Complete degradation of high-loaded phenol using tungstate-based ionic liquids with long chain substituent at mild conditions

Phenol in waste water threatens human health and is difficultly to be decomposed by nature.Efficient degradation of high-loaded phenol in water under mild condition is still a great challenge.Herein,ionic liquids with tungstate anion were designed and prepared.It was found that dodecyltrimethylammonium tungstate could catalyzed degradation of phenol into gases and water thoroughly at 323 k in 8 h.Tungstate anion revealed good catalytic oxidative activity and long carbon chain group connecting with cation of ionic liquids enriched phenol around catalysts,which induced the complete degradation of phenol at mild conditions.Increasing the amounts of hydrogen peroxide benefited to the total degradation of phenol.In addition,the ionic liquid could be reused for its excellent thermal stability.Our work provided a different strategy to treat waste water containing phenol efficiently.

Study on the hydrogen absorption properties of a YGdTbDyHo rare-earth high-entropy alloy

This study investigated the microstructure and hydrogen absorption properties of a rare-earth high-entropy alloy(HEA),YGdTbDyHo.Results indicated that the YGdTbDyHo alloy had a microstructure of equiaxed grains,with the alloy elements distributed homogeneously.Upon hydrogen absorption,the phase structure of the HEA changed from a solid solution with an hexagonal-close-packed(HCP)structure to a high-entropy hydride with an faced-centered-cubic(FCC)structure without any secondary phase precipitated.The alloy demonstrated a maximum hydrogen storage capacity of 2.33 H/M(hydrogen atom/metal atom)at 723 K,with an enthalpy change(ΔH)of-141.09 kJ·mol^(-1)and an entropy change(ΔS)of-119.14 J·mol^(-1)·K^(-1).The kinetic mechanism of hydrogen absorption was hydride nucleation and growth,with an apparent activation energy(E_(a))of 20.90 kJ·mol^(-1).Without any activation,the YGdTbDyHo alloy could absorb hydrogen quickly(180 s at 923 K)with nearly no incubation period observed.The reason for the obtained value of 2.33 H/M was that the hydrogen atoms occupied both tetrahedral and octahedral interstices.These results demonstrate the potential application of HEAs as a high-capacity hydrogen storage material with a large H/M ratio,which can be used in the deuterium storage field.

Critical current degradation in an epoxy-impregnated rare-earth Ba_(2)Cu_(3)O_(7-x)coated conductor caused by damage during a quench

High-temperature superconducting(HTS)rare-earth Ba_(2)Cu_(3)O_(7-x)(REBCO)coated conductors(CCs)have significant potential in high-current and high-field applications.However,owing to the weak interface strength of the laminated composite REBCO CCs,the damage induced by the thermal mismatch stress under a combination of epoxy impregnation,cooling,and quenching can cause premature degradation of the critical current.In this study,a three-dimensional(3D)electromagnetic-thermal-mechanical model based on the H-formulation and cohesive zone model(CZM)is developed to study the critical current degradation characteristics in an epoxy-impregnated REBCO CC caused by the damage during a quench.The temperature variation,critical current degradation of the REBCO CC,and its degradation onset temperature calculated by the numerical model are in agreement with the experimental data taken from the literature.The delamination of the REBCO CC predicted by the numerical model is consistent with the experimental result.The numerical results also indicate that the shear stress is the main contributor to the damage propagation inside the REBCO CC.The premature degradation of the critical current during a quench is closely related to the interface shear strength inside the REBCO CC.Finally,the effects of the coefficient of thermal expansion(CTE)of the epoxy resin,thickness of the substrate,and substrate material on the critical current degradation characteristics of the epoxy-impregnated REBCO CC during a quench are also discussed.These results help us understand the relationship between the current-carrying degradation and damage in the HTS applications.

