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Solvent-free Method to Encapsulate Polyoxometalate into Metal-Organic Frameworks as Efficient and Recyclable Photocatalyst for Harmful Sulfamethazine Degrading in Water
摘要： Through a less-investigated in-situ hot-pressing synthesis method, the phosphotungstic acid H3PW12O40 (denoted as PW12) was rapidly incorporated into a metal-organic framework MFM-300(In) in a short time, affording novel PW12@MFM-300(In) composites. This solvent-free preparation process is not only environment-friendly but also energy/time-saving. The inclusion of PW12 in MFM-300(In) was demonstrated by different physical and chemical characterizations. It was interesting to find that PW12@MFM-300(In) as new heterocatalysts display synergistic activity for the visible-light-driven catalytic degradation of pharmaceutically active compound sulfamethazine (SMT). 4-PW12@MFM-300(In) with excellent robustness possesses the high removal efficiency of about 98% toward SMT within 2 h at room temperature, and can also be recycled multiple times for this catalytic process.
关键词： polyoxometalate,metal-organic framework,solvent-free,sulfamethazine,photocatalytic materials
更新于2025-09-23 15:23:52
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A Silicotungstate-Based Silver(I) Compound with Octanuclear Core: Synthesis, Crystal Structure and Luminescent Property
摘要： A novel silicotungstate-based silver(I) compound, formulated as [{Ag8(H3mtz)12}{SiW12O40}2]·8H2O (1) (H3mtz = 3-Mercapto-1,2,4-triazole) has been hydrothermally synthesized. This compound was identified by the single-crystal X-ray diffraction, and also characterized by FT-IR, UV, TG, PXRD and elemental analyses. The data show that it possesses the octanuclear silver(I) clusters and the anionic silicotungstates, which were connected via the hydrogen bonds and weak Ag–O bonds. Interestingly, the estimated optical bandgap of compound 1 is 1.95 eV, which falls into the range of semiconductors.
关键词： Polyoxometalate,Crystal structure,Luminescence,Silver(I)-based cluster
更新于2025-09-23 15:22:29
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A new formaldehyde optical sensor: detecting milk adulteration
摘要： A sensor consisting of an optic fibre with the exposed tip coated with a the polyoxometalate salt [(C4H9)4N]4H[PMo10V2O40], specially designed to be insoluble in water, which UV-Vis spectrum changed in contact with formaldehyde, is presented. The sensor limit of detection for formaldehyde was 0.2 mg L-1, and the limit of quantification was 0.6 mg L-1, which were close to the conventional spectrophotometric method values of 0.2 mg L-1 and 0.5 mg L-1, respectively, and lower than the tolerable limit for ingested food. The sensor was tested for formaldehyde quantification in milk, as its deliberate addition is a matter of concern. The results obtained analysing formaldehyde in milk samples by the optical sensor and by the conventional method were not statistically different (α=0.05).
关键词： acetylacetone method,milk,formaldehyde,polyoxometalate,food adulteration,optical fibre sensor
更新于2025-09-23 15:21:01
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A polyoxometalate-based metal–organic polyhedron constructed from a {V <sub/>5</sub> O <sub/>9</sub> Cl} building unit with rhombicuboctahedral geometry
摘要： The design and construction of metal–organic polyhedra has received much attention by chemists due to the intriguing diversity of architectures and topologies that can be achieved. There are several crucial factors which should be considered for the construction of metal–organic polyhedra, such as the starting materials, reaction time and temperature, solvent and suitable organic ligands. Recently, polyoxometalates (POMs), serving as secondary building units to construct POM-based metal–organic polyhedra, have been the subject of much interest. The title compound, dodecakis(dimethylammonium) octakis(μ-benzene-1,3,5-tricarboxylato)hexa-μ-chlorido-tetracosa-μ-oxido-triacontaoxidotriacontavanadium, (NH2Me2)12[(V5O9Cl)6(C9H3O6)8], was synthesized successfully by self-assembly of VOCl3 and benzene-1,3,5-tricarboxylic acid under solvothermal conditions. The title polyhedron has an rdo topology when the {V5O9Cl} building unit and the benzene-1,3,5-tricarboxylate (BTC3?) ligand were simplified into 4-connected and 3-connected vertices. Interestingly, when the {V5O9Cl} building unit and the BTC3? ligand are considered as quadrangular and triangular faces, the structure displays rhombicuboctahedral geometry with an outer diameter of 21.88 ?. The packing of the polyhedra produces a circular channel with a diameter of 8.2 ?. The title compound was characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, thermogravimetric analysis and powder X-ray diffraction.
