一种新的光致变色膜：Na2WO4-PAA-Glycerol体系研究

A method for preparing Na₂WO₄-PAA-Glycerol photochromic films was reported. The film was composed of Na₂WO₄, PAA and Glycerol, which were coated on a glass substrate. The film turned blue in the sun, and bleached to transparent in the darkness. The UV-Visible spectra showed strong absorbance at 300～500 nm, and the ABS changed signifanctly at 500～800 nm. The film showed the best photochromic behavior when n_Na2WO4∶n_PAA is 4%～5%. The mechanism was suggested that after irradiation, poly tunstate produced by Na₂WO₄ and PAA formed the tungsten blues. The tungsten blues were bleached due to oxidation back to poly tunstate by oxygen. The film showed not only an excellent photochromism property with rapid response and good reversibility, but also the simple techniques and good stability.     

稀土钨青铜K0.71Nd0.028WO3的制备及其电性能

Tetragonal tungsten bronze K_0.71Nd_0.028WO₃ was synthesized by rare earth co-permeation method using Keggin type POMs of α-K₁₀[SiCu₃(OH₂)W₉O₃₇]·6H₂O (abbreviated as SiW₉Cu₃) as precursor. XRD, XPS, XRF, TG-DTA were used to characterize the resulting material. The XPS results indicate that Nd has permeated and diffused into the body of the sample and exists in tungsten bronze in the form of K_0.71Nd_0.028WO₃. The results of TG-DTA show that K_0.71Nd_0.028WO₃ begins to decompose at 320 ℃. The consequence of DC four-probe shows that the conductivity of the sample permeated by rare earth is 10³ times higher than that of the sample only permeated by methanol at room temperature. The conductivity of the sample only permeated by methanol is only 10^-3 S·cm^-1 but the conductivity of the sample permeated by rare earth is 1.65 S·cm^-1.     

单分散超细ZnO粉体的制备与表征

Monodispersed superfine ZnO powders with particle size of about 200～400nm were successfully prepared by the decompressed distillation process with n-butyl alcohol as the solvent. The starting materials were Zn(NO₃)2·6H₂O and NH₃·H₂O. TG-DSC， XRD， TEM and BET surface areas techniques were used to characterize the precursor and as-prepared superfine ZnO powders. In the preparation process of superfine ZnO powders， two techniques including the decompressed distillation with n-butyl alcohol and washing with absolute ethanol were used to avoid agglomeration. It is showed that the decompressed distillation process has a better effect in avoiding ag-glomeration than washing with absolute ethanol. The precursor obtained by the decompressed distillation technique has a lower calcination temperature than the one obtained by washing with absolute ethanol. Zincite phase of ZnO with some impurities was obtained when the precursor was calcined at 200℃ for 2h. After it was calcined at 300℃ for 2h， pure superfine ZnO powder was obtained.     

用稀土多元渗法制备钾稀土钨青铜KxLayWO3的XPS研究

Potassium tungsten bronze K_xLa_yWO₃ (x>0.5 and y<0.01) was synthesized by rare earth co-permeation method using α-K₇[SiMg₃(OH₂)₃W₉O₃₇] as the precursor. Binding energies of La, W, O and C were determined by XPS. From the XPS data, a peak at 34.21 eV indicates that some W⁶⁺ turned into W⁵⁺ by rare earth co-permeation. The binding energies La3d were the same in the surface and inner of the composite, showing that rare earth element La could diffuse into the body of the composite and the compound of K_xLa_yWO₃ was formed at the same time. The binding energies of O1s in K_xLa_yWO₃ surface were 531.4 eV and 532.0 eV, respectively, while peak at 531.4 eV disappeared through etching process. The result implies that the binding energy of 531.4 eV was due to the adsorbent O. In addition, the binding energies of C1s in the surface were 283.5 eV, 285.0 eV and 286.7 eV respectively, while the inner had only one peak at 285.0 eV due to standard C1s. This proves that there was no C in the core.     

