This mini-review provides coverage of chitosan-based adsorbents and their modified forms as sustainable solid-phase extraction (SPE) materials for precious metal ions, such as gold species, and their complexes in aqueous media. Modified forms of chitosan-based adsorbents range from surface-functionalized systems to biomaterial composites that contain inorganic or other nanomaterial components. An overview of the SPE conditions such as pH, temperature, contact time, and adsorbent dosage was carried out to outline how these factors affect the efficiency of the sorption process, with an emphasis on gold species. This review provides insight into the structure-property relationships for chitinaceous adsorbents and their metal-ion removal mechanism in aqueous media. Cross-linked chitosan sorbents showed a maximum for Au(III) uptake capacity (600 mg/g), while S-containing cross-linked chitosan display favourable selectivity and uptake capacity with Au(III) species. Compared to industrial adsorbents such as activated carbon, modified chitosan sorbents display favourable uptake of Au(III) species, especially in aqueous media at low pH. In turn, this contribution is intended to catalyze further research directed at the rational design of tailored SPE materials that employ biopolymer scaffolds to yield improved uptake properties of precious metal species in aqueous systems. The controlled removal of gold and precious metal species from aqueous media is highly relevant to sustainable industrial processes and environmental remediation.

To address the need to develop improved hybrid biopolymer composites, we report on the preparation of composites that contain chitosan and pectin biopolymers with tunable adsorption properties. Binary biopolymer composites were prepared at variable pectin–chitosan composition in a solvent directed synthesis, dimethyl sulfoxide (DMSO) versus water. The materials were characterized using complementary methods (infrared spectroscopy, thermal gravimetric analysis, pH at the point-of-zero charge, and dye-based adsorption isotherms). Pectin and chitosan composites prepared in DMSO yielded a covalent biopolymer framework (CBF), whereas a polyelectrolyte complex (PEC) was formed in water. The materials characterization provided support that cross-linking occurs between amine groups of chitosan and the –COOH groups of pectin. CBF-based composites had a greater uptake of methylene blue (MB) dye over the PEC-based composites. Composites prepared in DMSO were inferred to have secondary adsorption sites for enhanced MB uptake, as evidenced by a monolayer uptake capacity that exceeded the pectin–chitosan PECs by 1.5-fold. This work provides insight on the role of solvent-dependent cross-linking of pectin and chitosan biopolymers. Sonication-assisted reactions in DMSO favor CBFs, while cross-linking in water yields PECs. Herein, composites with tunable structures and variable physicochemical properties are demonstrated by their unique dye adsorption properties in aqueous media.

Rare-earth elements such as lanthanum and yttrium have wide utility in high-tech applications such as permanent magnets and batteries. The use of biopolymers and their composites as adsorbents for La (III) and Y (III) ions were investigated as a means to increase the uptake capacity. Previous work has revealed that composite materials with covalent frameworks that contain biopolymers such as pectin and chitosan have secondary adsorption sites for enhanced adsorption. Herein, the maximum adsorption capacity of a 5:1 Pectin-Chitosan composite with La (III) and Y (III) was 22 mg/g and 23 mg/g, respectively. Pectin-Chitosan composites of variable composition were characterized by complementary methods: spectroscopy (FTIR, ¹³C solids NMR), TGA, and zeta potential. This work contributes to the design of covalent Pectin-Chitosan biopolymer frameworks for the controlled removal of La (III) and Y (III) from aqueous media.