TiO2/P3HT纳米复合材料光催化降解甲基橙的动力学研究

用化学氧化聚合法制备了导电聚合物聚3-己基噻吩(P3HT).用聚3-己基噻吩改性纳米二氧化钛,合成TiO2/P3HT纳米复合微粒.对其光催化降解甲基橙的反应动力学进行了分析,测定了反应的表观活化能.结果表明,纯纳米TiO2和TiO2/P3HT纳米复合微粒光催化降解甲基橙的反应均为一级反应;纳米TiO2经聚3-己基噻吩(P3HT)修饰后在可见光下的光催化活性得到提高,且提高降解温度有利于提高甲基橙的降解率,纳米TiO2经P3HT修饰后降解甲基橙的表观活化能由23.44 KJ/mol下降到19.36 kJ/mol.     

Ce掺杂TiO2纳米复合薄膜的制备及光催化活性

采用溶胶-凝胶技术,以CTAB作为模板剂,提拉法镀膜制备了Ce掺杂TiO2纳米复合薄膜,利用XRD、N2吸附-脱附、UV-Vis、SEM及XPS对样品进行了表征.结果表明,铈离子以Ce4+和Ce3+两种形式存在于体系中,而CTAB有效抑制了TiO2晶粒的长大和二氧化钛晶相的转变,加入CTAB的Ce掺杂TiO2纳米复合薄膜的吸收带边较纯的TiO2发生了红移.光催化活性表明,这种处理方式明显提高了TiO2光催化活性.在紫外光照120 min下,CRAB(1.0;)/Ce(1.0;)-TiO2纳米复合薄膜的光催化活性最佳,对甲基橙降解率达到95.3;.     

不同结构TiO2-ZnO异质复合膜光催化活性的研究

采用多靶磁控溅射离子镀技术制备TiO2-ZnO和(TiO2-ZnO)/TiO2两种不同结构的复合薄膜.研究薄膜在pH值分别为5、7和9时对甲基橙的降解,并结合薄膜光催化实验后的透光率、表面形貌和电化学腐蚀性能,探讨TiO2顶层对TiO2-ZnO异质复合薄膜光催化活性的影响.结果表明:两种薄膜的光催化活性均在酸性中最好,依次为碱性和中性,但(TiO2-ZnO)/TiO2薄膜的降解率和降解速率始终高于TiO2-ZnO薄膜,且酸、碱性环境下更明显.光催化实验后,(TiO2-ZnO)/TiO2薄膜表面无变化,TiO2-ZnO薄膜出现明显的腐蚀、溶解形貌,且薄膜透光率在不同环境中的变化相差4～5倍.在不同pH值的3.5wt; NaCl溶液中,(TiO2-ZnO)/TiO2复合薄膜的腐蚀电位和腐蚀电流均优于TiO2-ZnO薄膜.由于TiO2顶层良好的耐酸碱腐蚀性能,(TiO2-ZnO)/TiO2薄膜在pH值较大范围的溶液中表现出更好的光催化活性.     

铋铁共掺纳米TiO2复合薄膜的制备及光催化性能

本文以钛酸丁酯、硝酸铋、硝酸铁为主要原料,采用溶胶-凝胶法制备了铋铁共掺的纳米TiO2复合薄膜.用XRD、UV-VIS、SEM及降解率等方法对样品进行了表征.以甲基橙为降解物,考察Bi3+和Fe3+掺杂对TiO2复合薄膜催化剂的光催化活性影响及其机理研究.结果表明Bia+和F3+掺杂后,纳米TiO2复合薄膜光催化活性有了明显的提高.     

PAN/TiO2复合微粒在可见光下的光催化性能研究

采用水相沉淀法合成聚丙烯腈(PAN),并通过化学吸附法将聚丙烯腈附着在纳米TiO2上,制备得到PAN/TiO2复合微粒.通过在可见光下降解罗丹明B,考察了制备过程中复合比例、热处理时间与温度、分子量对光催化活性的影响.光催化活性较高的制备条件是:AN/TiO2摩尔比为1∶120,热处理时间为30 min,热处理温度为270℃.通过在可见光下降解甲基橙、孔雀石绿等,表明PAN/TiO2复合微粒降解污染物具有普适性.     

