Superselective Hg(II) Removal from Water Using a Thiol-Laced MOF-Based Sponge Monolith: Performance and Mechanism

Point-of-use (POU) devices with satisfying mercury (Hg) removal performance are urgently needed for public health and yet are scarcely reported. In this study, a thiol-laced metal-organic framework (MOF)-based sponge monolith (TLMSM) has been investigated for Hg(II) removal as the POU device for its benchmark application. The resulting TLMSM was characterized by remarkable chemical resistance, mechanical stability, and hydroscopicity (>2100 wt %). Importantly, the TLMSM has exhibited high adsorption capacity (∼954.7 mg g^-1), fast kinetics (k_f ∼ 1.76 × 10^-5 ms^-1), broad working pH range (1-10), high selectivity (K_d > 5.0 × 10⁷ mL g^-1), and excellent regeneration capability (removal efficiency >90% after 25 cycles). The high applicability of TLMSM in real-world scenarios was verified by its excellent Hg(II) removal performance in various real water matrices (e.g., surface waters and industrial effluents). Moreover, a fixed-bed column test demonstrated that ∼1485 bed volumes of the feeding streams (∼500 μg L^-1) can be effectively treated with an enrichment factor of 12.6, suggesting the great potential of TLMSM as POU devices. Furthermore, the principal adsorption complexes (e.g., single-layer -S-Hg-Cl and double-layer -S-Hg-O-Hg-Cl and -S-Hg-O-Hg-OH) formed during the adsorption process under a wide range of pH were synergistically and systematically unveiled using advanced tools. Overall, this work presents an applicable approach by tailoring MOF into a sponge substrate to achieve its real application in heavy metal removal from water, especially for Hg(II).