PMW-PNN-PT陶瓷的制备及介电性能研究

0.29Pb(Mg_1/2W_1/2)O₃-0.41Pb(Ni_1/3Nb_2/3)O₃-0.30PbTiO₃ ＋ 0.002 5MnO₂＋xWO₃(PMW-PNN-PT) ceramics were prepared by Semichemical Method. The Mg(Ac)₂, Ni(Ac)₂, and Mn(NO)₃ solution rather than MgO, NiO and MnO₂ were added to the slurry of PbO, WO₃, Nb₂O₅ and TiO₂ and then calcined at 850 ℃ for 2 h. Then the sample was sintered at 1 100～1 200 ℃ for 2 h. The effect of sintering temperature and WO₃-excess amounts on the phase constitute, microstructure and the dielectric characteristics was investigated. The result showed that the PMW-PNN-PT powders with pure pervoskite phase were prepared by single-step calcination. The development of sintered temperature contributes to the increase of dielectric constant and the flatness of dielectric temperature dependence. But the dielectric properties will be worse if the sintered temperature is too high. The increase of WO₃-excess level lead to an increase of Pb₂WO₅ phase and the flatness of dielectric curves, but the dielectric constant will be decreased. The proper WO₃-excess amount of X7R type PMW-PNN-PT ceramics is 5mol% and the proper sintering condition is 1 150 ℃ for 2 h, the maximum dielectric constant is 5 395.     

溶胶-凝胶法制备掺锰钛酸钡纳米粉体及其陶瓷

The Mn-doped barium titanate nanosized powders and ceramics were prepared via the sol-gel process. The powders and ceramics were characterized by XRD， SEM and TEM. The dielectric properties of the ceramics were also measured. The influences of calcination temperature and Mn concentration on the microstructure， dielectric properties and phase composition of BaTiO₃ nano-powders and ceramics were discussed. The results indicated that the BaTiO₃-based powders doped with 1.0mol% Mn were mainly in cubic BaTiO₃ phase， but the tetragonal phase became more evident when the calcination temperature increased. After sintering， Mn-doped ceramics were mainly composed of cubic BaTiO₃. Specially， a new phase of hexagonal crystal BaTiO₃ and BaMnO₃ existed in the ceramics doped with 5.0mol% Mn and the ceramic grains were in ‘clintheriform’. The structure of ‘clintheriform’ led to the poor densification of ceramics， reducing the dielectric constant obviously. The dielectric constants of BaTiO₃ ceramics first increased and then decreased as the Mn concentration increased. The room temperature dielectric constant was 2 290 and the lowest dielectric loss was 0.004 when the Mn concentration was 0.5mol%.     

混合价钨氧化物的制备及其性质研究

Precursors were synthesized with hydrazine oxalic acid and tungstic acid in different ratios and a series of tungsten oxides， O/W ratios from 2.90 to 2.30，were obtained by thermal decomposition from the precursors under nitrogen atmosphere at 640～760℃. This kind of tungsten oxides were found to belong to mixed valence compounds which have some special electrical properties. The experimental result indicated that the electrical conductivity of this tungsten oxide has a close relation with its O/W ratio and reach the maximum at WO_2.50. Seclecting WO_2.50 as an example， its conductivity was measured at different temperatures from -197 ℃ to -2.5 ℃ and it was found that the mixed valence tungsten oxide as conductor belongs to the class of metal ones. Owing to their relatively high electrical conductivity and stability in air， mixed valence tungsten oxide shows some potential use in polymer products as additives.     

钛酸锌的制备及其对高氯酸铵热分解的催化性能

ZnTiO₃ nanocrystals were prepared by sol-gel method, using Zn(NO₃)₂ and Ti(C₄H₉O)₄ in the topic. The as-prepared ZnTiO₃ nanocrystals were characterized by XRD, FTIR and TEM, and the catalytic performance of ZnTiO₃ nanocrystals of different contents for the ammonium perchlorate(AP)decomposition was investigated by thermal analysis. The results indicate that ZnTiO₃ with pure cube structure can be synthesized at 600 ℃ by this procedure,which was spheroid with particle size of about 60~100 nm. The results expressed that the low temperature decomposition peaks of AP is advanced by 17 ℃ and the high temperature decomposition peaks of AP is advanced by 24 ℃ when adding 5% nanoparticle ZnTiO₃ powder. The catalytic effects of ZnTiO₃ powders on the high temperature decomposition of AP are less than that of nanometer metal powders, but all the micron metal powders decrease the low decomposition temperature of AP.     