关键词： POV,crystal structure,SQUEEZE,nanoball,rhombicuboctahedron,MOP,molecular polyhedra,nanocage,topological analysis,metal–organic polyhedron,circular channel,polyoxometalate
更新于2025-09-23 15:21:01
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Smart yolk/Shell ZIF-67@POM Hybrids as Efficient Electrocatalysts for the Oxygen Evolution Reaction
摘要： The purpose of this research is to develop an effective and inexpensive oxygen evolution reaction (OER) electrocatalysts to achieve high-efficiency water decomposition. Herein, Keggin-type polyoxometalate (POM) nanoparticles coated with zeolitic imidazolate framework (ZIF-67) are successfully synthesized by facile methods. An efficient ZIF-67@POM catalyst with yolk/shell structure is reported. The POM nanomaterials are uniformly dispersed in the surface of ZIF-67. This unique yolk/shell structure with potential synergistic interaction between POM and ZIF-67 result in superior electrocatalytic activity in OER. When the current density is 10 mA cm-2, the overpotential is only 287 mV, and the Tafel slope is 58 mV per decade. Moreover, the as-prepared yolk/shell ZIF-67@POM catalysts exhibit excellent cycling stability, high surface area, abundant surface active sites and high diffusion efficiency comparable to the traditional noble-metal-free OER electrocatalyst.
关键词： polyoxometalate,metal-organic framework,electrocatalysis,oxygen evolution reaction
更新于2025-09-19 17:15:36
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Zr <sub/>4</sub> -Substituted polyoxometalate dimers decorated by <scp>d</scp> -tartaric acid/glycolic acid: syntheses, structures and optical/electrochemical properties
摘要： In this article, two new tetra-Zr(IV)-substituted sandwich-type Keggin polyoxometalates functionalized by chiral D-tartaric acid and glycolic acid, K2H10[Zr4(H2O)2(μ-OH)(μ3-O)2(D-tartH)(GeW10O37)2]·27H2O (1, D-tartH4 = D-tartaric acid) and K2H10[Zr4(H2O)2(μ3-O)2(gly)2(GeW10O37)2]·32H2O (2, glyH2 = glycolic acid), have been synthesized under hydrothermal conditions and characterized by FT-IR spectra, elemental analysis, single-crystal X-ray structure analysis, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), ultraviolet-visible absorption spectroscopy (UV-vis) and cyclic voltammetry (CV). The structure analysis reveals that both 1 and 2 contain a [Zr4(H2O)2(μ3-O)2(GeW10O37)2] cluster. UV-vis spectra indicate that both compounds are a wide-gap semiconductor. In addition, compound 1 is a chiral Zr(IV)-substituted sandwich-type Keggin cluster because the D-tartH ligand is chiral and the Flack divisor of 1 is 0.00, showing non-linear optical properties. The cyclic voltammograms indicate that compounds 1 and 2 have good electrocatalytic activity in the reduction of H2O2.
关键词： Zr4-Substituted polyoxometalate dimers,optical properties,electrochemical properties,structures,syntheses,D-tartaric acid,glycolic acid
更新于2025-09-19 17:15:36
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Self-Assembly of Hybrid Oxidant POM@Cu-BTC for Enhanced Efficiency and Long-Term Stability of Perovskite Solar Cells
摘要： The controllable oxidation of Spiro-OMeTAD and improving stability of hole transport materials (HTMs) layer are crucial for good performance and stability of perovskite solar cells (PSCs). Herein, we report a hybrid polyoxometalate@metal-organic framework (POM@MOF) material – [Cu2(BTC)4/3(H2O)2]6[H3PMo12O40]2 or POM@Cu-BTC – for oxidation of Spiro-OMeTAD with Li-TFSI and TBP. When POM@Cu-BTC is introduced to the HTM layer as dopant, the PSCs achieve a superior fill factor of 0.80 and enhanced power conversion efficiency 21.44%, as well as improved long-term stability in an ambient atmosphere without encapsulation. The enhanced performance is attributed to the oxidation activity of POM anions and solid-state nanoparticles. Therefore, this research presents a facile way by using hybrid porous materials to accelerate oxidation of Spiro-OMeTAD, further improving the efficiency and stability of PSCs.
