High Capacity Arsenate Removal from Real Samples Using Dihydrotetrazine Decorated Zirconium-Based Metal-Organic Frameworks.

Abstract

Zirconium metal-organic frameworks (Zr-MOFs) are potential candidates for decontamination of water resources from harmful pollutants due to their modulable porosity and chemical stability in aqueous solutions. Linker functionalization is an approach for tuning the host-guest chemistry of Zr-MOFs and extends their applications in environmental monitoring. In this work, the structure of UiO-66(Zr) (formulated Zr6(OH)4O4(BDC)6, BDC2- = benzene-1,4-dicarboxylate) was functionalized with dihydrotetrazine group via postsynthesis linker exchange (PSLE) method. The functionalized framework, UiO-66(Zr)-DHTZ, was applied for the removal of arsenate ions from aqueous solutions. The results show that UiO-66(Zr)-DHTZ can adsorb 583 mg g-1 of As(V) at pH = 7 after 2 h, which is significantly higher than that of the UiO-66(Zr). According to X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared (FTIR), the removal mechanism is based on possible hydrogen bindings between free -C-NH and -C═N- sites of dihydrotetrazine function with -O- and -OH sites of As(V) species. Removal tests in real samples show that UiO-66(Zr)-DHTZ still has a high capacity (220 mg g-1) to As(V) ions in complex matrixes and also can decrease the concentration of As(V) below the detection limit (0.05 ppm) of the inductively coupled plasma optical emission spectroscopy (ICP-OES) method. Since the dihydrotetrazine-decorated UiO-66(Zr)-DHTZ reaches one the highest adsorption capacities to As(V) species, it can be considered a potential candidate for water treatment in real-life applications.