Enhanced photoreduction efficiency of Cr(VI) driven by visible light in a new Zr-based metal-organic framework modified by hydroxyl groups.

While metal-organic framework (MOF) photocatalysts have demonstrated a unique Cr(VI) photoreduction capability in recent decades, their performance is still insufficient for practical applications because of their low Cr(VI) uptake and poor visible light response. To cope with these drawbacks, a new OH-modified Zr-based MOF, termed HCMUE-1, was successfully prepared via a solvothermal method in this work. The complete characterization of HCMUE-1 was performed through various techniques, including powder X-ray diffraction (PXRD), Raman spectroscopy, Fourier transform infrared (FT-IR), thermogravimetric analysis and differential scanning calorimetry (TGA-DSC), scanning electron microscopy combined with energy-dispersive X-ray (SEM-EDX), and X-ray photoelectron spectroscopy (XPS). The obtained data exhibited the excellent Cr(VI) photoreduction efficiency of HCMUE-1, reaching up to 98% after 90 min and almost 100% after 120 min under visible light illumination in a low acidic medium. Noteworthily, HCMUE-1 retained the same Cr(VI) removal rate for at least seven cycles without considerable loss. Further experimental investigations demonstrated that the structural stability and surface morphology of HCMUE-1 were retained after photoreduction. Moreover, the photocatalytic reduction mechanism of Cr(VI) to Cr(III) was interpreted through a series of systematic experimental measurements. These results indicate that HCMUE-1 possesses potential as an efficient photocatalyst for reducing toxic Cr(VI) species from wastewater in real-life conditions.

Influence of ZIF-9 and ZIF-12 structure on the formation of a series of new Co/N-doped porous carbon composites as anode electrodes for high-performance lithium-ion batteries.

A series of new Co/N-doped porous carbon composites, denoted as Co/CZIF-9 and Co/CZIF-12, containing Co nanoparticles encapsulated in nitrogen-doped carbon matrices were prepared by annealing Co-based zeolite imidazolate framework materials, ZIF-9 and ZIF-12, as the efficient precursors at different temperatures. The structural features of the as-synthesized composites at 900 °C were determined by analytical methods with high reliability. Consequently, Co/CZIF-12_900 exhibits a high first specific discharge capacity of 971.0 mA h g-1 at a current density of 0.1 A g-1. Notably, the specific discharge/charge capacity of Co/CZIF-12_900 reaches about 508.8 mA h g-1 at 0.1 A g-1 after 100 cycles. The outstanding behaviors can be accounted for by the efficient incorporation of hetero-nitrogen doping and the Co nanoparticles within the layered structure of porous carbon, enhancing electrical conductivity and structural stability and limiting volume change during the intercalation/deintercalation of Li+ ions. These findings suggest that the Co/CZIF-12_900 material could be employed as a promising anode electrode for energy storage products.

An efficient combination of Zr-MOF and microwave irradiation in catalytic Lewis acid Friedel-Crafts benzoylation.

A zirconium-based metal-organic framework, an effective heterogeneous catalyst, has been developed for the Friedel-Crafts benzoylation of aromatic compounds under microwave irradiation. Constructed by a Zr(iv) cluster and a linker 1,4-bis(2-[4-carboxyphenyl]ethynyl)benzene (H2CPEB), the MOF, possessing large pores and high chemical stability, was appropriate for the enhancement of Lewis acid activity under microwave irradiation. The reaction studies demonstrated that the material could give high yields for a few minutes and maintain its reactivity and structure over several cycles.

A Titanium-Organic Framework as an Exemplar of Combining the Chemistry of Metal- and Covalent-Organic Frameworks.

A crystalline material with a two-dimensional structure, termed metal-organic framework-901 (MOF-901), was prepared using a strategy that combines the chemistry of MOFs and covalent-organic frameworks (COFs). This strategy involves in situ generation of an amine-functionalized titanium oxo cluster, Ti6O6(OCH3)6(AB)6 (AB = 4-aminobenzoate), which was linked with benzene-1,4-dialdehyde using imine condensation reactions, typical of COFs. The crystal structure of MOF-901 is composed of hexagonal porous layers that are likely stacked in staggered conformation (hxl topology). This MOF represents the first example of combining metal cluster chemistry with dynamic organic covalent bond formation to give a new crystalline, extended framework of titanium metal, which is rarely used in MOFs. The incorporation of Ti(IV) units made MOF-901 useful in the photocatalyzed polymerization of methyl methacrylate (MMA). The resulting polyMMA product was obtained with a high-number-average molar mass (26 850 g mol(-1)) and low polydispersity index (1.6), which in many respects are better than those achieved by the commercially available photocatalyst (P-25 TiO2). Additionally, the catalyst can be isolated, reused, and recycled with no loss in performance.

Tailoring the Optical Absorption of Water-Stable Zr(IV)- and Hf(IV)-Based Metal-Organic Framework Photocatalysts.

New Zr(IV)- and Hf(IV)-based metal-organic framework photocatalysts, termed VNU-1 and VNU-2 (where VNU = Vietnam National University), were synthesized and their resulting structures fully characterized. By employing a highly π-conjugated linker, namely 1,4-bis(2-[4-carboxyphenyl]ethynyl)benzene, the optical absorption properties were effectively red-shifted into the visible light region. This strategy, coupled with the high water stability of the materials, led to enhanced MOF-driven photocatalytic degradation, under ultraviolet-visible light, of organic dye pollutants commonly found in wastewater.