十一钨钛杂多酸盐MnXW11TiO40(X=Si, B, Zn)的合成及其氧化还原性质

本文报道了十一钨钛杂多酸盐ＭｎＸＷ１１ＴｉＯ４０·ＸＨ２Ｏ（Ｘ＝Ｂ,Ｓｉ,Ｚｎ;Ｍ＝Ｋ,Ｈ）的合成方法及其氧化还原性质。三种杂多酸盐的１８３ＷＮＭＲ谱均是六线谱,表明其阴离子仍保持Ｋｅｇｇｉｎ结构。合成的化合物对烯烃环氧化反应具有催化作用。     

氢氧化铝镁正电溶胶稳定性研究

氢氧化铝镁正电溶胶 (以下简称溶胶 )是近几年研制开发的一种新型正电溶胶 ,在油田、化妆品、涂料、污水处理等领域具有广阔的应用前景 .我们曾对溶胶制备、组成、结构[1～ 4] 及其在油田钻井液中的应用做了大量研究工作[5 ,6] ,但关于溶胶的稳定性研究尚少 .本文从恒表面电荷密度模型出发 ,对溶胶进行了近似处理 ,得到了势能曲线 ,并采取动态法研究了无机电解质对溶胶的聚沉规律 .1　实验部分1 .1　氢氧化铝镁正电溶胶的合成　按文献 [1 ]非稳态共沉淀法制备 ,ＡｌＣｌ3·6Ｈ2 Ｏ与ＭｇＣｌ2 ·6Ｈ2 Ｏ的物质的量比为 1∶1 .1 .2　组成和电…     

微波辐射快速合成2-(2′-羟苯基)-5(6)取代苯并咪唑衍生物

苯并咪唑衍生物具有一定的抗病毒能力[1 ] ,一些苯并咪唑衍生物已用作农用抗植物病毒剂[2 ] 。一锅煮合成反应时间较长 ,产率中等[3,4] 。本文用取代邻苯二胺和水杨酸为原料 ,吡啶为溶剂 ,ＰＯＣｌ3为催化剂 ,微波辐射法合成了标题化合物。合成路线如下 :1　实验部分1 1　仪器ＷＣ 1型熔点测定仪 (温度计未校正 ) ;日本岛津ＩＲ 435红外光谱仪 (ＫＢｒ压片 ) ;ＴＥＯＬ ＦＸ90Ｑ核磁共振仪 ,ＤＭＳＯ ｄ6 为溶剂 ;日本柳公Ｃ·Ｈ·Ｎ元素分析仪ＭＴ 3;苏州三星电子有限公司产新天地Ｍ9Ｋ88型微波炉 ,输出功率 85 0Ｗ ,2 4 5 0Ｈｚ。1 2　…     

催化褪色光度法测定痕量锰

1　引　　言测定痕量锰有高碘酸钾 天青 (检出限 2 4× 1 0 - 9ｇ ｍＬ)、过氧化氢 铬黑Ｔ(检出限 1 0× 1 0 - 9ｇ ｍＬ)、高碘酸钾 氨三乙酸 ＰＡＮ ＴｒｉｔｏｎＸ 1 0 0 (检出限 3 .6×1 0 - 9ｇ ｍＬ)和高碘酸钾 ＰＡＮ ＴｒｉｔｏｎＸ 1 0 0 (检出限 3 .2× 1 0 - 9ｇ ｍＬ)等催化光度法。实验表明 :在加热 1 0 0℃、1 0ｍｉｎ和聚丙烯酰胺 (ＰＡＭ)存在下 ,Ｍｎ2 + 能催化氯酸钾氧化铬天青Ｓ(ＣＡＳ)的褪色反应 ,ＰＡＭ对该体系有增稳作用 ,据此建立了氯酸钾氧化铬天青Ｓ催化褪色光度法测定痕量锰的新方法 (检出限 4 0× 1 0 - 1…     

