Zirconium modified mesoporous materials were successfully synthesized by different methods including direct synthesis and post synthesis (grafting and impregnating). Meanwhile, the corresponding catalysts were prepared. A series of techniques, including small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM) and pyridine adsorption Fourier-transform infrared (Py-IR), were used to characterize the properties of supports and catalysts. The results of SASX and TEM characterization proved that all the modified materials retained the well-ordered mesoporous structure from the FDU-12 material. N2 adsorption–desorption results showed that the Zr-FDU-12 material obtained by direct synthesis (Zr-in-F) possessed higher specific surface area (709 m2 g−1), pore volume (0.65 cm3 g−1) and larger pore size (18.7 nm) than the Zr-FDU-12 materials obtained by the post synthesis. According to the characterization result of UV-Vis, Zr-in-F exhibited better dispersion of Zr species than materials obtained by the post synthesis. It was found that the incorporation of Zr species not only increased acidities but also enhanced the sulfidities of the Mo species. All the catalysts were evaluated for their activities in the hydrodesulfurization of dibenzothiophene, and the NiMo/Zr-in-F catalyst exhibited the best catalytic performance (97.3%), attributed to its higher specific surface area, larger pore size, higher sulfidity, and more acidic sites.
As (V) poses significant environmental and health risks due to its toxicity, making efficient wastewater treatment technologies essential. In this study, we introduce a novel composite material: MOF-like zirconium (Zr)-doped Prussian blue (PB) analogs decorated on polytetrafluoroethylene microporous membranes (Zr-PBAs x -PDA/PEI-M) for As (V) adsorption. Comprehensive characterization techniques, confirmed the successful incorporation of Zr into PB crystals and its growth on the membrane surface through PDA/PEI interlayers. We systematically explored the effects of varying Fe-Zr modification ratios, finding that Zr-PBAs 3 -PDA/PEI-M (Fe: Zr = 2:3) exhibited the optimal performance for As (V) removal and adsorption capacity, with a more intact and densely distributed crystal structure. It demonstrated that Zr-O bonding plays a crucial role in the adsorption mechanism, forming a double-dentate mononuclear structure with As (V). Moreover, the Zr-PBAs 3 -PDA/PEI-M’s adsorption capacity of As (V) was comprehensively assessed by key factors such as temperature, pH, operating pressure, natural organic matter (NOM), and initial As (V) concentration during wastewater treatment, which exhibited the excellent resistance to interference in removing As (V). Remarkably, Zr-PBAs 3 -PDA/PEI-M retained its high adsorption capacity across three cycles of reuse, highlighting its excellent stability and reusability. When tested on simulated Pearl River water samples containing As (V), the material achieved filtrate concentrations well below 0.5 mg/L, in compliance with China’s Comprehensive Wastewater Discharge Standard. This study presents a promising solution for efficient As (V) removal in wastewater, offering practical insights into its potential application for real-world water treatment challenges.
In the present study, the ultra-large specific surface area Zr-decorated hyper-cross-linked polymers (HP) were firstly developed for the catalytic production of furfuryl alcohol (FOL) from furfural (FAL) using isopropanol as both the hydrogen source and solvent. Comprehensive characterizations were performed to uncover the basic physicochemical properties. The as-prepared Zr/HP showed large specific surface area of ∼1000 m 2 /g, good dispersion of Zr species, plentiful acidity and basicity. 2.5Zr/HP presented the highest activity in the FAL-to-FOL transformation, wherein 97.4 % FAL conversion and 92.9 % FOL yield were achieved within 2 h at 160 °C. The recycling experiments revealed that the as-fabricated Zr-decorated hyper-cross-linked polymers presented good recyclability without significant loss of reactivity even after two consecutive cycles, owing to the strong interaction between hyper-cross-linked polymers and grafted Zr species. Kinetical analysis verified that the activation energy for transfer hydrogenation of FAL could be lowered to a certain degree, especially in the case of lower Zr loadings. More gratifyingly, the Zr-decorated hyper-cross-linked polymers were capable of catalyzing other unsaturated compounds with high conversion rates. In addition, the plausible pathway for the FAL-to-FOL transformation over Zr-decorated hyper-cross-linked polymers was proposed.
危险品化学品经营许可证（带存储）