一步低温法制备可见光响应的棕色纳米TiO_2及其光催化性能（英文）

光催化作为一种具有前景的技术,被广泛运用于有机物降解、废水处理、空气净化、抗菌、太阳能电池等领域.在众多的光催化材料中,纳米TiO_2因具有性质稳定、耐腐蚀、廉价和无毒等优点而受到广泛关注.但纳米TiO_2禁带宽度较大(3.2 eV)、只对紫外光有响应及电子-空穴对易复合等特性限制了它的应用.因此,提高纳米TiO_2的可见光响应一直是研究的热点.本文发展了一种在低温下制备棕色纳米TiO_2的改良溶胶-凝胶法.该法以钛酸四丁酯为钛源,无水乙醇为溶剂,形成溶胶后无需陈化和高温高压,在简单温和的条件下即可制备出棕色纳米TiO_2.比较了低温干燥和高温焙烧两种处理方法,结果表明,随着制备温度的升高,样品的粒子尺寸增大,比表面积减小,颜色从白色转变为棕色,在更高的温度又变浅.样品的可见光吸收在180°C时达到最大,随后减弱.在优化温度180°C下制备的TiO_2-180°C纳米粒子不仅具有较小的粒径(5.0 nm),较大的比表面积(213.45 m~2/g),且在整个紫外-可见光区都具有较强的吸收,其禁带宽度低至1.84 eV.X-射线光电子能谱结果表明,TiO_2粒子表面的–OH/H_2O含量随制备温度升高而先增加后下降.Raman光谱中Eg峰的移动和变宽表明TiO_2晶格可能存在缺陷或氧空位,而TiO_2-180°C纳米粒子的电子顺磁共振图谱的g值在2.003左右,对应氧空位中的未成对电子,验证了以上推测.其中TiO_2-180°C纳米粒子呈现为最强的EPR信号,表明其晶格内存在最高浓度的氧空位,这是其具有强可见光吸收的原因.光催化实验结果表明,在可见光照射下,TiO_2-180°C可高效降解亚甲基蓝(MB).当C(MB)=10mg/L,p H=4,催化剂添加量为0.07 g时,TiO_2-180°C催化剂的光催化活性达到最佳,光照1 h后MB降解率达到99.33%,反应速率常数(0.08287 mg/(L×min))约为同条件下P25(0.01342 mg/(L×min))的6倍.同时,TiO_2-180°C催化剂在不同单色光下的光催化活性与它对单色光的光响应大致相符.循环降解实验证明TiO_2-180°C催化剂具有很好的稳定性.光猝灭实验表明,?OH在光催化降解过程占主导作用,而TiO_2-180°C样品表面含有较多的–OH,有利于?OH的产生,乃至光催化反应.研究表明,晶格内高浓度的氧空位导致的强可见光响应,得益于低温制备条件而保留了大量–OH/H_2O的纳米粒子表面以及更大的比表面积,共同促成了TiO_2-180°C优越的光催化活性.所制备的棕色纳米TiO_2经过进一步修饰后有望运用于实际应用中.     

聚吡咯、聚甲基吡咯电子能带结构的计算

采用LACO SCFabinito晶体轨道方法计算了聚吡咯、β取代甲基聚吡咯平面构型及它们扭曲 30°、6 0°、90°时的导带和价带结构 ,对扭曲角度同能隙、离子化势、最高占据带之间的关系进行了分析 ,较好地解释了结果 .     

电子背散射衍射法研究马氏珠母贝珍珠层中文石择优取向

贝壳珍珠层中的文石相对于在自然环境中生长的文石来说具有更优异的力学性能,这种力学性能取决于其独特的晶体排布方式。通过电子背散射衍射(EBSD)技术获得了马氏珠母贝中不同文石的结晶学取向信息,结果表明珍珠层中文石晶体的c轴均垂直于珍珠层层面,而a、b轴在平行珍珠层方向上具有两级取向畴结构:在初级畴结构内,相邻畴绕c轴偏转,导致不同畴之间a轴或b轴的取向差约64°。在次级畴结构内,文石板片围绕c轴偏转,导致不同畴之间a轴或b轴取向差在10°或20°左右。这种畴结构为我们认识珍珠层中文石的生长机理提供了有益线索。     

Influence of the angle between two crown ether moieties on supramolecular copolymerization of bis(crown ether)s and bisparaquat homoditopic monomers

Bis(crown ether) homoditopic monomers containing two bis(p-phenylene)-34-crown-10 moieties with different angles(180° for monomer 3,120°for monomer 4,and 60°for monomer 5) and a complementary bisparaquat homoditopic monomer(7) were designed and synthesized.The three bis(crown ether) monomers could organize into linear supramolecular polymers in concentrated solutions in CHCl3/CH3CN with the bisparaquat monomer 7,as demonstrated by 1 H NMR and viscosity studies. The pseudorotaxanes or supramolecular polymers...     

