纳米级CdS粒子尺寸量子化的化学效应研究

研究了无机半导体硫化镉超微团簇粒子界面光反应行为,结果表明,纳米粒子的尺寸量子化效应不仅体现在其光物理特性上,而且也体现在其所引发的表面光催化反应行为中,即随着粒子尺寸的变化,被吸附于粒子界面的化合物的光反应方向和机理或反应强度也随之有所变化.这是由于粒子的氧化还原电位也随着粒子尺寸而改变所致.这种效应对于控制界面反应的机理及提高其选择性有重要意义.     

纳米粒子尺寸效应引起的内层电子结合能位移

用XPS测定了氩离子溅射前后的Pt-PVP纳米粒子和TiO2、ZnO及SiO2纳米粒子的内层电子结合能, 并与其对应的体材料进行了比较. 结果表明, Ar+溅射前Pt-PVP的Pt 4f结合能比体材料Pt的稍低, 但Ar+溅射后由于PVP包覆层被除去, 裸露的Pt 纳米粒子的结合能明显高于Pt体材料. 与非纳米氧化物比较, 纳米氧化物TiO2、ZnO 和SiO2的内层电子结合能也向高结合能方向位移, 其位移大小的顺序为TiO2相似文献   

纳米晶钛酸钡的Sol-gel法制备及其尺寸效应

采用sol-gel法制备了不同粒径的钛酸钡（BT）纳米晶粉. XRD、Raman光谱和DSC测试结果显示,随着退火温度的升高，晶粒长大，晶胞的a轴逐渐减小， c轴逐渐增大.粒径在54 nm左右时，钛酸钡由顺电立方相向铁电四方相结构转变，在立方-四方相变过程中，晶胞略微膨胀.随着粒径的减小，正交-四方相变温度升高，四方-立方相变温度降低， Raman谱峰降低和宽化，粒径为38 nm左右时四方相的特征峰消失.     

DBC—AsA吸光光度法测定锆酸钙烧结物中游离氧化锆

二溴羧基偶氮胂(DBC-AsA)是一种新显色剂,已用于铈的测定.本文研究了二溴羧基偶氮胂与锆的显色反应,并用于锆酸钙烧结物中微量锆的测定,结果令人满意.1试验部分1.1主要试剂锆标准溶液0.1mg·ml~(-1),准确称取二氧化锆0.1351g于瓷坩埚中,加焦硫酸钾4.0g,于750℃熔融10～15min,用盐酸(2mol·L~(-1))100ml浸出熔块,加热至完全溶解,移入1000ml量瓶中,以盐酸(2mol·L~(-1))稀释至刻度,摇匀.用时稀释至10μg·ml~(-1).     

纳米TiO2微胶粒的光化应制备机理及量子尺寸效应

研究了由水相Ｔｉ＾３＋制备纳米极Ｔｉ＾Ｏ２微胶粒的光化反应机理及反应动力学，给出反应速率方程。讨论了ＴｉＯ２微胶粒的量子尺寸效应，经电镜测试ＴｉＯ２粒子的直径为１５－２５ｎｍ。反应过程中由气相色谱仪监测生成物Ｈ２。     

中药玄精石的物相与结构分析

中药玄精石的物相与结构分析;中药; 玄精石; X射线衍射; 晶粒尺寸; 微量元素; 热分析     

Q态硫化镉纳米晶的制备、形态、量子尺寸效应与光催化性能

分别引入辛基硫醇作配体, 十六烷基三甲基溴化铵(或四丁基溴化铵)作有机正离子合成CdS纳米簇合物. 采用后沉淀分离技术, 分别制备得到粒度分布窄、粒径2~5 nm的Q态CdS纳米晶粒. 用紫外吸收光谱、透射电子显微镜、小角X射线衍射来测定粒径的大小. 在紫外光谱、荧光光谱和X射线衍射上, 表现出明显的量子尺寸效应. 当粒径大到一定程度(大于10 nm)时, 量子尺寸效应就不明显. 用ESR研究Q态纳米粒子的光催化性能, 结果表明加入纳米硫化镉颗粒可明显促使甲醇、乙醇发生光催化反应, 释放出CH3-·CHOH(对乙醇体系)或·CH2OH(对甲醇体系), 在有机合成上有着重要的应用价值.     

