Multithiol functionalized graphene bio-sponge via photoinitiated thiol-ene click chemistry for efficient heavy metal ions adsorption

Heavy metals contamination in the natural waters remains an unresolved environmental challenge pressing for the development of purification technologies. This paper presents the green engineering of a new bio-sponge for heavy metals adsorption composed of alginate bio-polymeric network encapsulated with reduced graphene oxide (rGO) modified with iron oxide nanoparticles and covalently attached multithiol (pentaerythritol tetrakis-mercaptopropionate) molecules using photoinitiated thiol-ene click chemistry. The multithiol functionalized graphene bio-sponge (SH-Graphene bio-sponge) is designed to enhance adsorption performances of heavy metals including structural approach combined with oxygen functionalities and high density of sulfur-containing groups (10.2 at % S, confirmed by X-ray Photoelectron Spectroscopy, XPS) with high binding affinity towards specific heavy metals (Cd and Pb). It was shown that the level of thiol functionalization on the graphene structure within the bio-sponge can be controlled by tuning the Ultraviolet (UV) irradiation time without adjusting the concentration of the precursors. SH-functionalized graphene bio-sponge showed outstanding adsorption capacity for Pb (II): 101.01 mg/g and Cd (II): 102.99 mg/g, outperformed commercial and literature reported adsorbents in highly competitive selectivity studies using co-existing heavy metal ions (Cu, Co, Pb and Cd) spiked- sea water. The multithiol modified bio-sponge also showcased an excellent stability and reusability feature with only 0.015 mg/L Pb (II) detected, conforming the strict United States Environmental Protection Agency (US EPA) maximum contaminant level (MCL) for lead, after five recurring cycles using mixed heavy metal ions solution and acidic eluent. The outcomes from this work present valuable and promising contribution towards the development of a scalable and sustainable adsorbents for efficient remediation of heavy metals from waters.