高温快速合成纳米MAZ分子筛

作为重要的离子交换、吸附、分离与催化材料,沸石分子筛广泛地应用于不同的工业过程中.MAZ(Omega)分子筛的合成往往需要较长的晶化时间,从而限制了它的广泛应用.根据阿伦尼乌斯公式可以判断,提高MAZ沸石分子筛的晶化温度可以大幅度地缩短晶化时间,达到快速合成沸石分子筛的目的.本文将分子筛晶化温度从100提高到180°C,在3.6 h制得MAZ沸石分子筛.X射线粉末衍射测试(XRD)表明,所合成的样品是具有高纯度和高结晶度的MAZ沸石分子筛.从扫描电镜(SEM)图片可以看出, MAZ-180 (MAZ-T, T代表晶化温度)是由宽200 nm、长2–3μm的纳米棒状组成.为了探究这些纳米棒状构成的形貌是否稳定,将样品进行了超声处理.XRD和SEM结果表明,经过处理的样品仍然具有原来的结晶度与形貌,确认了它们的结构稳定性.高分辨透射图进一步确认了MAZ-180样品的规整微孔结构.热重分析显示该样品在500–700°C出现两个放热峰,这归因于有机模板的燃烧.氮气吸附测试表明, MAZ-180的比表面积为187m~2/g,甚至超过低温合成MAZ的表面积,与它的高结晶度相一致.将氢型MAZ-180(H-MAZ-180)和MAZ-100(H-MAZ-100)分子筛浸渍0.5%Pt后,用于正十二烷的加氢异构反应,发现Pt/H-MAZ-180催化剂总是具有更高的异构产物选择性和更低的裂化产物选择性.这可能是因为MAZ-180样品具有更小的尺寸,更有利于反应中的扩散.MAZ-180沸石分子筛可快速合成的特点及其所表现出的优异的催化性能使其在未来广泛应用于催化反应中成为可能.     

具有然陷模的氧化铝光子晶体的光学传感性能

采用在周期性氧化电压信号中插入恒压波形的方法成功制备了具有缺陷模的一维氧化铝光子晶体. 这种晶体的透射光谱研究表明,缺陷的厚度对缺陷模的透过率具有显著影响,当缺陷厚度在180 nm时,光子禁带内部出现透过率为55%、半峰宽约为18 nm的缺陷模. 该缺陷模能够对进入到氧化铝孔道内部的液体物质做出响应,其位置与液体的折射率线性相关.     

硫醇对炔属化合物的加成反应的研究 Ⅰ.苯硫酚与苯乙炔的加成反应

苯硫酚与苯乙炔在0°和室温下进行加成反应时生成反式β-苯硫基苯乙烯,在-20°或-40°时加成则生成约等量的反式和顺式β-苯硫基苯乙烯.顺式β-苯硫基苯乙烯在加热至180°时变化为其反式异构体.苯硫酚的钠盐与苯乙炔在无水乙醇中起加成时则只生成顺式β-苯硫基苯乙烯. 苯硫酚对苯乙炔的直接加成可能按自由基链式历程进行,加成反应的立体化学与中间生成的自由基C_6H_5C=CHSC_6H_5在反应温度下的稳定性有关,在低温下反式加成较为有利. 文中述及顺式和反式β-苯硫基苯乙烯及其砜的紫外吸收光谱.     