纳米二氧化钛的量子尺寸效应及掺杂氧化锡对其光吸收的影响

采用溶胶-凝胶法制备了量子尺寸的纳米氧化钛和锡掺杂的纳米氧化钛,经过不同温度的热处理得到不同尺寸的粉末样品.通过X射线衍射(XRD)和电子衍射(ED) 表征了不同样品的物相组成和粒径(3～12 nm),通过反射谱(RS)深入研究了纳米氧化钛的量子尺寸效应及掺杂氧化锡对于纳米氧化钛光吸收性质的影响.实验结果表明纳米氧化钛有明显的光吸收量子尺寸效应,掺杂氧化锡促进了二氧化钛的锐钛矿向金红石相的转变,降低了相变起始温度.由于相变和尺寸变化两方面相反的作用,掺杂氧化锡对于二氧化钛光吸收边的位移影响不大.     

CeO2纳米晶的光伏特性和量子尺寸效应

对制备的ＣｅＯ２纳米晶进行了反射吸收光谱研究，对其在３００－４５０ｎｍ的宽带吸收指认为Ｏ２ｐ→Ｃｅ４ｆ电荷转移跃迁，发现这个吸收带随着样品粒径变小而红移，利用表面光电压谱方法和场调制表面光电压谱方法不同粒径的ＣｅＯ２纳米晶的光伏特性进行了研究。并对吸收谱带进行了解析。当样品粒径达到纳米尺寸时，在ＣｅＯ２价带上大约０．９ｅＶ处明显地形成一个新能带。这个能带具有较强的定域性，在相应的跃迁的过程中产生具     

纳米氧化锆的制备与应用

综述了纳米ZrO2粉体的制备与应用,展望了其发展前景。目前,纳米ZrO2粉体的制备方法以化学法为主。文章介绍了共沉淀法、金属醇盐法、溶胶-凝胶法、反胶团法、水热法、溶剂蒸发法、共蒸馏法及化学气相法等制备方法,并对上述各种方法作出评价。文章还介绍了纳米ZrO2粉体的应用研究,将其分散于陶瓷基体中以降低陶瓷的烧结温度,提高陶瓷的韧性和强度;将纳米ZrO2用作催化剂,在催化加氢及土壤固氮等方面呈现良好的催化活性和选择性。     

Phase Diagram at Low Temperature of the System ZrO2/Nb2O5

Various compositions of the ZrO₂/Nb₂O₅ system were synthesized and the experimental conditions for obtaining reproducible results were established. The gel was precipitated at constant pH = 10, aged at room temperature for 18 h and, after filtration, dried at 110 °C for 24 h. The phase diagram of the ZrO₂/Nb₂O₅ system was established between 600 and 1300 °C. Phase transitions of ZrO₂ and Nb₂O₅ were observed with XRD; and two ternary compounds, 6 ZrO₂ · Nb₂O₅ and 12 Nb₂O₅ · ZrO₂, were identified. The samples with a Nb₂O₅ content between approximately 10 and 40 mole% showed the greatest specific area and are thus best for use as catalyst supports.     

Au/ZrO2催化剂中ZrO2的尺寸效应:1,3-丁二烯加氢反应

在不同温度(673～1073K)下,于流动N2气中焙烧ZrO(OH)2醇(乙醇)凝胶,制备了不同尺寸的ZrO2-AN纳米晶(6～30nm).采用沉积-沉淀方法制备了相应的质量分数为0.7%的Au/ZrO2-AN催化剂.用XRD,XRF,TEM/HRTEM,EDS,N2吸附和1,3-丁二烯加氢反应对ZrO2-AN和Au/ZrO2-AN催化剂进行了表征.结果表明,在所有的Au/ZrO2-AN样品中,Au粒子的平均尺寸为4～5nm,ZrO2-AN的颗粒大小没有因为负载Au粒子而发生改变.1,3-丁二烯在Au/ZrO2-AN催化剂催化下能以100%的选择性进行加氢反应生成单烯烃.随着Au/ZrO2-AN催化剂中ZrO2-AN纳米晶尺寸的增加或“载体”焙烧温度的升高,1,3-丁二烯的转化率明显降低;1-丁烯的选择性先增加后减小,2-丁烯中反/顺异构体的摩尔比在0.5～1.0的范围内逐渐增大,TEM/HRTEM表征结果清楚地表明,Au/ZrO2-AN催化剂中Au粒子与ZrO2-AN颗粒接触界面/周边随ZrO2-AN颗粒尺寸的减小而明显增加,这很可能是含有更小尺寸ZrO2-AN纳米粒子的Au/ZrO2-AN催化剂具有更高的催化活性的重要原因.     