Thermodynamic study on phosphorus removal from tungstate solution via magnesium salt precipitation method

The thermodynamic equilibrium diagrams of Mg2＋- 3-4PO - ＋4NH -H2O system at 298 K were established based on the thermodynamic calculation. From the diagram, the thermodynamic conditions for removing phosphorus from the tungstate solution by magnesium salt precipitation were obtained. The results show that when the concentration of total magnesium increases from 0.01 mol/L to 1.0 mol/L, the optimal pH for the phosphorus removal by magnesium phosphate decreases from 9.8 to 8.8. The residual concentration of total phosphorus almost keeps the level of 4.0×10-6 mol/L in the system. MgHPO4, Mg3（PO4）2 and the mixture of Mg3（PO4）2 and Mg（OH）2 are stabilized in these system, respectively. However, increasing the total concentration of magnesium has little effect on phosphorus removal by magnesium ammonium phosphate, while it is helpful for phosphorus removal by increasing the total ammonia concentration. The calculated results demonstrate that the residual concentration of total phosphorus can decrease to 5.0×10-7 mol/L as the total concentration of ammonia reaches 5.0 mol/L and the optimal pH value is 9-10. Finally, verification experiments were conducted with home-made ammonium tungstate solution containing 50 g/L WO3 and 13 g/L P. The results show that when the dosage of MgCl2 is 1.1 times of the theoretical amount, the optimum pH for removing phosphorus is 9.5, which matches with the results of the theoretical calculation exactly.

Preparation of Na specific absorbent and application of sodium removal from ammonium tungstate solution

An adsorbent, Na1.6Al0.6Ti1.4（PO4）3 （or NATP）, was prepared by controlled crystallization of glasses in the Na2O-Al2O3-CaO-TiO2-P2O5 system. The crystalline phases characterized by X-ray diffraction （XRD） show that the sample glasses crystallizes into two phases, i.e. NATP and Ca9Al（PO4）7, while the Ca9Al（PO4）7 phase can be leached selectively with HCl, leaving a massive number of pores in the material. Through the experimental research, the effects of contact time, solution pH, and the initial concentration of Na＋on the cation exchange properties were investigated. The batch sorption kinetics and equilibria can be described by Pseudo-second-order kinetic equations and Langmuir isotherm equations respectively. Furthermore, the experiments with an industrial solution show that the removal rate of sodium from industrial （NH4）2WO4 is higher than 97%. Cycle experiment also shows that the NATP has a good cyclic performance.

Nanostructured Ternary Metal Tungstate-Based Photocatalysts for Environmental Purification and Solar Water Splitting:A Review

Visible-light-responsive ternary metal tungstate(MWO_4) photocatalysts are being increasingly investigated for energy conversion and environmental purification applications owing to their striking features, including low cost,eco-friendliness, and high stability under acidic and oxidative conditions. However, rapid recombination of photoinduced electron–hole pairs and a narrow light response range to the solar spectrum lead to low photocatalytic activity of MWO_4-based materials, thus significantly hampering their wide usage in practice. To enable their widespread practical usage, significant efforts have been devoted, by developing new concepts and innovative strategies. In this review, we aim to provide an integrated overview of the fundamentals and recent progress of MWO_4-based photocatalysts. Furthermore, different strategies, including morphological control, surface modification, heteroatom doping, and heterojunction fabrication, which are employed to promote the photocatalyticactivities of MWO_4-based materials, are systematically summarized and discussed. Finally, existing challenges and a future perspective are also provided to shed light on the development of highly efficient MWO_4-based photocatalysts.

Alkali salts of heteropoly tungstates: Efficient catalysts for the synthesis of biodiesel from edible and non-edible oils

Alkali salts of tungsten based heteropoly acids with different central atom such as P, Si and Co were prepared and evaluated for transes- terification of both edible and non-edible oils to their corresponding fatty acid methyl esters. The catalyst of sodium salt of tungstic acid with Co as central atom （Na5CoW12O40） showed optimum activity towards transesterification compared with other heteropoly tungstates. The catalysts activities were correlated with the observed physico-chemical characteristics derived from FT-infrared （FT-IR）, X-ray diffraction （XRD）, temperature-programmed desorption of ammonia （NH3-TPD） and carbon dioxide （CO2-TPD）. The Na5CoW12O40 catalyst exhibiting high activity even at 65 ℃ is due to the presence of strong acidic as well as basic sites. The disclosed catalyst is tolerable towards water and free fatty acids present in the oils. The influence of catalyst loading, reaction time and reaction temperature is studied to optimize the reaction parameters.