磷钨钴和磷钨镍杂多酸化学修饰电极的研究

杂多酸由于组成和结构上的特点,在电化学和电分析化学领域有着广泛应用[1,2]。迄今为止,有关磷钨钴和磷钨镍三元杂多酸化学修饰电极还未见报道。本文按文献方法[3]合成了磷钨钴(Ｈ3ＰＷ11ＣｏＯ40·ｘＨ2Ｏ)和磷钨镍(Ｈ3ＰＷ11ＮｉＯ40·ｘＨ2Ｏ)杂多酸,分别以Ｈ3ＰＷ12Ｏ40·ｘＨ2Ｏ、Ｈ3ＰＷ11ＣｏＯ40·ｘＨ2Ｏ和Ｈ3ＰＷ11ＮｉＯ40·ｘＨ2Ｏ杂多酸(以下简写为Ｈ3ＰＷ11ＭＯ40·ｘＨ2Ｏ,其中Ｍ代表Ｗ,Ｃｏ和Ｎｉ)为修饰剂,采用电化学方法在导电基体玻碳(ＧＣ)电极上制备了Ｈ3ＰＷ11ＭＯ40/ＧＣ膜修饰电极,制备过程简便、快速。对膜电极的…     

吸光光度法测定硝酸银中微量铜

硝酸银制成后测定杂质含量是鉴定纯度的一个重要环节。杂质铜的含量多少直接影响到硝酸银的纯度。本文研究了 0 .1～ 0 .3ｍｏｌ·Ｌ- 1ＫＯＨ介质中 ,用ＫＩＯ4 作为显色剂 ,采用巯基棉分离 ,吸光光度法测定了硝酸银中微量铜 ,结果满意。1　试验部分1.1　主要仪器与试剂756ＭＣ紫外可见分光光度计 (上海第三分析仪器厂 )Ｃｕ2 +标准溶液 :称取ＣｕＳＯ4 ·Ｈ2 Ｏ 1.96 4 4 ｇ于烧杯中 ,加水溶解后 ,再加几滴硫酸 ,移入 50 0ｍｌ容量瓶 ,稀至刻度 ,配成 1ｍｇ·ｍｌ- 1储备液。逐级稀释成10 μｇ·ｍｌ- 1工作液。ＫＩＯ4 溶液 :称取ＫＩＯ4…     

铁矿中全铁、二氧化硅和氧化钙的测定

铁矿的质量检查和入炉铁矿全铁、二氧化硅和氧化钙的测定 ,是中小型铁厂化验室相当繁重的一项日常工作 ,表现为试样数量多 ,测试频率高 ,同时要求较快地报出结果。采用既经济又快速实用的分析方法 ,对指导高炉生产有着十分重要的意义。1　试验部分1.1　主要仪器与试剂72 1ＳＸ分光光度计钨酸钠溶液 :5 0ｇ·Ｌ- 1,称取Ｎａ2 ＷＯ4 ·2Ｈ2 Ｏ 5ｇ溶于 5 0ｍｌ水中 ,加磷酸 10ｍｌ,用水稀释至 10 0ｍｌ ,摇匀。三氯化钛溶液 :将 15 0～ 2 0 0ｇ·Ｌ- 1三氯化钛用盐酸 (1+ 1)稀释 3倍硫酸铜溶液 :2 0ｇ·Ｌ- 1硫 磷混酸 :Ｈ2 ＳＯ4 ∶Ｈ2 ＰＯ…     

用Grignard试剂C6H5MgBr合成苯甲醛

苯甲醛广泛用于医药、农药、染料、香料等行业[1] 。为了寻找产率高、成本低的新合成方法 ,人们进行了广泛的研究[1 7] 。本文用Ｇｒｉｇｎａｒｄ试剂与苯并咪唑盐[8] 合成苯甲醛。合成路线如下 :1　实验部分ＸＴ 2型数字显微熔点仪 (温度计未经校正 ) :ＰＥ 2 40 0ＣＨＮ元素分析仪 ;ＶａｒｉａｎＩＮＯＶＡ 40 0核磁共振仪 ;试剂均为化学纯。参考文献 [9]合成Ｇｒｉｇｎａｒｄ试剂Ｃ6 Ｈ5ＭｇＢｒ,以四氢呋喃作溶剂。1 1　苯并咪唑的合成在 1 0 0ｍｌ圆底烧瓶中加入 1 0 8ｇ(0 1ｍｏｌ)邻苯二胺和 8ｍｌ(0 2ｍｏｌ) 90 %甲酸 ,90℃下…     