混合溶剂前体法制备纳米CuO粉体及其性能表征

Nano-CuO was prepared by heating nano-Cu₂(OH)₂CO₃ precursors in different calcination temperatures. The precursor was synthesized from water-alcohol mixed solution of Cu(Ac)₂ using mixed solution of NaOH and Na₂CO₃as precipitants. XRD, FT-IR, TEM, TG-DTA and surface area measurement techniques were used to investigate the properties of the CuO powder. The results show that the spherical, well dispersed nano-CuO powder with the average size of 15 nm and higher catalytic activity for H₂O₂ decomposition was obtained at 300 ℃. With the increasing of calcination temperature, crystal of CuO grows up, agglomeration of the powder becomes heavier and catalytic activity decreases. FT-IR patterns revealed that the vibration fine structure of Cu-O bond in nano-CuO powder disappears and main absorption is red-shifted with the average size of nano-CuO reducing.     

磷酸盐直接共沉淀法制备K0.6Sr0.7Zr4P6O24纳米粉末

Nanometer K_0.6Sr_0.7Zr₄P₆O₂₄ (KSZP)powders were synthesized from KNO₃, Sr(NO₃)₂, NH₄H₂PO₄ and ZrOCl₂·8H₂O by direct co-precipitation method. The as-prepared precipitates and KSZP powders were characterized by thermal analysis, XRD, particle-size analyzer and SEM measurements. The results showed that the precipitates could be heat-treated at near 580 ℃ and 900 ℃, and the crystallization of the KSZP powder product depends on treatment temperature. It was non-crystalline after dried at 80 ℃, became incomplete crystalline KSZP after heat-treated at 900 ℃ and was single-phase KSZP after calcined at 1 380 ℃. The mean particle size and particle-size distribution of KSZP powder after heat-treated at 900 ℃ were smaller and narrower than those after dried at 80 ℃ and calcined at 1 380 ℃, and were 62 nm and 40～100 nm, respectively. The particle shape of the powder after heat-treatment was spheric, and the reuniting or agglomeration was found. Phosphate direct co-precipitation was more suitable than phosphate converse co-precipitation to synthesize nanometer single-phase KSZP powder and the sintered body with the nanometer powder possesses better integral sintering properties.     

钨元素的发现及其概念的发展

1781年,瑞典化学家舍勒在白钨矿中发现了钨酸,预测其中一定含有一种新金属元素,并将其命名为钨(Tungsten)。1783年,西班牙化学家德鲁亚尔兄弟从黑钨矿中成功提取出了舍勒所说的新金属单质,将其命名为钨(Wolfram)。1803年,英国化学家道尔顿原子论的提出,赋予钨元素新的含义:具有一定质量的钨原子。1930年以后,钨同位素的发现使人们对钨元素有了新认识,并逐渐形成了现代钨元素的概念。关于钨元素的认识经历了从假说到客观存在、从定性到定量、从宏观到微观的发展历程。钨元素概念的演变体现了科学思想和科学方法的进步。     

“能干而低调”的钨元素

较为详细地介绍了钨元素的发现历程,钨金属与合金、含钨杂多配合物、氧化钨、碳化钨、钨硫族化合物和含有W-W四重键的化合物的应用。     

重量法测定高锡钨精矿中的钨

为消除重量法测定钨精矿中钨时锡的干扰,在溶解过程中用氢溴酸反复冒烟进行消除,利用ICP–OES法测定残渣和滤液中剩余钨量,再与传统重量法相结合进行钨的定量测定。结果表明,该方法的检出限为0.01μg/m L,测定结果的相对标准偏差为3.53%~5.26%(n=5),加标回收率为98.78%~100.93%。该分析方法不仅能够消除锡的干扰,而且可以相对快速得到稳定可靠的结果。     

Tungsten-Based Nanocatalysts: Research Progress and Future Prospects

The high price of noble metal resources limits its commercial application and stimulates the potential for developing new catalysts that can replace noble metal catalysts. Tungsten-based catalysts have become the most important substitutes for noble metal catalysts because of their rich resources, friendly environment, rich valence and better adsorption enthalpy. However, some challenges still hinder the development of tungsten-based catalysts, such as limited catalytic activity, instability, difficult recovery, and so on. At present, the focus of tungsten-based catalyst research is to develop a satisfactory material with high catalytic performance, excellent stability and green environmental protection, mainly including tungsten atomic catalysts, tungsten metal nanocatalysts, tungsten-based compound nanocatalysts, and so on. In this work, we first present the research status of these tungsten-based catalysts with different sizes, existing forms, and chemical compositions, and further provide a basis for future perspectives on tungsten-based catalysts.     