Simultaneous determination of some trace metal impurities in high-purity sodium tungstate using coprecipitation and inductively coupled plasma atomic emission spectrometry

A method based on the combination of coprecipitation with inductively coupledplasma atomic emission spectrometry (ICP-AES) was developed for the determination of impurities inhigh-purity sodium tungstate. Six elements (Co, Cu, Fe, Mn, Ni, and Pb) were coprecipitated bylanthanum hydroxide so as to be concentrated and separated from the tungsten matrix. Effects of somefactors on the recoveries of the analytes and on the residual amount of sodium tungstate wereinvestigated, and the optimum conditions for the coprecipitation were proposed. Matrix-matchingcalibration curve method was used for the analysis. It is shown that the elements mentioned abovecan be quantitatively recovered. The detection limits for Co, Cu, Fe, Mn, Ni, and Pb are 0.07, 0.4,0.2, 0.1, 0.6, and 1.3 μg·g^(-1), respectively. The recoveries vary from 92.5% to 108%, and therelative standard deviations (RSDs) are in the range of 3.1%-5.5%.

Hydrothermal Synthesis,Crystal Structure and Spectral Characterization of a New Copper Isopolytungstate: [Cu(phen)_3][W_6O_(19)]

An unusual inorganic-organic hybrid hexatungstate complex [Cu（phen）3][W6O19] 1 （C36H24 CuN6O19W6, Mr= 2011.20） was hydrothermally synthesized and characterized by singlecrystal X-ray diffraction, IR spectrum, UV-VIS spectrum and elemental analyses. This compound crystallizes in the monoclinic system, space group C2/c with a = 19.1005（11）, b = 11.2585（11）, c = 20.2867（15） A, β= 102.177（2）°, V= 4264.4 A^ 3, μ（MoKa） = 16.691 mm^-1, Dc = 3.133 g/cm^3, Z = 4, F（000） = 3628, the final R = 0.0338 and wR = 0.0798 for 4090 observed reflections with I 〉 2σ（I）. The result of structure determination shows that the crystal structure is constructed from [W6O19]^2- cluster anions and [Cu（phen）3]^2＋ complex fragments, which are held together into a three-dimensional network through hydrogen-bonding interactions.

Effect of sodium tungstate on visual evoked potentials in diabetic rats

AIM： To evaluate the effect of sodium tungstate on visual evoked potentials（VEPs） in diabetic rats.· METHODS： Wistar rats were randomly divided into three groups as normal control, diabetic control and diabetic rats treated with sodium tungstate. Diabetes was induced by single intraperitoneal injection of streptozotocin（50 mg/kg）. Sodium tungstate [40 mg/（kg·d）]was administered for 12 wk and then VEPs were recorded.Additionally, thiobarbituric acid reactive substance（TBARS） levels were measured in brain tissues.·RESULTS： The latencies of P1, N1, P2, N2 and P3 waves were significantly prolonged in diabetic rats compared with control group. Diabetes mellitus caused an increase in the lipid peroxidation process that was accompanied by changes in VEPs. However, prolonged latencies of VEPs for all components returned to control levels in sodium tungstate-treated group. The treatment of sodium tungstate significantly decreased brain TBARS levels and depleted the prolonged latencies of VEP components compared with diabetic control group.· CONCLUSION： Sodium tungstate shows protective effects on visual pathway in diabetic rats, and it can be worthy of further study for potential use.

Effect of bismuth tungstate with different hierarchical architectures on photocatalytic degradation of norfloxacin under visible light

The photocatalytic degradation of norfloxacin by bismuth tungstate(Bi2WO6)with different hierarchical architectures wasinvestigated under visible light irradiation.Bi2WO6was prepared by hydrothermal method with the reaction solution pH rangingfrom4to11.The relatively ultrathin Bi2WO6nanoflakes prepared at pH4showed excellent adsorption and photodegradationefficiency towards norfloxacin.The characterization results showed that Bi2WO6prepared at pH4had a larger specific area andfaster photo-generated carrier separation rate.The decay rate reached the maximum in weak alkaline reaction solution,which couldbe attributed to the presence of moderate OH-anions.The present study demonstrated that the smaller size of Bi2WO6could be anefficient photocatalyst on the degradation of norfloxacin in the aquatic environment.

