New approach to environmentally benign epoxidation: the solid-phase-system using urea–H2O2 and recyclable dodecatungstate on apatite

On the basis of new concept using a solid disperse phase we have developed an efficient catalytic solid-phase-system for epoxidations of alkenes using urea–hydrogen peroxide (urea–H₂O₂) complex and cetylpyridinium dodecatungstate ((CetylPy)₁₀[H₂W₁₂O₄₂]) catalyst on fluorapatite (FAp). The recovered solid catalyst phase was reused to keep the catalytic activity after several times. In the conceptual idea it is a key point that in situ solid-phase-activation of the catalyst with urea–H₂O₂ proceeds to form microcrystals of the active species dispersed on the solid phase. The dispersion of the catalyst on FAp in the case of tungstic acid (H₂WO₄) was suggested by EPMA analysis. We proposed the peroxo type of species keeping the parent polyoxometalate framework as novel active species from FT-IR spectroscopic studies. FAp phase plays important roles of dispersing the active species on its surface to have high catalytic activity and of stabilizing the active species to lead to high reusability.     

Hydroxyl-and-carboxyl ligand concatenating multi-lanthanide substituted tellurotungstates and electrochemical detection of noradrenaline

Developing and exploring organic–inorganic hybrid multi-lanthanide (Ln) implanted heteropolyoxometalates (HPOMs) has bloomed into an emerging research field. In this article, two neoteric d-gluconic acids (H₆GA) concatenating multi-Ln^III implanted heteropolytungstates K₁₄H₁₀[Ln₄(H₂O)₄W₆(H₂GA)₄O₁₂(B-α-TeW₉O₃₃)₄]·60H₂O (Ln = La³⁺ (1), Pr³⁺ (2)) were obtained in acidic aqueous system. Attractively, in the polyanion structure of 1 and 2, six W^VI and four Ln^III centers are connected by four flexible H₂GA^4? ligands via carboxyl and hydroxyl groups, resulting in the heterometallic [Ln₄(H₂O)₄W₆(H₂GA)₄O₁₂]⁸⁺ cluster and then the heterometallic cluster is surrounded by four [B-α-TeW₉O₃₃]^8– segments. Electrochemical measurements for the 1@CFMCN/GCE sensor (CFMCN = carboxyl-functionalized multiwalled carbon nanotube; GCE = glass carbon electrode) demonstrate that 1@CFMCN/GCE shows benign recognition response to detecting noradrenaline (NDA). This research expands the structural diversity of Ln-implanted HPOMs and presents an electrochemical platform of recognizing NDA in the field of biosensors.     

Multicolor electrochromic ultrathin films based on neutral red and polyoxometalate

Electrochromic ultrathin films composed of the polyoxometalate cluster K₁₀[P₂W₁₇O₆₁]·17H₂O (P₂W₁₇), polyallylamine hydrochloride (PAH) and Neutral Red (NR) were fabricated on quartz, silicon wafer and indium-tin oxide substrates by the layer-by-layer self-assembly method. The multilayer [P₂W₁₇/PAH/P₂W₁₇/NR]_n films were characterized by UV-vis spectroscopy, scanning electron microscopy, cyclic voltammetry and chronoamperometry and in-situ spectral electrochemical measurements, which exhibited suitable response time, high optical contrast and low operation potential. The monolacunary polyoxometalate-based electrochromic film displays adjustable colors and undergoes transitions from deep pink to light purple, then to dark purple-blue over the potential range from +0.2 V to − 1.0 V. Furthermore, two types of data storage using optical changes of the [P₂W₁₇/PAH/P₂W₁₇/NR]₃₅ film are proposed. The results provide valuable information for exploring applications in tunable-color electrochromic devices and data-storage devices.     

表面包覆的多金属氧酸盐在膨胀阻燃电缆材料中的抑烟作用

利用硅烷偶联剂对一种Keggin型多金属氧酸盐(十二钼磷酸盐)进行表面包覆处理,然后与膨胀阻燃(IFR)电缆材料共混制备出一种低烟阻燃复合材料,研究了表面包覆的多金属氧酸盐在该复合材料中的抑烟作用,以及对材料性能的影响。结果表明:多金属氧酸盐的引入可以一定程度上抑制材料在燃烧过程中的烟气释放,其中,添加了0.8%-3.0%包覆处理的多金属氧酸盐的IFR电缆材料,其烟密度可以降低15%;另外,该多金属氧酸盐基抑烟剂对IFR电缆材料的力学性能、阻燃性能及电性能等的影响很小。     

Polyoxometalate-based silica-supported ionic liquids for heterogeneous oxidative desulfurization in fuels

With the aim of deep desulfurization, silica-supported polyoxometalate-based ionic liquids were successfully prepared by a one-pot hydrothermal process and employed in heterogeneous oxidative desulfurization of various sulfur compounds. The compositions and structures of the hybrid samples were characterized by various methods such as FT-IR, XPS, Raman,UV–Vis, wide-angle XRD and N_2 adsorption–desorption. The experimental results indicated that the hybrid materials presented a high dispersion of tungsten species and excellent catalytic activity for the removal of 4,6-dimethyldibenzothiophene without any organic solvent as extractant, and the sulfur removal could reach 100.0% under mild conditions.The catalytic performance on various substrates was also investigated in detail. After cycling seven cycles, the sulfur removal of the heterogeneous system still reached 93.0%. The GC-MS analysis results demonstrated that the sulfur compound was first adsorbed by the catalyst and subsequently oxidized to its corresponding sulfone.     