磁控溅射（TiO2-ZnO）/TiO2梯度复合薄膜的制备及光致亲水性研究

采用磁控溅射离子镀设备制备了(TiO2-ZnO)/TiO2梯度复合薄膜,通过TEM、AFM、Raman、XPS分析了复合薄膜的结构、形貌和表面羟基含量,以甲基橙作为有机降解物,研究了(TiO2-ZnO)/TiO2梯度复合薄膜与普通TiO2-ZnO复合薄膜和TiO2薄膜在光催化性能和光致亲水性能上的差异。结果表明:(TiO2-ZnO)/TiO2梯度复合薄膜具有以主体为TiO2-ZnO层、顶层为TiO2的梯度结构,且薄膜表面致密、粒径均匀(10～14 nm),光催化性和亲水性均优于普通TiO2-ZnO复合薄膜和TiO2薄膜,且其光波响应范围红移至450 nm、表面羟基含量高达12.53%,同时梯度复合薄膜的抗光腐蚀性能良好,4 h以后其润湿角仍保持不变。     

PAN/TiO2复合微粒的制备与表征

采用沉淀法合成聚丙烯腈(PAN),并通过化学吸附法制备得到PAN/TiO2纳米复合微粒.采用透射电镜(TEM)、X射线衍射(XRD)、红外光谱(IR)、X射线光电子能谱(XPS)、紫外可见漫反射吸收光谱(DRS)等方法对复合微粒的结构和性能进行了分析表征.结果表明,复合微粒的形貌、晶型和粒径和纯二氧化钛比较基本没有发生改变;PAN/TiO2纳米复合微粒在可见光区的光吸收能力增强.对甲基橙降解实验研究结果表明,所制备的PAN/TiO2纳米复合微粒具有良好的光催化降解性能,其14 h对甲基橙的降解去除率可以达到86.5;.     

Ce/TiO2纳米管阵列的制备及光催化性能的研究

采用电化学阳极氧化法在钛表面制备TiO2纳米管阵列,并用稀土铈对其修饰改性.以甲基橙为目标降解物,考察了Ce3+溶液浓度、甲基橙溶液的初始浓度和初始pH对铈改性的TiO2纳米管光催化活性的影响.结果表明:Ce3+溶液的浓度存在一个最佳值,当Ce3+溶液浓度为0.01 mol/L,在10 mg/L,pH =3的甲基橙溶液中光催化活性最好.光照4h后,甲基橙的降解率达83％.     

MoO3/TiO2复合催化剂的制备及光活性

以商业锐钛矿TiO2和钼酸铵水溶液作为前驱体,利用浸渍-焙烧的方法制备了MoO3与TiO2不同质量比率的MoO3/TiO2复合光催化剂.采用X射线衍射、高分辨透射电镜和紫外-可见漫反射对其进行了表征.以甲基橙为光催化反应的模型化合物,评价了其紫外光催化活性和MoO3/TiO2复合光催化剂的紫外产氢活性.通过添加各种自由基清除剂研究了甲基橙在光催化反应过程中的活性物种.结果表明:与纯的MoO3和TiO2相比,20; MoOJTiO2光催化剂在400 ～ 700 nm区域具有更强的光吸收性能并且吸收带边向长波方向移动.在所有MoO3/TiO2样品中,20; MoO3/TiO2光催化剂具有最高的紫外光活性.·OH,h+,·O2-和H2O2,特别是h+,共同支配了甲基橙的光催化降解过程.     

爆轰法合成超小TiO2的光催化性能分析

颗粒尺寸是影响TiO2光催化活性的重要因素,颗粒越小其光催化效率越高.在密闭的反应釜内引爆用含钛前驱体、硝酸铵、黑索金与一定量的聚苯乙烯小球制备的浆状混合炸药制备了超小的TiO2纳米颗粒.研究了炸药配比对TiO2的形貌、分散性、颗粒尺寸的影响,并通过降解甲基橙溶液表征超小TiO2的光催化性能.结果发现:制备的TiO2由金红石相与锐钛矿相组成,大部分颗粒呈球形或不规则四边形,尺寸在10nm左右,少量颗粒尺寸大于20nm,结晶度较好.炸药配比对TiO2的结晶度、颗粒大小、分散性等有较大影响.TiO2的禁带宽度在2.8eV左右,低于锐钛矿相与金红石相的禁带宽度,能够提高太阳光的利用率.爆轰制备的超小TiO2催化降解甲基橙溶液50min时,甲基橙的降解率为30;,明显高于爆轰法制备的颗粒较大的TiO2与铜粒子掺杂的纳米TiO2的光催化速率,光催化性能得到明显提高.     