NON-ISOTHERMAL KINETIC STUDY ON THE THERMAL DEHYDRATION OF SODIUM TUNGSTATE DIHYDRATE

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Expanded Industrial Experiments of Free-alkali Recovery from Sodium Tungstate Solution by the Membrane Electrolysis Process

The expanded industrial experiments were conducted with practical industrial liquor to separate free alkali from sodium tungstate solution by electrolysis with cation-exchange membrane. Experimental results show that on the condition that the temperature is 50-55 degreesC and the current density is 1000 A/m(2), the single electrolysis cell is operated stably and 80% free-alkali in mass fraction is separated from the anode feed liquor of sodium tungstate, with electric efficiency up to more than 88% and the unit energy consumption E lower than 1900 kWh/t; while three electrolysis cells in series are operated, under the condition that the temperature is 60-65 degreesC and the current density is 1000 A/m(2), the electric efficiency can reach higher than 88% and the unit energy consumption E can be lower than 2250 kWh/t.

New cadmium and rare earth metal tungstates with the scheelite type structure

New cadmium and rare earth metal tungstates with the formula Cd0.25RE0.50 0.25WO4 （RE=Nd, Sin, Eu, Gd, D-statistical distrib- uted vacancies in cation sublattice） were synthesized by the solid-state reaction between CdWO4 and corresponding RE2W209. The obtained phases crystallize in the scheelite type structure. The Cd0.25RE0.5 0.25WO4 compounds were characterized by X-ray diffractometer （XRD）, （DTA-TG）, infrared （IR） and EPR methods.

Iodine-doping-assisted tunable introduction of oxygen vacancies on bismuth tungstate photocatalysts for highly efficient molecular oxygen activation and pentachlorophenol mineralization

In this work,the tunable introduction of oxygen vacancies in bismuth tungstate was realized via asimple solvothermal method with the assistance of iodine doping.With the predictions afforded bytheoretical calculations,the as-prepared bismuth tungstate was characterized using various tech-niques,such as X-ray diffraction,Raman spectroscopy,scanning electron microscopy,transmissionelectron microscopy,X-ray photoelectron spectroscopy,electron spin resonance spectroscopy,anduV-Vis diffuse reflectance spectroscopy.The different concentrations of the oxygen vacancies onbismuth tungstate were found to be intensely correlated with iodine doping,which weakened thelattice oxygen bonds.Owing to the sufficient oxygen vacancies introduced in bismuth tungstate as aresult of iodine doping,the molecular oxygen activation was remarkably enhanced,thus endowingbismuth tungstate with high activity for the photocatalytic degradation of sodium pentachloro-phenate.More encouraging is the total organic carbon removal rate of sodium pentachlorophenateover iodine-doped bismuth tungstate that exceeded 90%in only 2 h and was 10.6 times higher thanthat of the pristine bismuth tungstate under visible light irradiation.Moreover,the mechanism,through which the degradation of sodium pentachlorophenate over iodine-doped bismuth tung-state is enhanced,was speculated based on the results of radical detection and capture experiments.This work provides a new perspective for the enhanced photocatalytic degradation of organochlo-rine pesticides from the oxygen vacancy-induced molecular oxygen activation over iodine-dopedbismuth tungstate.