Polyoxometalate-based catalysts for photocatalytic,chemical catalytic and electrocatalytic water oxidation

Complex [Fe₁₁ (H₂O)₁₄(OH)₂(W₃O₁₀)₂(α-SbW₉O₃₃)₆]^27?(2) has been studied independently under photocatalytic or chemical catalytic or electrocatalytic conditions by our group. (1) Under the optimal photocatalytic conditions (photoirradiation at λ = 420 nm, [Ru(bpy)₃](ClO₄)₂ as the photosensor, Na₂S₂O₈ as the oxidant in borate buffer (pH = 10.0)], the turnover number (TON) can reach as high as 1815, the initial quantum yield and the initial turnover frequency (TOF) for the first 60 s was 47% and 6.3 s^?1, respectively. (2) We report herein that 2 are highly active homogeneous water oxidation catalysts when [Ru(bpy)₃]³⁺ is used as the terminal oxidant, with a turnover number (TON) of higher than 78. (3) The current densities achieved during cyclic voltammetry (CV) show that 2 exhibit no electrocatalytic activity at pH 10.0. This study discusses the catalytic behaviors and mechanism of 2 in different experimental conditions (driving forces) for water oxidation.     

Polyoxometalate catalyzed ozonation of chemical pulps in organic solvent media

Polyoxometalate (POM) catalyzed ozonation of chemical pulps in organic solvent media was found to be particularly effective and selective environmentally benign bleaching approach providing a way for substantial increase in pulp brightness, viscosity and degree of delignification in comparison with other ozone-based bleaching techniques. A series of tested low-boiling polar aprotic and protic organic solvents showed a well-defined capacity for ozonation improvement in the presence of Keggin-type heteropolyanion [PMo₇V₅O₄₀]⁸⁻ (HPA-5). Even moderate solvent proportion of 6% (w/w) in the reaction solution caused additional gain in brightness up to 3.4% ISO with simultaneous increase in pulp viscosity up to 8.8% and lignin removal up to 18.9% after HPA-5 catalyzed ozonation (0.8% O₃; 0.5 mM HPA), as compared with the control solvent-free process. An aqueous acetone solution was found to be the preferred reaction medium in terms of pulp brightening and delignification. Under optimized conditions, the POM-catalyzed ozonation of eucalypt kraft pulp in acetone/water solution showed remarkable brightness improvement by 15.1% ISO with additional lignin removal by 39.4% and increase in intrinsic viscosity by 3% in comparison with pulp bleached in water media.     

Inorganic-organic hybrid polyoxometalate containing supramolecular helical chains: Preparation, characterization and application in chemically bulk-modified electrode

An inorganic-organic hybrid polyoxometalate (POM) (Hbpy)₄[SiMo₁₂O₄₀] (1) (bpy = 2,4-bipyridine), has been prepared and characterized. X-ray diffraction study reveals that compound 1 contains interesting organic double helical chains. The hybrid nanoparticles was used as a solid bulkmodifier to fabricate a three-dimensional chemically modified carbon paste electrode (1-CPE) by direct mixing. The electrochemical behavior and electrocatalysis of 1-CPE has been studied in detail. The results indicate that 1-CPE has a good electrocatalytic activity toward the reduction of nitrite in 1 M H₂SO₄ aqueous solution. 1-CPE shows remarkable stability that can be ascribed to the interactions existed between POM anions and organic double helical bpy chains, which are very important for practical applications in electrode modification.     

Contribution of intermolecular interactions to constructing supramolecular architecture: Synthesis, structure and Hirshfeld surface analysis of a new hybrid of polyoxomolybdate and ((1H-tetrazole-5-yl) methyl)morpholine

A new soluble organic–inorganic hybrid based on polyoxomolybdate, [C₆H₁₂N₅O]₃[(PO₄)Mo₁₂O₃₆]·6H₂O (1), has been successfully synthesized and characterized by using elemental analysis, IR, UV spectroscopies, ¹H NMR technique, and single-crystal X-ray diffraction. According to the results of X-ray crystallography the anion [(PO₄)Mo₁₂O₃₆]³⁻ has a typical Keggin structure and the Mo–O distances of Mo–O–Mo bonds are alternately short and long in the polyoxoanion structure. Hirshfeld surface analyses, especially d_norm surface and fingerprint plots, are used for decoding intermolecular interactions in the crystal network and contribution of component units for the construction of the 3D architecture. The results indicate that in 1 the hydrogen bond interaction play a main role in the construction of the 3D architecture, especially the CHO interaction which overruns the classic NHO, NHO hydrogen bond interactions; van der Waals force between the peripheral atoms of component units cannot be ignored.     

Photocatalytic hydrogen evolution under visible light irradiation by the polyoxometalate α-[AlSiW11(H2O)O39] -Eosin Y system

It is important to construct a stable and efficient dye sensitization system for visible-light photocatalytic hydrogen evolution. Eosin Y (EY)-sensitized α-[AlSiW₁₁(H₂O)O₃₉]⁵⁻ (AlSiW₁₁) (an Al³⁺ substituted Keggin polyoxometalate (POM)) for the hydrogen evolution under visible light irradiation (λ > 420 nm) has been carried out in the presence of triethanolamine as electron donor and Pt as co-catalyst. EY can coordinate with AlSiW₁₁. The coordination association between AlSiW₁₁ and EY is beneficial to the charge transfer from EY to AlSiW₁₁ and to stability of EY. The system displays efficient and stable photocatalytic hydrogen evolution. The average apparent quantum efficiency and turnover number of EY during 20 h irradiation (λ > 420 nm) are 10.3% and 473, respectively. The highest quantum efficiency amounts to 28.0% under 520 nm monochromatic light irradiation. The present study highlights linking between dye and POM molecule as a way to develop new visible-light stable photocatalyst or system.