A review of measurement of thermophysical properties of silicon melt

Measurements of thermophysical properties of Si melt and supplementary study of X-ray scattering/diffraction by the authors' group were reviewed. The values obtained differed variously from those of literature. Density was 2–3% larger, surface tension 20–30% smaller, viscosity up to 40% larger, electrical conductivity 8% smaller, spectral emissivity more or less in good agreement with literature values, and thermal diffusivity a few percent larger. An anomalous density jump was found near the melting point. Surface tension and viscosity also showed anomaly. A strange time-dependent change of density was observed over 3 h after melting. X-ray analyses suggested a slight change in local atom ordering, but showed no sign of cluster formation. An addition of 0.1 at% gallium caused the density jump to disappear, while that of boron caused no change. An EXAFS study of the former melt indicated a strong interaction between Ga and Si atoms as if molecules of GaSi₃ existed. The implications of the measured properties are a possibility of soft-turbulence in an Si melt in a relatively large crucible, a more complicated manner of intake of oxygen depleted molten Si from the free surface region to underneath the growing crystal, and a relaxation of the melt after melting arising from trapped gas species.     

Mesomorphism Dependence on the Position of Substitution of a Pair of Esters

A novel homologous series of ethylene derivatives of thermotropic liquid crystals has been synthesized. The methoxy to octyloxy derivatives are nematogenic, the decyloxy to tetradecyloxy derivatives are smectogenic, in addition to nematogenic, and the hexadecyloxy homologue is smectogenic only. All the members of the series are enantiotropically mesogenic. Thermotropic behavior was determined by an optical polarizing microscope equipped with a heating stage and Differential Scanning Calorimetry (DSC) study. Analytical and spectral data confirm the molecular structures of homologues (infrared, nuclear magnetic resonance, mass spectra, X-ray, and DSC data). Textures of the nematic phase are threaded or Schlieren and that of smectic phase are focal conic fan-shaped of smectic A or C. Transition curves of the phase diagram behave in a normal manner except one or two deviations from the normal trend. The mesophase range (Sm+N) varies from 3°C to 44°C. The average thermal stability for smectic is 93°C and that for nematic 117.4°C. The LC behavior of the novel series is compared with a structurally similar known series.     

原位氮化法制备TiN纳米粉体

用溶胶凝胶法合成的纳米TiO2粉体作为原料,将该粉体在氨气中进行原位氮化制备了TiN纳米粉体.用XRD,TEM,化学分析等手段对合成的TiN纳米粉体的物相组成、形貌、成分进行了分析.实验分析表明:在1000℃和1100℃下分别氮化5h,可以制备粒径大约为40nm和80nm的TiN粉体,其TiN的含量分别为95.40;和98.37;;而在1000℃条件下氮化时间减少到2h时,TiN的含量仅为58.36;.氮化温度和氮化时间是合成纳米TiN的重要因素,提高合成温度和延长氮化时间均可形成纯度较高的TiN纳米粉体,但延长氮化时间更有利于获得粒径小的氮化钛粉体.     

电子显微分析在表征纳米晶体化学组分中的应用

纳米材料的化学组分及含量影响其光、电、声、热、磁等物理性能,电子显微分析是表征纳米晶体化学组分的重要方法之一.本文综述了X-射线能谱(EDS)、X-射线波谱(WDS)、电子能量损失谱(EELS)和选区电子衍射(SAED)等现代电子显微分析技术在表征纳米晶体化学组分、形貌、尺寸和结构等方面的应用及其研究进展,并比较了这些分析方法存在的差异,提出了其应用中存在的不足及今后的研发方向.     