不同模拟环境中胆红素钙的成核与晶体生长

用FT-IR、XRD、SEM和TGA等研究了4种不同模拟体系中胆红素钙晶体的成核与生长情况,考察了生物大分子和CO2对胆红素钙的成核与结晶等的影响。结果表明,水溶液中胆红素钙很难结晶形成晶体结构,但在暴露大气中的葡聚糖水溶液模拟体系中则形成了含质量分数为12%碳酸钙的胆红素钙/碳酸钙复合晶体。在此过程中,CO2气体促进了碳酸钙晶体的形成,碳酸钙晶体不同晶面的选择吸附性能和葡聚糖分子的含O功能团为胆红素钙的成核提供了有效位点和定向调控作用,共同模板作用诱导调控了在2θ为19.8°、21.8°有强衍射峰的胆红素钙晶体的形成。晶态胆红素钙具有明显的热分解温度,而处于非晶态时则无此种现象。     

热处理对聚四氟乙烯-聚苯胺系列导电复合膜性能的影响

对电化学制备的聚四氟乙烯-聚苯胺系列导电复合膜进行热处理,采用热重、红外和X衍射等手段研究了在空气和真空氛围中,热处理对复合膜的电导率及力学性能的影响。热分析结果表明：此系列复合膜在100～180°C失重较少,在此温度区间内对聚苯胺-聚四氟乙烯复合膜热处理,其电导率在空气和真空氛围中均随热处理温度升高而下降,聚苯胺-聚四氟乙烯-银复合膜在空气氛围中的电导率也随热处理温度升高而下降,两种复合膜的强度不变,断裂伸长率降低;聚苯胺-聚四氟乙烯-银复合膜在真空氛围中经120°C热处理后电导率提高最显著,力学强度也有所提高,但断裂伸长率降低。X衍射研究表明复合膜经180°C热处理后结晶度降低。红外分析结果表明聚苯胺-聚四氟乙烯复合膜经180°C热处理,发生了磺基水杨酸的脱掺杂和聚苯胺的结构热氧化、分子链的断裂和交联,复合膜电导率降低。     

{[Eu(2,5-PDA)(OAc)(H2O)]·1.5H2O}n稀土配合物的晶体结构及荧光性质

在水热条件下合成了一个新的2,5-吡啶二羧酸的稀土配合物{[Eu(2,5-PDA)(Oac)(H2O)]·1.5H2O}n.通过元素分析和X射线单晶衍射确定了该化合物的组成和晶体结构, 并对荧光性质进行了表征.该晶体属单斜晶系, P21/n空间群, 晶胞参数a=0.935 01(15) nm, b=0.834 77(13) nm, c=1.677 9(3) nm, β=106.18°;V=1.257 8(3) nm3, Z=4, 最后的一致性因子[I＞2σ(I)]: R1=0.024 3, Wr2=0.060 5.标题化合物中醋酸根的羧基以螯合-桥联三齿的方式将2个不对称单元中的铕离子连接起来形成二核单元, 2,5-PDA配体分别从与醋酸根和铕离子的平面成88°和56°夹角的方向将二核单元连接起来, 从而形成了由配位键构筑的三维结构, 未配位水分子通过氢键存在于晶体中.     

Low temperature sintering study of nanosized Mn–Zn ferrites synthesized by sol–gel auto combustion process

The objective of present research was to sinter nanosized Mn–Zn ferrites (MZF) at low temperature (≤1,000 °C) by avoiding the formation of nonmagnetic phase (hematite). For this purpose, MZF powder was synthesized by sol–gel auto combustion process at 220 °C and further calcined at 450 °C. In calcined powder, single phase (spinel) was confirmed by X-ray diffraction analysis. Pellets were pressed, having 43% of the theoretical density and showing 47 emu gm⁻¹ saturation magnetization (M _s). Various combinations of heating rate, dwelling time and gaseous environment were employed to meet optimum sintering conditions at low temperature (≤1,000 °C). It was observed that sintering under air or N₂ alone had failed to prevent the formation of nonmagnetic (hematite) phase. However, hematite phase can be suppressed by retaining the green compacts at 1,000 °C for 180 min in air then further kept for 120 min in nitrogen. Under these conditions, spinel phase (comprising of nano crystallites), 90% of theoretical density and 102 emu gm⁻¹ of saturation magnetization has been achieved.     