MgSO4-NaOH-H2O四元交互体系160℃水热相作用

在ＭｇＯ-ＭｇＳＯ4-Ｈ2Ｏ体系中存在多种硫氧镁化合物[1-4],其中5Ｍｇ(ＯＨ)2·ＭｇＳＯ4·2Ｈ2Ｏ晶须(简称ＭＯＳ)被开发用作塑料、树脂和橡胶等复合材料添加剂,提高基底材料的抗冲击力、抗弯曲力和耐磨性,也可以用作填料和过滤材料和阻燃剂[5-8]。由于ＭＯＳ价廉、安全,同时具有多种功能,具有广阔的应用前景。本文对ＭｇＳＯ4-ＮａＯＨ-Ｈ2Ｏ四元交互体系160℃水热条件下相作用进行研究,得到同一组成形貌不同的晶须,同时还存在另外两种硫氧镁化合物。1　实验用分析纯ＭｇＳＯ4·7Ｈ2Ｏ(西安化学试剂厂)分别配制质量百分比浓度为6%、1…     

二安替比林甲烷光度法测定工业硅中钛

工业硅中杂质元素的测定 ,一般只测定其中的铁、铝、钙含量[1,2 ] 。在近年的出口工业硅检验中 ,对钛也提出检测要求。本法采用二安替比林甲烷光度法[3 ] 测定工业硅中钛 ,方法简便、稳定 ,结果准确。1　试验部分1.1　仪器与试剂ＴＵ 190 1分光光度计 (北京普析通用仪器公司 )Ｔｉ(Ⅳ )标准溶液 :0 .1ｍｇ·ｍｌ- 1,称取高纯二氧化钛 0 .16 6 8ｇ于铂金坩埚中 ,加焦硫酸钾 5～ 7ｇ于6 0 0℃熔融 ,冷却 ,用Ｈ2 ＳＯ4 (5 + 95 ) 10 0ｍｌ浸提熔块后移入 1Ｌ容量瓶中 ,并以Ｈ2 ＳＯ4 (5 + 95 )稀至刻度。使用时再稀释成 5 μｇ·ｍｌ- 1标准工…     

Keggin结构钨磷酸/聚乙烯吡咯烷酮复合膜的制备和光致变色性质研究

近年来,由于无机－有机复合材料具有潜在的应用前景和特殊性能,尤其是光致变色性能,引起研究者们的广泛兴趣^[1-3],以杂多化合物为多核配合物,通过化合键或氢键作用与高分子底物结合,形成电荷转移物质,可以大大提高复合材料的化学和物理性能。目前,这一领域的研究在国外已经成为热点^[4-7]。本文以Keggin结构钨磷酸和聚乙烯吡咯烷酮为原料,报道了该类复合物的合成、表征及光致变色性质。     

Photophysical property and photostability of J-aggregate thin films of thiacyanine dyes prepared by the spin-coating method

By use of electrostatic interactions of dye molecules and poly(diallyldimethylammonium chloride) (PDDA), the spin-coating technique has been successfully applied to the preparation of stable J-aggregate thin films of thiacarbocyanine dyes on a polycarbonate or quartz plate. The J-aggregate thin films were prepared by the spin-coating of PDDA aqueous solution on dye thin films prepared on a substrate by the spin-coating of 2,2,3,3-tetrafluoro-1-propanol solution of dyes. Photophysical properties of the dye thin films and J-aggregate thin films were studied by measuring the fluorescence spectra, quantum yields, and lifetimes. Coherent size of the J-aggregates was estimated to be 3-12 by means of the absorption bandwidth (full width at half maximum) or radiative lifetime. Photostability of the J-aggregate thin films was also studied in terms of photodegradation efficiency under argon and oxygen in comparison with the dye thin films, and J-aggregate thin films were found to be more stable than the corresponding dye thin films.     