On the influence of structural features of DNA on the possibility of metabolic transfer of electrons

Abstract

A fragment of a DNA molecule is considered as one of the channels of metabolic electron transfer. The heterogeneity of the complementary chains is effectively taken into account. This made it possible to find the speed of the electron injected into the DNA conduction band and the current density that it creates. Estimates of electron mobility in nucleic acid chains are made. They were an order of magnitude smaller than that of typical semiconductors. For the specific conductivity of nucleic acid chains, estimates provide a conductivity of one to two orders of magnitude lower than in graphite.     

Effect of alumina on enthalpy of mixing of mixed alkali silicate glasses

The enthalpy of mixing of mixed alkali (Na₂O and K₂O) silicate glasses containing various concentrations of alumina was determined using an ion-exchange equilibrium method. For glasses with a constant alkali concentration, the enthalpy of mixing was found to become less negative with alumina addition. Consistent with our previous results on the enthalpy of mixing of alumina-free mixed alkali silicate glasses, the magnitude of enthalpy of mixing exhibited a good correlation with the molar volume mismatch of the corresponding two single alkali glasses as well as with the extent of conductivity mixed alkali effect, e.g. excess activation energy of conductivity, ΔE. The reduction of the magnitude of the enthalpy of mixing with alumina addition can be attributed to the reduction of non-bridging oxygen and ionic field strength. Combining the present results with results obtained earlier, the magnitude of the enthalpy of mixing for all mixed alkali (Na₂O and K₂O) silicate glasses with and without alumina was expressed by a simple function of a modified Tobolsky parameter, which takes into account the alkali concentration and the difference in cation-to-effective anion distances. The enthalpy of mixing data of the mixed alkali glasses was then compared with reported experimental data on the conductivity of mixed alkali aluminosilicate glasses. What appears to be conflicting experimental data can be understood in terms of the magnitude of the enthalpy of mixing and we can conclude that the mixed alkali effect is closely correlated with the negative enthalpy of mixing.     

Ni-ZrO2纳米复合电铸层的制备及纳米颗粒分布均匀性研究

研究了在复合电铸过程中,当其它工艺参数一定时,复合电铸层的沉积速率及其厚度随时间的变化趋势, 以及复合电铸层表面微观形貌随电沉积时间的变化趋势.测定了复合电铸层的组织成分,并就纳米颗粒在复合电铸层表面和横截面上分布的均匀性进行了评价.结果表明,复合电铸层表面平整,组织均匀致密,其组成主要是镍和所复合的纳米颗粒,纳米颗粒较为均匀地分散在复合电铸层中.     

Evolution of the Defect Structure of Zinc-Oxide as a Consequence of Tribophysical Activation

Zinc-oxide powder was tribophysically activated in a high-energy vibro mill in a continual regime in air for 3, 30 and 300 minutes with the purpose of modifying the powders physico-chemical properties. By analyzing of data obtained by X-ray powder diffraction, electron diffraction and transmission electron microscopy, the values of distances between corresponding crystallographic planes, average domain sizes of coherent scattering, i.e. crystallites, width of diffraction lines due to the existence of microstrains, and microstrain values, minimal dislocation densities, dislocation density due to microstrain and real dislocation density, and also average distances between dislocations were determined. The dependence of these values on the activation time was established, which enabled analysis of the evolution of the defect structure of zinc-oxide powders during tribophysical activation by grinding in the described regime.     

Some peculiarities of spectral proprieties of leukocytes

This article presents the results of spectral investigations of white blood human cells including absorption, fluorescence and phosphorescence (using low-temperature measurements). For this research, the main optical centres were identified and local distribution of emitting and absorbing centres into white blood human cells was determined. In addition, the spectra of normal and pathological (B-cell chronic lymphocytic leukemia, B-CLL) cells were compared.     

立方晶系晶体本征铁弹相变序参量的选取

在本征铁弹相变的软模理论的基础上,依据弹性本构关系和居里原理,给出了立方晶系晶体所有可能的自发应变的种类,研究了立方晶系晶体本征铁弹相变序参量的选取问题.以Th群和Oh群为例,阐明了不同类的序参量导致晶体对称性变化相同的的原因,提出了该情况下序参量选取的“就少不就多”的原则.得到了发生本征铁弹相变时所有可能的序参量及晶体的对称性的变化.