N 掺杂TiO2光催化剂的制备及其可见光活性研究

A visible-light-active photocatalyst was prepared by calcination of the hydrolysis product of tetrabutyl titanate with ammonia as precipitant. The photocatalyst was characterized by X-ray diffraction (XRD), UV-Vis diffuse reflection spectra (DRS), thermal gravimetric-differential thermal analysis (TG-DTA), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM). The color of the photocatalyst was yellow and could absorb light wavelength under 550 nm as measured by DRS. The catalyst calcined at higher temperature will give lower absorbance for visible light. Structures of the sample were characterized mainly to be anatase by XRD except for the sample calcined at 700 ℃ which gave mixtures of anatase and rutile. TG-DTA results showed that temperature for anatase formation was 415 ℃. XPS results showed that doped-nitrogen was presented in the sample, they are important to show visible-light absorbency. The photocatalytic activities were evaluated using methyl orange and phenol as model pollutants, the results showed that over 90% of phenol could be degraded under visible light using N/TiO₂ as the catalyst after 4 hours reaction. Almost the same activity was found for the TiO₂ photocatalyst calcined at different temperature under sunlight but activities were different when the treatment was under UV light.     

离子层气相反应法(ILGAR)制备CuInS2薄膜的研究

CuInS₂ thin films have been prepared by ion layer gas reaction (ILGAR) using C₂H₅OH as solvent, CuCl and InCl₃ as reagents and H₂S gas as sulfuration source. The effects of cationic concentrations and numbers of cycle on the properties of CuInS₂ film were investigated. The chemical composition, crystalline structure, surface topography, deposited rate, optical and electronic properties of the films were characterized by X-ray diffractrometry (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), ultraviolet-visible spectrometry (UV-Vis) and Hall System. The results show that the crystalline of CuInS₂ thin films and the deposition rate have been improved with the increase of cationic concentration, while CuxS segregation phases appear with further increasing cationic concentration. The deposition rate is close to constant as cationic concentration is fixed. CuInS₂ thin film derived form lower cationic concentration is uniform, compact and good in adhesion to the substrates. The absorption coefficient of CuInS₂ thin films is larger than 10⁴ cm^-1, and the band gap E_g is in the range of 1.30～1.40 eV. The dark resisitivity of the thin film decreases from 50 to 10 Ω·cm and the carrier concentration ranges are over 10¹⁶ cm^-3.     

锂离子电池正极材料LiMn2O4的合成与晶体结构（英）

Spinel LiMn₂O₄ powders were prepared using two-step synthesis method consisting of solid-state reaction method and citrate modified sol-gel method. The effects of the calcination temperature and the Li/Mn ratio of raw materials were studied on the physicochemical and electrochemical properties of the spinel LiMn₂O₄ powders, such as crystallinity, lattice constant and density. The title compound was characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Polycrystalline LiMn₂O₄ powers calcined at 750 ℃ were found to be composed of very uniformly-sized microcrystal with an average particle size of 300 nm. The improvement in electrochemical properties was mainly attributed to the process of re-grinding by absolute alcohol.     

Sr2CeO4蓝色荧光粉体材料的柠檬酸盐分解法合成与表征

Pure Sr₂CeO₄ nanosized phosphors has been successfully synthesized via a citrate decomposition method at a temperature as low as 900 ℃. The particle sizes were estimated to be 80～120 nm by X-ray diffractometry (XRD) and transmission electron microscopy (TEM). The particle sizes were determined at the temperature of pre-decomposition, and would increase with the annealed temperature. Meanwhile, the photoluminescence properties of nano-Sr₂CeO₄ were investigated.     

Li4Ti5O12溶胶-凝胶法合成及其机理研究

The precursors of Li₄Ti₅O₁₂ were prepared from tetrabutyl titanate and lithium acetate by sol-gel process. The Li₄Ti₅O₁₂ samples were synthesized by calcining the gel precursors at 400～900 ℃ in air for 6～20 h. Its reaction mechanism was investigated by infrared spectroscopy(IR), thermogravimetry(TG) and X-ray diffraction(XRD). The effects of sinter-temperature, calcination-time and thermal-treatment for the products were discussed. The samples were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM). The results showed that the single-phase products were obtained by calcining the gel precursors at 800 ℃ in air for 20 h, the sinter-temperature was lower than that of solid-state method, the particles were narrowly distributed, well crystallized with a size range from 0.3μm to 0.5 μm.     