Structure and photochromic properties of molybdenumphosphoric acid/TiO<Subscript>2</Subscript> composite films

TiO₂ sol-gel composite films with dropping molybdenumphosphoric acid (PMoA) have been prepared by sol-gel method. The structure and constitute of composite thin films were studied with Fourier transforms infrared spectroscopy (FT-IR) atomic force microscopy (AFM), and X-ray diffraction (XRD) patterns, respectively. The photochromic behavior and mechanism of composite thin films were investigated with ultraviolet-visible spectra (UV-vis) and electron spin resonance (ESR). FT-IR results showed that the Keggin geometry of PMoA was still preserved inside PMoA/TiO₂ composite thin films, and a charge transfer bridge was built at the interface of PMoA and TiO₂ through the Mo-O-Ti bond. Surface topography of the composite film showed obvious changes before/after adding PMoA, and the surface topography of composite films showed obvious changes before/after irradiating as well. Composite thin film had reversible photochromic properties. Irradiated with UV light, transparent films changed from colorless to blue and they can bleach completely with ambient air in the dark. ESR results showed that TiO₂ were excitated by UV light to produce electrons, which deoxidized PMoA to produce heteropolyblues. The photochromic process of PMoA/TiO₂ system was carried through electron transfer mechanism.     

PHOTOACOUSTIC SPECTRA OF SOME BIOLOGICAL MOLECULES BETWEEN 300 AND 130 nm

Photoacoustic spectra of the biological molecules thymine, adenine, tyrosine, ergosterol and polyadenylic acid were obtained in the 300-130 nm region of photon wavelength using synchrotron radiation as a light source. Photoacoustic measurements were performed with thin solid films of these molecules made by vacuum evaporation, except for polyadenylic acid whose thin films were made from the aqueous solution. It was found that the spectra exhibit absorption structures which are in good agreements with those found from conventional transmission measurements. Some of the spectra, however, exhibit a marked deviation from the transmission data in the region below 145 nm, which may be indicative of photon absorption with subsequent photoelectron emission.     

EPR analysis of copper particles in aqueous systems

Experimental and theoretical EPR spectra of nanodispersed copper synthesized by the reduction of copper dichloride in aqueous solutions, thin films of electrolytic copper, and copper ions are analyzed. It is established that the reduction of copper dichloride in an aqueous solution in the presence of a surfactant yields copper nanoparticles. The EPR spectra are shown to be sensitive to the oxidation of copper nanoparticles in both an aqueous medium and in thin copper films prepared by electrolytic deposition.     

Functional Monomers and Polymers. LX. Effects of Counterions on the Structure of Cu(II)-Polyvinylimidazole and Cu(II)lmidazole Complexes in Aqueous Solution

The effect of counterion types on the structure of Cu(II) complexes of imidazole and poly-4(5)-vinylimidazole in aqueous solution was studied by spectroscopic and electron spin resonance (ESR) techniques. Visible and ESR spectra of both complexes in aqueous solution containing NaClO₄, KNO₃, KC1, and KBr showed only a slight change from each other in the presence of different counterions. On the other hand, the frequency of the center of absorption band in the visible region (λ_max) and ESR parameters of the complex in aqueous solution did not correspond to those reported for its crystalline state, and in addition, those of the polymeric Cu(II) complex were different from those of the low molecular weight Cu(II) complex. It was proposed that in aqueous solution, water molecules are coordinated to the axial position of the complex where counterion molecules are present in the crystalline state, and that the structure of the polymeric Cu(II) complex is different from that of the low molecular weight Cu(II) complex due to steric hindrance of the polymeric ligand.     

