Enhanced arsenite removal from water using zirconium-ferrocene MOFs coupled with peroxymonosulfate:oxidation and multi-sites adsorption mechanism.

The efficient removal of arsenite (As(III)) poses a significant challenge to traditional water treatment technologies due to its high toxicity and mobility. In this work, multifunctional Zirconium-Ferrocene Metal Organic Framework (ZrFc-MOF) fabricated with redox-active 1,1-ferrocene dicarboxylic acid ligands and Zr4+ precursors were elaborated to achieve remarkably enhanced As(III) removal via activation by peroxymonosulfate (PMS). The adsorption affinity coefficient increased from 0.097 to 2.035 L mg-1 and the maximum adsorption capacity increased from 59.79 to 111.34 mg g-1 compared with that without PMS. Besides the conventional homogeneous PMS oxidation and the following adsorption through Zr-O clusters of ZrFc-MOFs, the enhanced As(III) removal synergistic combines the oxidation mechanism of As(III) by reactive oxygen species (•OH, SO4•-, O2•- and 1O2) formed in Ferrocene (Fc) activating PMS process with the simultaneous formed extra adsorption sites of Ferrocenium (Fc+). PMS also help ZrFc-MOF to avoid destruction in harsh alkaline condition, making the effluent in this advanced treatment meet the World Health Organization (WHO) threshold of 10 µg L-1 over a wide range of initial pH (2-11) with high selectivity and durability. These results indicate that this novel Fc-based MOFs activating PMS system has potential applicability for As(III) in oxidation and selectively capturing in the water environment.

An ICT-based fluorescent probe with a large Stokes shift for measuring hydrazine in biological and water samples.

As a strong reductant and highly active alkali, hydrazine (N2H4) has been widely used in chemical industry, pharmaceutical manufacturing and agricultural production. However, its high acute toxicity poses a threat to ecosystem and human health. In the present study, a ratiometric fluorescent probe for the detection of N2H4 was designed, utilizing dicyanoisophorone as the fluorescent group and 4-bromobutyryl moiety as the recognition site. 4-(2-(3-(dicyanomethylene)-5,5-dimethylcyclohex-1-enyl) phenyl 4-brobutanoate (DDPB) was readily synthesized and could specially sense N2H4 via an intramolecular charge transfer (ICT) pathway. The cyclization cleavage reaction of N2H4 with a 4-bromobutyryl group released phenolic hydroxyl group and reversed the ICT process between hydroxy group and fluorophore, turning on the fluorescence in the DDPB-N2H4 complexes. DDPB exhibits a low cytotoxicity, reasonable cell permeability, a large Stokes shift (186 nm) and a low detection limit (86.3 nM). The quantitative determination of environmental water systems and the visualization fluorescence of DDPB test strips provides a strong evidence for the applications of DDPB. In addition, DDPB is suitable for the fluorescence imaging of exogenous N2H4 in HeLa cells and zebrafish.