The Thermal Expansion of Wood Cellulose Crystals

We have investigated tension wood cellulose obtained from Populus maximowiczii using X-ray diffraction at temperatures from room temperature to 250 °C. Three equatorial and one meridional d-spacings showed a gradual linear increase with increasing temperature. For temperatures above 180 °C, however, the equatorial d-spacing increased dramatically. Thus, the linear and volume thermal expansion coefficients (TECs) below 180 °C were determined from the d-spacings. The linear TECs of the a-, b-, and c-axes were: α _a = 13.6 × 10⁻⁵ °C⁻¹, α _b = −3.0× 10⁻⁵ °C⁻¹, and α _c =0.6× 10⁻⁵ °C⁻¹, respectively, and the volume TEC was β = 11.1× 10⁻⁵ °C⁻¹. The anisotropic thermal expansion in the three coordinate directions was closely related to the crystal structure of the wood cellulose, and it governed the macroscopic thermal behavior of solid wood.     

TiO2 nanotube array film prepared by anodization as anode material for lithium ion batteries

TiO₂ array film fabricated by potentiostatic anodization of titanium is characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and charge–discharge measurements. The XRD results indicated that the TiO₂ array is amorphous, and after calcination at 500 °C, it has the anatase form. The pore size and wall thickness of TiO₂ nanotube arrays synthesized at different anodization voltages are highly dependent on the applied voltage. The electrochemical performance of the prepared TiO₂ nanotube array as an electrode material for lithium batteries was evaluated by galvanostatic charge–discharge measurement. The sample prepared at 20 V shows good cyclability but low discharge capacity of 180 mA h cm⁻³, while the sample prepared at 80 V has the highest discharge capacity of 340 mA h cm⁻³.     

Design and fabrication of an ultraviolet photoelectron spectrometer for the study of free molecules

An ultraviolet photoelectron spectrometer for the study of free atoms and molecules has been designed and fabricated with indigeneous components. The spectrometer consists of a 100 mA HeI discharge lamp, 180° hemispherical electron energy analyser (127 mm mean dia) and electron multiplier ratemeter electron detection systems. The resolution of the spectrometer is 90 meV/and the intensity of N₂ (5σ) band is 10⁵ c/sec. The sample inlet and the collision chamber can be heated to 500 K so that solids of low vapour pressure can be studied. Typical spectra of molecules recorded with the instrument are shown. Contribution No. 373 from the Solid State and Structural Chemistry Unit.     

Electrochemical capacitance of nickel oxide nanotubes synthesized in anodic aluminum oxide templates

Nickel oxide (NiO) nanotubes for supercapacitors were synthesized by chemically depositing nickel hydroxide in anodic aluminum oxide templates and thermally annealing at 360 °C. The synthesized nanotubes have been characterized by scanning electron microscopy, transmission electron microscopy, and X-ray diffraction. The capacitive behavior of the NiO nanotubes was investigated by cyclic voltammetry, galvanostatic charge–discharge experiment, and electrochemical impedance spectroscopy in 6 M KOH. The electrochemical data demonstrate that the NiO nanotubes display good capacitive behavior with a specific capacitance of 266 F g⁻¹ at a current density of 0.1 A g⁻¹ and excellent specific capacitance retention of ca. 93% after 1,000 continuous charge–discharge cycles, indicating that the NiO nanotubes can become promising electroactive materials for supercapacitor.     

Synthesis of high surface area transitional alumina from Al(OPh)<Subscript>3</Subscript>

Al(OPh)₃ involving sterically hindered phenyl groups on ultrasonic assisted micro hydrolysis yielded a mixture of boehmite and bayerite as deduced from the FTIR and powder X-ray diffraction pattern. In the thermogravimetric trace, the complete removal of decomposable moieties of the hydrolyzed gel occurred around 530 °C. Calcining the gel at temperatures 600, 700, 800 and 900 °C showed crystalline tetragonal δ-Al₂O₃ to be the product at 900 °C as deduced from FTIR, ²⁷Al NMR and PXRD techniques. δ-Al₂O₃ showed a surface area of 135 m²/g with rectangular bar like morphology with the sizes below 50 nm in the TEM images.     

Complex Formation Between Erythritol and 4-hexylresorcinol

The interaction between erythritol and 4-hexylresorcinol during heating was investigated by thermal analysis, powder X-ray diffractometry and infrared spectroscopy. A phase diagram was constructed by measuring the thermal behaviour of various resolidified physical mixtures of erythritol and 4-hexylresorcinol. The phase diagram revealed complex formation between erythritol and 4-hexylresorcinol with incongruent melting at 84°C; the stoichiometry was a molar raio of 1:2 erythritol:4-hexylresorcinol. The complex gave diffraction peaks at 2θ=5.6° and 11.2° in the X-ray powder diffraction pattern. In the infrared spectrum, a new peak due to the complex was observed at 3504 cm^–1. The complex prepared by grinding and evaporation had the same molecular arrangement as the complex prepared by sealed heating. This revised version was published online in July 2006 with corrections to the Cover Date.     