ZnO/eosin-Y混合薄膜的生长机理和形态

Thin hybrid films of ZnO/eosin-Y were prepared by electrodeposition at-0.8 and-0.9 V in aqueous and non-aqueous baths at temperatures ranging from 40 to 90 ℃ with dye concentrations of 100 and 400 μmol·L-1.The films were characterized by X-ray diffraction (XRD),scanning electron microscopy (SEM),energy-dispersive X-ray analysis (EDX),and absorption spectroscopy.The films prepared in a non-aqueous bath were non-porous and did not adsorb dye molecules on their surface.However,the films grown in aqueous media were porous in nature and adsorbed dye during the deposition of ZnO.Preferential growth of the film along the (002) face was observed,and the highest crystallinity was achieved when the film was deposited at 60 ℃.The maximum absorption was achieved for the films grown at 60 to 70 ℃,a deposition potential of-0.9 V,and a dye concentration of 100 μmol·L-1.     

新型阴极材料Ba0.5Sr0.5Co0.8Fe0.2O3-σ制备与性能研究

Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-σ(BSCF), a new cathode material for solid oxide fuel cell (SOFC), was synthesized by polyacrylicacid (PAA) method. The lattice structures of samples calcined at different temperatures were characte-rized by XRD. Shrinkage, porosity and pore size of the porous BSCF as a function of sintering temperature were investigated. It was found that the cubic perovskite structure could be formed after calcination at 800 ℃ for 2 h, but not well crystallized as seen from some unknown phases, and the pure cubic perovskite structure was formed after calcination at 1 150 ℃ for 2 h. The particle size of BSCF was less than 1～2 μm. The shrinkage of the porous BSCF increased with sintering temperature, but the opposite was true for the porosity. After sintering at 1 100 ℃ for 4 h, the porous BSCF was still in an appropriate structure, with porosity of 29% and electrical conductivity above 400 S·cm^-1.     

Sr3Al2O6∶Eu2+红色发光纳米晶的新型形貌与发光性能的研究

A red luminescent Sr₃Al₂O₆∶Eu²⁺ nanocrystallites with new morphology were synthesized by sol-gel route assisted by microwave irradiation. The phosphor powders were characterized by X-ray diffraction (XRD)， scanning electron microscopy (SEM) and fluorescence spectroscopy. The results reveal that the calcination temperature of the Sr₃Al₂O₆∶Eu²⁺ phosphor crystallites greatly affects its morphology. With temperature increasing， the phosphor crystallites morphology showed primarily from nanorod-like， mixture of nanorod and flower-like to homogeneous flower-like morphology. The effects of new morphology on luminescent properties of phosphors were investigated. Uniformly dispersed flower-like Sr₃Al₂O₆∶Eu²⁺ phosphor powders showed the strongest luminescent intensity and the longest afterglow time.     

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.     

LB膜诱导Ba(NO3)2晶体取向生长

In this work, Ba(NO₃)₂ crystals with single crystal face were induced by using the the method of bio-mimetic mineralization and double LB films of behenic acid (BA) as the template. The crystals were characterized by Scanning Electron Microscope (SEM) and X-Ray Diffraction (XRD). The crystals were observed in regular square shape with uniform size about 5～8 μm by SEM, and they were found by XRD to grow along the (111) plane. From these experiments, we can conclude that the good selection of the (111) crystal face of Ba(NO₃)₂ is due to the electrostatic interactions , the match between this crystal face and the definite lattice structure of the LB films.     

Near infrared study of aqueous rare-earth ethylsulfates

The near infrared spectra of aqueous solutions of the ethylsulfates of La, Nd, Gd, Tb, Er, Yb, Lu, Y, and Na have been determined from about 0.2 mol-dm^–3 to nearly saturation. The extinction coefficients of water have been calculated taking into account the absorption of ethylslfate anions determined in separate experiments. Their values appeared to be nearly the same as that of pure water. The relative contents of free OH groups in 0.5 and 0.7M solutions have been estimated from the absorbances at 1160 nm. They were lower in solutions of the heavy rare-earth ethylsulfates (Tb, Er, Yb, Lu) than in equimolar solutions of the lighter ones (La, Nd), confirming our previous view that secondary hydration of the heavy trivalent rare-earth cations is distinctly stronger than that of the lighter ones. A comparison of the spectra of these aqueous ethylsulfates with those of perchlorates shows that the structure-breaking ability of the C₂H₅SO ₄ ^– ion is much smaller than that of perchlorate anion.     