Nanocrystalline structure and soft magnetic properties of nickel–molybdenum alloy thin films electrodeposited from acidic and alkaline aqueous solutions

Nanocrystalline nickel–molybdenum (Ni–Mo) alloy thin films were electrochemically synthesized in acidic and alkaline aqueous solutions. Transmission electron microscope bright-field images and electron diffraction patterns of the electrodeposits made it obvious that pure Ni consists of a submicron crystalline phase with the grain diameter of several hundred nanometers, while Ni–20 %Mo alloy was composed of a nanocrystalline phase with the grain diameter of a few nanometers. It was estimated that the nanocrystalline phase of electrodeposited Ni–Mo alloy thin films was introduced by the formation of supersaturated Ni–Mo solid solution phase with Mo content in the deposit more than 20 %. Submicron crystalline pure Ni thin films were hardly magnetized in perpendicular direction to the film plane while the nanocrystalline Ni–20 %Mo alloy thin films were isotropically magnetized. It was suggested that the isotropical magnetization behavior was caused by decreasing the demagnetizing field and the magneto crystalline anisotropy with a decrease in the magnetic moment and the average crystal grain size. Coercive force of a submicron crystalline pure Ni thin film electrodeposited from an acidic aqueous solution was ca. 100 Oe while that of a nanocrystalline Ni–20 %Mo alloy thin film electrodeposited from an alkaline aqueous solution was only 1～2 Oe. Soft magnetic properties of Ni–Mo alloy thin films electrodeposited from an alkaline aqueous solution were better than that from an acidic aqueous solution and it was improved with an increase in Mo content in the deposit. It was estimated that the electrodeposited Ni–Mo alloy catalysts could be easily recovered with magnetic field less than 1 kOe.     

Systematic study on structural phase behavior of CdSe thin films

Cadmium selenide (CdSe) thin films were chemically deposited at room temperature, from aqueous ammoniacal solution using Cd(CH(3)COO)(2) as Cd2+ and Na(2)SeSO(3) as Se2- ion sources. The as-deposited films were uniform, well adherent to the glass substrate, specularly reflective, and red-orange in color. The as-deposited CdSe layers grew with nanocrystalline sphalerite cubic structure along with the amorphous phase present in it, with optical band gap E(g) = 2.3 eV. The films were annealed in air atmosphere for 4 h at different temperatures and characterized for compositional, structural, morphological, and optical properties. XRD and SEM studies clearly revealed the systematic phase transformation of CdSe films from metastable nanocrystalline cubic (zinc blende type) to a mixture of cubic and hexagonal (wurtzite type), and finally into stable hexagonal through different intermediate phases with an improvement in the crystal quality. The films showed a red shift in their optical spectra after annealing.     

Solution Combustion Synthesis: Towards a Sustainable Approach for Metal Oxides

Solution combustion synthesis (SCS) has been widely used to produce simple and complex oxides with a desired morphology (size and shape). SCS is valuable due to low cost, simplicity and energy efficient synthesis. To guarantee the best molecular-level mixing of reactants in an aqueous or solvent-based solution some parameters need to be controlled, such as fuel type, metal cations precursors, stoichiometry ratio (φ), pH effect, atmosphere and initiation type. These determine the final properties of the oxide materials, providing the potential to reach different morphologies, which are essential for their final applications. This Review article focuses on the crucial parameters in SCS and how these affect the overall materials properties from nanostructures to thin films. To finalize, special attention is given to the application of SCS to form metal oxide thin films at low temperature and their application in thin film transistors (TFTs).     

聚乙撑二氧噻吩的导电性及现场ESR响应的研究

聚乙撑二氧噻吩(PEDOT)因为具有很高的稳定性和导电性，近年来受到了广泛 的注意并开始在许多方面得到实际应用．电化学聚合方法具有操作简便、易于控制 等优点．本文采用恒电位电化学聚合方法，在水溶液中Pt电极上制备了聚乙撑二氧 噻吩．研究了单体浓度、支持电解质种类、聚合电位等因素对聚合得到的PEDOT膜 导电性的影响．首次运用电化学现场ESR技术研究了水溶液中PEDOT膜的ESR响应， 结合电化学现场的膜电阻测量研究了PEDOT膜的导电性随所加电位的变化规律．结 果表明，PEDOT膜随不同电位的导电性的变化规律符合极化子—双极化子理论．