Fabrication of Two‐Dimensional Lateral Heterostructures of WS2/WO3⋅H2O Through Selective Oxidation of Monolayer WS2

Two‐dimensional (2D) lateral heterostructures have emerged as a hot topic in the fast evolving field of advanced functional materials , but their fabrication is challenging. The layer‐structured WS₂ was theoretically demonstrated to be inert to oxidation except for the monolayer, which can be selectively oxidized owing to the simultaneous interaction of oxygen with both sides. Combined with the theoretical calculations, a new method was developed for the successful construction of 2D lateral heterostructures of WS₂/WO₃?H₂O in an ambient environment, based on a simple liquid‐phase solution exfoliation. These lateral heterostructures of WS₂/WO₃?H₂O have interesting properties, as indicated by enhanced photocatalytic activity toward the degradation of methyl orange (MO).     

ICP–OES法测定八氧化三铀中杂质元素钨

以ICP–OES法测定八氧化三铀中杂质元素钨。采用浓HNO3–浓HCl、浓HNO–HF、3 mol/L HNO3三步酸溶方案,利用CL–TBP萃淋树脂将铀基体分离,淋洗液基质为3 mol/L HNO3,淋洗液流速为1 mL/min。弃去最初2 mL死体积淋洗液后接收10 mL,分离回收率平均值为95.93%,线性方程为y=539.71x+16.6,相关系数r2=0.999 7,4水平样品测定结果的相对标准偏差为0.39%~3.12%(n=6)。用该方法对标准物质进行测定,测定结果在参考值范围内。     

Electrochemical Detection of Nitrite Using an Asymmetrically Substituted Cobalt Phthalocyanine Conjugated to Metal Tungstate Nanoparticles

This paper explores the synthesis and characterisation of an asymmetrical Co phthalocyanine (CoPc), and its covalent linking to two tungsten nanoparticles: bismuth tungsten oxide (Bi₂WO₆) and nickel tungsten oxide (NiWO₄). The nanoparticles were also mixed with the CoPc. The CoPc, nanoparticles and their respective conjugates were used as electrocatalysts in the electrochemical detection of nitrite. The electrocatalysts studied in this work had sensitivities ranging from 3–133 μA/mM while the limits of detection (LoDs) ranged between 0.063 μM and 1.7 μM. Bi₂WO₆ and its conjugate exhibited better LoD than corresponding NiWO₄ and conjugate.     

Electrochemical approaches to generation of phosphinidene complexes of tungsten pentacarbonyl

An alternative approach to synthesis of electrophilic terminal phosphinidene complexes of tungsten pentacarbonyl with various substituents at the phosphorus atom has been developed. The approach is based on the reaction of the electrochemically generated tungsten pentacarbonyl ion with trivalent phosphorus acyl chlorides. Electrochemical reduction of ethyldichlorophosphines in the presence of α-diimines is a one-step process that forms 1,3,2-diazaphospholenes containing an exocyclic P-C bond.     

Gasochromic Effect in Platinum-Doped Tungsten Trioxide Films Prepared by the Sol-Gel Method

Tungsten oxide doped by a complex of platinum exhibits a gasochromic effect. A reversible coloration is observed on successive exposure to hydrogen and air. The films were prepared by the sol-gel method at room temperature. They showed strong darkening (blue color) on exposure to hydrogen and were bleached completely when exposed to air. The proccess has been reproduced completely hundreds of times without any losses. The cycling of the coloration was obtained from UV-Vis spectra and the mechanism deduced from both visible and Fourier transform infrared (FTIR) spectra. Colorimetric properties of the gasochromic films were expressed in color space chromaticity diagram.