Microstructures of Some Bi-W-Nb-O Phases

Microstructures of three Bi-W-Nb-O phases have been examined by using high-resolution transmission electron microscopy. Bi₁₇W₂Nb₃O₃₉ and Bi₁₇WNb₃O₃₆ have incommensurate superstructures derived from the defect fluorite-type δ-Bi₂O₃ and can be regarded as intermediate phases between the type II solid solutions in the Bi-Nb-O and Bi-W-O systems. Bi₈W₂Nb₂O₂₃ has a Bi₂WO₆-like subunit cell with a stepped superstructure. Formation mechanisms of various superstructures are discussed.     

Reactivity of Binary Mixtures of La(III) Oxide and Cu(II) Oxalate or Nitrate and Synthesis of La(III) Cuprate

Reactivity of mixtures of La(III) oxide and Cu(II) oxalate/nitrate in hydrated as well as anhydrous state was studied using TG, DTA and XRD. Cu(II) oxide formed in the endothermic decomposition of mixture containing hydrated Cu(II) nitrate and La(III) oxide could not form La₂CuO₄ while Cu(II) oxide formed in the exothermic decomposition of mixture containing hydrated/anhydrous Cu(II) oxalate and La(III) oxide reacts with La(III) oxide and develops the phases CuLaO₃ and La₂CuO₄. The maximum reactivity with respect to the formation of La₂CuO₄phase was observed in mixture containing anhydrous Cu(II) oxalate. This revised version was published online in July 2006 with corrections to the Cover Date.     

Preparation of ZrO2-TiO2-CeO2 and Its Application in the Selective Catalytic Reduction of NO with NH3

TiO₂,ZrO₂-TiO₂,andZrO₂-TiO₂-CeO₂ were prepared by co-precipitation method and characterized by X-ray diffraction (XRD), specific surface area measurements (BET), temperature programmed desorption (NH₃-TPD), oxygen storage capacity (OSC), and temperature programmed reduction (H₂-TPR). The results showed that ZrO₂-TiO₂-CeO₂ exhibited large number of surface strong acid, possessed some oxygen storage capacity, and strong redox property. The three materials were used as supports and the monolith catalysts were prepared with 1% (w) V₂O₅ and 9% (w)WO₃ for selective catalytic reduction (SCR) of NO with ammonia in the presence of excessive O₂, and the results of catalytic activity showed that the catalyst used ZrO₂-TiO₂-CeO₂ as support yielded nearly 100% NO conversion at 275 °C at a gas hourly space velocity (GHSV) of 10000 h⁻¹, and it had the best catalytic activity and showed great potential for practical application.     

电感耦合等离子体光谱法测定铜冶炼烟尘中锌

本实验介绍了电感耦合等离子体光谱法测定铜冶炼烟尘中锌含量的分析方法。针对样品碳,硅含量高的特点,有针对性的研究了样品的消解方法,确定采用盐酸、硝酸、氢氟酸、高氯酸对铜冶炼烟尘样品进行消解。同时进行了干扰试验,确定样品中高含量的铜,铅,砷等对样品测定结果没有影响。并对仪器的工作参数进行了优化。方法检出限为为0.011 mg/L,测定下限为0.019 mg/L,3个样品的相对标准偏差在0.54%~0.92%之间,加标回收率在96%~101.14%之间。该方法样品消解完全,流程短,操作简单,快速,测定准确度高,可以满足铜冶炼烟尘中锌含量的测定。     

α-Fe2O3掺杂对In2O3电导和气敏性能的影响

用化学共沉淀法制备了α Fe2O3掺杂的In2O3纳米晶微粉,研究了α Fe2O3掺杂对In2O3电导和气敏性能的影响. 结果表明, α Fe2O3和In2O3间可形成有限固溶体In2－xFexO3(0≤x≤0.40); Fe3＋对In2O3晶格中In3＋格位的部分取代,大大增强了阴阳离子间的结合力,导致材料中氧空位VO×数骤降、 自由电子的浓度变稀和电导下降. n(Fe3＋):n(In3＋)=5 :5的共沉淀粉于800 ℃下灼烧4 h所得的α Fe2O3掺杂In2O3传感器元件,对45 μmol•L－1 C2H5OH的灵敏度达54.0,为相同浓度干扰气体汽油的8倍多.     