关键词： metal-organic frameworks,oxidation,polyoxometalate,stability,PSCs
更新于2025-09-19 17:13:59
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Application of Polyoxometalate-Ionic Liquids (POM-ILs) in Dye-Sensitized Solar Cells (DSSCs)
摘要： Polyoxometalates (POMs) as anionic metal oxides are promising candidates for application in dye-sensitized solar cells (DSSCs) due to their peculiar properties including a reversible and multi-electron redox behavior. In this work, four polyoxometalate as ionic liquids (POM-ILs) based on the combination between phosphomolybdate anion (PMo12O40 3-) and organic cations such as [BMIM]+, [BPy]+, [HDPy]+ and [P6,6,6,14]+ were prepared and characterized. A detailed chemical structural elucidation by elemental analysis, ATR-FTIR, 1H and 31P NMR spectroscopies have been performed. These POM-ILs were tested as photosensitizers by adsorption to the photoanode (TiO2 film) for different times (15 minutes to 17 hours). The DSSCs performance can be highly improved comparing the commercially available compound and POM-ILs. The electrodeposition process is an excellent alternative to adsorption in order to improve the overall efficiencies. In general, [BPy]3[PMo12O40] and [P6,6,6,14]3[PMo12O40] are the most promissory compounds for DSSC approaches.
关键词： Dye-Sensitized Solar Cells,Electrodeposition,Ionic Liquids,Polyoxometalate,Energy Conversion Efficiency
更新于2025-09-16 10:30:52
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Polyoxometalate‐derived multi‐component X/W2C@X, N‐C (X=Co, Si, Ge, B and P) nanoelectrocatalysts for efficient triiodide reduction in dye‐sensitized solar cells
摘要： A series of multi-component X/W2C@X,N-C hybrid catalysts have been prepared to systematically investigate the electro-catalytic activity of triiodide reduction in DSSCs. Different components in catalyst promote photovoltaic performance by synergistic effect. The electronegativity of dopants can directly influence the catalytic activity of catalysts.
关键词： nanocomposite,dye-sensitized solar cells,counter electrode,tungsten carbide,polyoxometalate
更新于2025-09-12 10:27:22
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Organic-inorganic Hybrid Clusters Assembled from Phosphomolybdate Anions and Thioarylated Tetrathiafulvalenes with Diversiform Electron States and Configurations
摘要： A series of organic–inorganic hybrid clusters comprising thioarylated tetrathiafulvalene derivatives (A-S-TTFs) and Keggin-type polyoxometalates have been prepared via proton-induced intermolecular charge transfer or electrochemical oxidation methods, and their structural features have been intensively studied by X-ray diffraction. The generation of co-crystals occurs due to the flexible structure of the A-S-TTF and its electrostatic interaction with the polyoxometalate anions. The complexes can be divided into three types, i.e., type I, type II, and type III, which have organic/inorganic ratios of 3:1, 2:1, and 1:1, respectively. Multiple intermolecular interactions are observed between the organic and inorganic moieties, which stabilize the structures of the resulting hybrid clusters. In the clusters, Ar-S-TTFs are oxidized into radical cations (except in complex (TTF4)·(PMA) ·(TBA), where TTF4 is presented as a +2 cation). There are two factors affecting the packing styles and compositions of the hybrid clusters: 1) valence state of the Ar-S-TTF and 2) volume of the aryl groups thereon.
关键词： Thioarylated tetrathiafulvalene,Keggin-type polyoxometalate,self-assembly,crystal structure
更新于2025-09-12 10:27:22