable adsorbents for the removal of cationic contaminants from acidic medium. � 2023 Elsevier B.V.