ABSTRACT
Hazardous heavy metals and organic substances removal is of great significance for ensuring the safety of aquatic-ecosystem, yet the highly effective and selective extraction always remains challenging. To address this problem, magnetic hollow microcubes were fabricated through thermal carbonization of Fe3O4-COOH@ γ-CD-MOFs, and core-shell structured precursors were in-situ greenly constructed on a large scale via microwave-assisted self-assembly strategy. As noted, the development of secondary crystallization was utilized to achieve uniform dispersion of cores within MOFs frameworks and thus improved magnetic and adsorption ability of composites. Acquired magnetic Fe3O4 @HC not only can harvest excellent extraction of heavy metals (Cd, Pb, and Cu of 129.87, 151.05, and 106.98 mg·g-1) but also exhibit highly selective adsorption ability for cationic organics (separation efficiency higher than 95.0 %). Impressively, Fe3O4 @HC achieved outstanding adsorption (60-80 %) of Cd in realistic mussel cooking broth with no obvious loss in amino acid. Characterizations better offer mechanistic insight into the enhanced selectivity of positively charged pollutants can be attributed to synergistic effect of ions exchange and electrostatic interaction of abundant oxygen-containing functional groups. Our study provides a feasible route by rationally developing core-shell structured composites to promote the practical applications of sustainable water treatment and value-added utilization of processing by-products.
ABSTRACT
Building of metal-organic frameworks (MOFs) homogeneous hydrogels made by spontaneous crystallization remains a significant challenge. Inspired by anisotropically structured materials in nature, an oriented super-assembly strategy to construct micro-scale MOFs superstructure is reported, in which the strong intermolecular interactions between zirconium-oxygen (ZrâO) cluster and glutamic acid are utilized to drive the self-assembly of flexible nanoribbons into pumpkin-like microspheres. The confined effect between water-flexible building blocks and crosslinked hydrogen networks of superstructures achieved a mismatch transformation of MOFs powders into homogeneous hydrogels. Importantly, the elastic and rigid properties of hydrogels can be simply controlled by precise modulation of coordination and self-assembly for anisotropic superstructure. Experimental results and theoretical calculations demonstrates that MOFs anisotropic superstructure exhibits dynamic double networks with a superior water harvesting capacity (119.73 g g-1 ) accompanied with heavy metal removal (1331.67 mg g-1 ) and strong mechanical strength (Young's modulus of 0.3 GPa). The study highlights the unique possibility of tailoring MOFs superstructure with homogeneous hydrogel behavior for application in diverse fields.