The aggressive search for unique materials in recent years has put forward chitosan and modified-chitosan as materials with unique structural and morphological characteristics for various important applications. Just as imidazolium-based ionic liquids are the commonly applied ionic liquids (ILs) type for chitosan modifications for various applications, their further modifications into beads for enhancing their properties is now gaining most attention. However, most of the currently prepared imidazolium ILs modified-chitosan beads are not in nano size due to preparation difficulties. In response to this and referencing the research works in the literature, the possible breakthrough directions including synthesis routes, and physical and mechanical transformation processes are proposed. These procedures are expected to provide certain theoretical and empirical basis, as well as technical guide for developing nano-micro size chitosan beads using imidazolium based ILs.
In recent times, research interest into the development of biodegradable, cost-effective and environmental friendly adsorbents with favourable properties for adsorption of pollutants is a challenge. Modification of chitosan via different physical and chemical methods have gained attention as a promising approach for removing organic (such as dyes and pharmaceuticals) and inorganic (such as metal/metal ions) pollutants from aqueous medium. In this regard, researchers have reported grafting and cross-linking approach among others as a potentially useful method for chitosan's modification for improved adsorption efficiency with respect to pollutant uptake. This article reviews the trend in chitosan modification, with regards to the summary of some recently published works on modification of chitosan and their adsorption application in pollutants (metal ion, dyes and pharmaceuticals) removal from aqueous medium. The review uniquely highlights some common cross-linkers and grafting procedures for chitosan modification, their influence on structure and adsorption capacity of modified-chitosan with respect to pollutants removal. Findings revealed that the performance of modified chitosan for adsorption of pollutants depends largely on the modification method adopted, materials used for the modification and adsorption experimental conditions. Cross-linking is commonly utilized for improving the chemical and mechanical stabilities of chitosan but usually decreases adsorption capacity of chitosan/modified-chitosan for adsorption of pollutants. However, literature survey revealed that adsorption capacity of cross-linked chitosan based materials have been enhanced in recently published works either by grafting, incorporation of solid adsorbents (e.g metals, clays and activated carbon) or combination of both prior to cross-linking.
In this study, chitosan/porous carbon composite (C-PC) modified in 1-Allyl-3-methyl imidazolium bromide [AMIM][Br] under airtight condition was prepared for the removal of Acid Blue-25 dye (AB-25) from aqueous medium. For comparison of adsorption efficiency of C-PC, chitosan-activated carbon composite (C-AC) was also prepared in 1% acetic acid. The adsorbents were characterised using SEM, EDX, XRD, BET, TGA and FTIR. The micrograph of C-PC revealed cavities and slightly rough surfaces dominated with similar sized and irregular shaped stone-like materials which differ from the precursors' micrograph. BET analysis revealed the domination of mesopores on the C-PC and C-AC surfaces, as the hydroxyl and amino group on C-PC are the main active sites for AB-25 dye uptake. The dye was better adsorbed onto C-PC at pH 2 and C-AC at pH 4. The adsorption capacity obtained for C-PC, C-AC, activated carbon (AC) and chitosan (CH) using Langmuir isotherm model are 3333.33 mg/g, 909.90 mg/g, 909.09 mg/g and 833.33 mg/g, respectively. The experimental data are well described by Langmuir and Fruendlich isotherms for adsorption of the dye onto C-PC, AC and CH. C-AC fitted into Langmuir isotherm only. The kinetics of the adsorption fitted into pseudo-second order indicating the possibility of chemical interactions in the adsorption process.
Adsorption efficiency of a duo-material blend featuring the fabrication of modified chitosan adsorbents (powder (C-emimAc), bead (CB-emimAc) and sponge (CS-emimAc)) for the removal of Cd(II) from aqueous solution was investigated. The chitosan@activated carbon (Ch/AC) blend was developed in a green ionic solvent, 1-ethyl-3-methyl imidazolium acetate (EmimAc) and its characteristics was examined using FTIR, SEM, EDX, BET and TGA. The possible mechanism of interaction between the composites and Cd(II) was also predicted using the density functional theory (DFT) analysis. The interactions of various blend forms (C-emimAc, CB-emimAc and CS-emimAc) with Cd(II) gave better adsorption at pH 6. The composites also present excellent chemical stability in both acidic and basic conditions. The monolayer adsorption capacities obtained (under the condition 20 mg/L [Cd], adsorbent dosage 5 mg, contact time 1 h) for the CB-emimAc (84.75 mg/g) > C-emimAc (72.99 mg/g) > CS-emimAc (55.25 mg/g), as this was supported by their order of increasing BET surface area (CB-emimAc (120.1 m2/g) > C-emimAc (67.4 m2/g) > CS-emimAc (35.3 m2/g)). The feasible adsorption interactions between Cd(II) and Ch/AC occurs through the O-H and N-H groups of the composites, as supported by DFT analysis in which an electrostatic interactions was predicted as the dominant force. The interaction energy (-1309.35 eV) calculated via DFT shows that the Ch/AC with amino (-NH) and hydroxyl (-OH) groups are more effective with four significant electrostatic interactions with the Cd(II) ion. The various form of Ch/AC composites developed in EmimAc possess good adsorption capacity and stability for the adsorption Cd(II).