Synthesis and Crystal Structure of Ammonium cis-Dioxo Dibenzilato Tungstate (VI) Dihydrate

A mononuclear tungsten-benzilate, (NH4)2[WO2(Ph2COCOO)2]?H2O was ob- tained by the reaction of ammonium tungstate(VI) with excess benzilic acid in ethanol solution at pH 5~6. The title compound crystallizes in monoclinic system, space group P21/n with a = 8.1078(5), b = 25.797(2), c = 13.6815(8) ? b = 91.001(1)? V = 2861.1(3) 3, Dc = 1.719 g/cm3, F(000) = 1472, C28H32N2O10W, Mr = 740.41, m(MoKa) = 4.097 mm-1 and Z = 4. The full-matrix least-squares refinement resulted in R = 0.033 and Rw = 0.068 for 3974 observed reflections with I >2s(I). The tungsten atom is six-coordinated by two cis-oxo groups and two bidentate benzilate ligands through deprotonated a-alkoxyl and a-carboxyl groups, forming a stable five-membered chelate ring. The compound has a distorted octahedral geometry, which is mainly attributable to the bulky ligand-ligand repulsions.

ELECTRODE SELECTION OF ELECTROLYSIS WITH MEMBRANE FOR SODIUM TUNGSTATE SOLUTION

Xiao Liansheng Wang Wei Zhang Qixiu Gong Bofan Cao Jiashu (Department of Metallurgical Science and Engineering, Central South University of Technology, Changsha 410083, China) Abstrac By measuring the electrode polarization curves of many kinds of materials and life spans of electrodes through intensifying electrolysis in the process, the appropriate electrode materials for different stages of electrolysis of sodium tungstate solution with membrane have been selected The effects of the electrodes with different shapes on electrolysis have been investigated. The result shows that network electrode is more suitable to electrolysis of sodium tungstate solution.

Preparation of High－purity Sodium Tungstate from Low－grade Tung－sten－concentrate with a High Content of Calcium and Other Impurities

A new technological process for production of talium tungstate from low-grade tungsten-concentrate witha high content of calcium and other impurities has been studied. The experiments showed that average tungstenleaching efficiency of more than 96. 92 % can be obtained with a low NaOH consumption by using the mechani-cal activating caustic decomposition , and the content of main impurities (P, As, Si) in Na_2WO_4 solution ob-tained is competitive with that from standard wolframite concentrate by traditional caustic decomposition. Afterrecovering caustic liquor by first crystallization, molylxlenum is removed from Na_2WO_4 solution by ion ex-change method. High-purity sodium tungstate is obtained by second crystallization of Na_2WO_4 solution. Thistechnology has the advantages of good adaptability for raw materials, high removing efficiency of impurities,high tungsten recovery and high economic benefit.

The strain rate sensitive and anisotropic behavior of rare-earth magnesium alloy ZEK100 sheet

To overcome the limitation in formability at room temperature,manufacturers have developed magnesium alloys with remarkable properties by adding rare-earth elements.The rare-earth magnesium alloys behave differently from the conventional alloys,especially with respect to their coupled anisotropic and strain rate sensitive behavior.In the current work,such behavior of the rare-earth Mg alloy ZEK100 sheet at room temperature is investigated with the aid of the elastic viscoplastic self-consistent polycrystal plasticity model.Different strain rate sensitivities(SRSs)for various deformation modes are employed by the model to simulate the strain rate sensitive behaviors under different loading directions and loading rates.Good agreement between the experiments and simulations reveals the importance and necessity of using different SRSs for each deformation mode in hexagonal close-packed metals.Furthermore,the relative activities of each deformation mode and the texture evolution during different loadings are discussed.The anisotropic and strain rate sensitive behavior is ascribed to the various operating deformation modes with different SRSs during loading along different directions.

Effects of sodium tungstate on properties of micro-arc coatings on magnesium alloys

Anodic coatings were prepared by micro-arc oxidation on AZ91HP magnesium alloys in a base solution containing 10 g/L NaOH and 12 g/L phytic acid with addition of 0-8 g/L sodium tungstate.The effects of sodium tungstate on the coating thickness, mass gain,surface morphology and corrosion resistance were studied by eddy current instrument,electronic scales,scanning electron microscope and immersion tester.With the addition of sodium tungstate,the electrolytic conductivity increases and the final voltage decreases.The sodium tungstate has a minor effect on the coating thickness,but lightens the coating color.With increasing sodium tungstate concentration,the size of micropores on the coatings is enlarged and the corrosion resistance of the anodized samples decreases.