Influence of coagulation temperature on pore size and properties of cellulose membranes prepared from NaOH–urea aqueous solution

The morphology and structure of the regenerated cellulose membranes prepared from its NaOH–urea aqueous solution by coagulating with 5 wt% H₂SO₄–10 wt% Na₂SO₄ aqueous solution with different temperatures and times were investigated. The pore size, water permeability and physical properties of the membranes were measured with scanning electron micrograph (SEM), wide X-ray diffraction (WXRD), Fourier transfer infrared spectroscopy (FTIR), flow rate method, and tensile testing. The SEM observation revealed that the structure and pore size of the membranes changed drastically as a function of the coagulation temperature. The membranes coagulated at lower temperatures tended to form the relatively small pore size than those at higher temperatures. On the contrary, the membranes coagulated at different times exhibited similar pore size. Interestingly, the mean pore size and water permeability of the membranes increased from 110 nm with standard deviation (SD) of 25 nm and 12 ml h⁻¹ m⁻² mmHg⁻¹ respectively to 1,230 nm with SD of 180 nm and 43 ml h⁻¹ m⁻² mmHg⁻¹ with an increase in coagulation temperature from 10 to 60°C. However, the membranes regenerated below 20°C exhibited the dense structure as well as good tensile strength and elongation at break. The result from FTIR and ultraviolet-visible (UV-vis) spectroscopy indicated that the relatively strong intermolecular hydrogen bonds exist in the cellulose membranes prepared at lower coagulation temperatures. This work provided a promising way to prepare cellulose materials with different pore sizes and physical properties by controlling the coagulation temperature.     

Structural and optical characterization of Zn doped TiO<Subscript>2</Subscript> nanoparticles prepared by sol–gel method

Undoped and zinc-doped TiO₂ nanoparticles (Ti_1−xZn_xO₂ where x = 0.00–0.10) were synthesized by a sol–gel method. The synthesized products were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM) and UV–VIS spectrometer. XRD pattern confirmed the tetragonal structure of synthesized samples. Average grain size was determined from X-ray line broadening using the Debye–Scherrer relation. The crystallite size was varied from 10 to 40 nm as the calcination temperature was increased from 350 to 800 °C. The incorporation of 3–5 mol% Zn²⁺ in place of the Ti⁴⁺ provoked a slight decrease in the size of nanocrystals as compared to undoped TiO₂. The SEM and TEM micrographs revealed the agglomerated spherical-like morphology with a diameter of about 10–30 nm and length of several nanometers, which is in agreement with XRD results. Optical absorption measurements indicated a blue shift in the absorption band edge upon 3–5 mol% zinc doping. Direct allowed band gap of undoped and Zn-doped TiO₂ nanoparticles measured by UV–VIS spectrometer were 2.95 and 3.00 eV at 550 °C, respectively.     

Deposition of Diamond-like Carbon Films using Graphite Sputtering in Neon Dense Plasma

This paper reports the deposition of diamond-like carbon (DLC) films on Si <100>, using a low energy (1.45 kJ) dense plasma focus assisted sputtering of graphite insert at the tip of the tapered anode. The substrates are placed in front of the anode at different axial and angular positions and are exposed to multiple focus shots. The information regarding the DLC structure is acquired by using Raman spectroscopy. The spectra are characterized by two broad bands known as “G-band” and “D-band”. The results point towards the formation of DLC films with both sp³ (diamond like) and sp² (graphite like) domains. In X-ray diffraction (XRD) pattern, no additional peak is observed except a peak at 2θ = 69° which corresponds to the silicon (Si) substrate. The intensity of Si peak is reduced after treatment indicating the deposition of amorphous carbon. Scanning electron microscopy (SEM) results demonstrate that the smoothness of the film increases with increasing the substrate angular positions with respect to the anode axis. Energy dispersive X-ray (EDX) analysis reveals that the films deposited at lower axial and angular positions are thicker which is complemented by the cross-sectional views of the films.