电感耦合等离子体光谱法(ICP-AES)测定银精矿中铜、铅、锌、砷、镉、钙、镁、锰含量

针对银精矿样品复杂,难消解的特点,研究了不同酸溶法和碱熔法对样品的消解情况,建立了硝酸,盐酸,氢氟酸,高氯酸消解银精矿的方法。根据元素灵敏度和抗干扰性,选定各元素的测定波长。通过酸溶样和碱熔样测定结果比对,验证了方法准确性。建立了四酸消解-电感耦合等离子体光谱法测定银精矿中铜、铅、锌、砷、镉、钙、镁、锰含量的方法,元素的线性相关系数均在0.9999以上。通过共存元素干扰实验,确定了银精矿中高含量元素(铜、铅、锌、铁、锑、铋等)对测定元素结果没有影响。方法检出限：Cu 0.0063 mg/L, Pb 0.0159 mg/L ,Zn 0.0090 mg/L,As 0.0192 mg/L, Cd 0.0093 mg/L ,Ca 0.0084 mg/L, Mg 0.0075 mg/L, Mn 0.0081 mg/L。测定下限：Cu 0.0105mg/L,Pb 0.0265 mg/L, Zn 0.0150 mg/L, As 0.0320 mg/L, Cd 0.0155 mg/L, Ca 0.0140 mg/L, Mg 0.0125 mg/L,Mn 0.0135 mg/L。3个样品的相对标准偏差在0.87%~3.56%之间,加标回收率在95.00%~103.56%之间。方法流程短,操作简单,快速,灵敏度和再现性高,结果准确可靠,可以满足银精矿中铜、铅、锌、砷、镉、钙、镁、锰含量的测定。     

Li_(1.3)Ti_(1.7)Al_(0.3)(PO_4)_3,Na_(1.3)Ti_(1.7)Al_(0.3)(PO_4)_3的离子交换研究

研究了在不同温度下的NaNO3和AgNO3水溶液中Li1.3Ti1.7Al0.3(PO4)3和Na1.3Ti1.7Al0.3(PO4)3离子交换行为.实验表明Li1.3Ti1.7Al0.3(PO4)3和Na1.3Ti1.7Al0.3(PO4)3均显示出了高选择性与Na+和Ag+进行离子交换的特征,且对Ag+的选择性高于Na+.升高温度可显著提高Ag/Li和Ag/Na的交换反应速度.     

Reactivity of Zn3V2O8 Towards ZnMoO4 in the Solid State

The reactivity of Zn₃ V₂ O₈ towards ZnMoO₄ was investigated by using DTA and XRD methods. A new compound of the formula Zn_2.5 VMoO₈ was found. It crystallises in an orthorhombic system. The melting temperature was determinated to be 845±5°C. This revised version was published online in August 2006 with corrections to the Cover Date.     

B2O3-Bi2O3-ZnO-Al2O3玻璃助烧剂对BaTiO3陶瓷烧结条件、晶体结构和介电性能的影响

通过调节B₂O₃-Bi₂O₃-ZnO-Al₂O₃(BBZA)玻璃的添加量研究其对钛酸钡(BaTiO₃)陶瓷烧结条件、晶体结构和介电性能的影响。结果表明：添加适量的BBZA玻璃能够有效地将BaTiO₃陶瓷烧结温度由1 350℃降至950℃,并使其致密化。同时,添加BBZA玻璃后,BaTiO₃的晶体结构随着烧结温度的升高而发生转变(立方相→四方相)。另外,BBZA玻璃的引入使BaTiO₃陶瓷的居里峰得到了有效的抑制和拓宽。陶瓷微观形貌显示,玻璃相均匀分布在BaTiO₃晶粒表面。优化的BaTiO₃陶瓷制备条件如下：BBZA添加量(质量分数)为2.0%,烧结温度为950℃。在该条件下制备的BaTiO₃陶瓷介电常数达到1 364,介电损耗低至1.2%。