Thiosemicarbazone modified zeolitic imidazolate framework (TSC-ZIF) for mercury(ii) removal from water

Zeolitic imidazolate frameworks (ZIF-8), and their derivatives, have been drawing increasing attention due to their thermal and chemical stability. The remarkable stability of ZIF-8 in aqueous and high pH environments renders it an ideal candidate for the removal of heavy metals from wastewater. In this study, we present the preparation of novel aldehyde-based zeolitic imidazolate frameworks (Ald-ZIF) through the integration of mixed-linkers: 2-methylimidazole (MIM) and imidazole-4-carbaldehyde (AldIM). The prepared Ald-ZIFs were post-synthetically modified with bisthiosemicarbazide (Bisthio) and thiosemicarbazide (Thio) groups, incorporating thiosemicarbazone (TSC) functionalities to the core of the framework. This modification results in the formation of TSC-functionalized ZIF derivatives (TSC-ZIFs). Thiosemicarbazones are versatile metal chelators, hence, adsorption properties of TSC-ZIFs for the removal of mercury(ii) from water were explored. Removal of mercury(ii) from homoionic aqueous solutions, binary and tertiary systems in competition with lead(ii) and cadmium(ii) under ambient conditions and neutral pH are reported in this study. MIM_3.5:Thio₁:Zn improved the removal efficiency of mercury(ii) from water, up to 97% in two hours, with an adsorption capacity of 1667 mg g⁻¹. Desorption of mercury(ii) from MIM_3.5:Thio₁:Zn was achieved under acidic conditions, regenerating MIM_3.5:Thio₁:Zn for five cycles of mercury(ii) removal. TSC-ZIF derivatives, designed and developed here, represent a new class of dynamically functionalized adsorption material displaying the advantages of simplicity, efficiency, and reusability.

Zeolitic imidazolate frameworks Ald-ZIF were obtained by mixing two imidazole-based linkers with zinc(ii). Post-synthetically modified Ald-ZIFs with thiosemicarbazide group improved mercury(ii) removal efficiency from water at a capacity of 1667 mg g⁻¹.