二氧化硅纳米管的稳定性及尺寸效应

运用密度泛函计算, 对无水(SiO2-NTs)和水合(SiO2-WNTs)的SiO2纳米管进行结构优化和频率计算, 研究了与尺寸有关的平均结合能和红外光谱. SiO2-WNTs中发现当纳米管的层数或长度相同时平均结合能相等. SiO2-WNTs比SiO2-NTs和二元环直链结构都要稳定. 对截面为四元环的纳米管红外光谱的分析发现, 振动峰值与实验值相吻合, 且切向和径向振动显示较强的尺寸效应. SiO2-WNTs是一维SiO2纳米管一种合适的结构模型.     

Phase behavior of undecane-tetradecane mixtures confined in SBA-15

Phase behavior of undecane-tetradecane (n-C11H24-C14H30, C11-C14) mixtures in bulk and confined in SBA-15 have been studied using differential scanning calorimetry. The bulk C11-C14 system shows multiple phase regions due to rotator phase. Confined in the pores of SBA-15 (pore diameters 3.8-7.8 nm), the mixtures only show a melting boundary of a straight line and a curve, respectively. In SBA-15 (17.2 nm), phase behavior of themixtures has some similarity to that of the bulk. Under confinement, the phase diagrams of the mixtures vary with the pore size, temperature, and compositions.     

CO2 Activation by Zr+ and ZrO+ in Gas Phase

The gas-phase reduction of carbon dioxide to carbon monoxide, induced by Zr⁺ and ZrO⁺ catalysts, was investigated at density functional level of theory. Calculations were carried out using both hybrid and pure exchange-correlation functionals in order to reproduce adequately the energetic gap between the Zr^{+ 4}F and ²D electronic states and experimental reaction heats. In agreement with a guided ion beam tandem mass spectrometer study, we have found that carbon dioxide activation by Zr⁺ presents a spin-forbidden mechanism because of a spin inversion process occurring during reaction in the rate- determining step. ZrO⁺ interacts with CO₂ through two possible pathways both endothermic: formation of ZrO ₂ ⁺ and CO products is less unfavourable. Information about ground and excited states of ZrO⁺ and ZrO ₂ ⁺ oxides and bond dissociation energies of species present on the reaction paths was also given.     

Nanostructured ZrO2 and Zr‐C‐N Coatings from Chemical Vapor Deposition of Metal‐Organic Precursors

Nanocrystalline zirconium carbonitride (Zr‐C‐N) and zirconium oxide (ZrO₂) films were deposited by chemical vapor deposition (CVD) of zirconium‐tetrakis‐diethylamide (Zr(NEt₂)₄) and ‐tert‐butyloxide (Zr(OBu^t)₄), respectively. The films were deposited on iron substrates and characterized by scanning electron microscopy (SEM), X‐ray diffraction (XRD) and X‐ray photoelectron spectroscopy (XPS). The Zr‐C‐N films show blue, golden brown or bronze colours, with colour stability depending upon the precursor composition (pure metal amide or mixed with Et₂NH). The deposition temperature showed no pronounced effect on the granular morphology of the Zr‐C‐N films. The XRD data of the films correspond to the formation of carbonitride phase whereas the XPS analyses revealed a strong surface oxidation and incorporation of oxygen in the film. The films deposited using a mixture of Zr(NEt₂)₄ and Et₂NH showed higher N content, better adhesion and scratch resistance when compared to films obtained from the CVD of pure Zr(NEt₂)₄. Subject to the precursor composition and deposition temperature (550‐750 °C), the microhardness values of Zr‐C‐N films were found to be in the range 2.11‐5.65 GPa. For ZrO₂ films, morphology and phase composition strongly depend on the deposition temperature. The CVD deposits obtained at 350 °C show tetragonal ZrO₂ to be the only crystalline phase. Upon increasing the deposition temperature to 450 °C, a mixture of tetragonal and monoclinic modifications was formed with morphology made up of interwoven elongated grains. At higher temperatures (550 and 650 °C), pure monoclinic phase was obtained with facetted grains and developed texture.     

Effect of CuO Doping on the Electrical Behavior of ZrO2

Electrical conductivity has been measured at different temperatures for ZrO2 doped with various molar ratios of CuO. The conductivity increases due to migration of vacancies, created by doping. The conductivity was found to increase with increase in temperature till 220℃ and thereafter decrease due to collapse of the fluorite framework. A second rise in conductivity around 500 ℃ was observed due to phase transition of ZrO2. X-ray powder diffraction, DTA and IR studies were carried out for confirming doping effect and phase transition in ZrO2.     

NOx在担载CeO2的纳米ZrO2上的吸附研究

通过反相微乳液法制备了纳米级高比表面积ZrO₂粉体材料,用TEM,XRD和氮气吸附BET比表面积等手段对其进行了表征,研究了Ce(NO₃)₃溶液浸渍的ZrO₂粉体对氮氧化物的吸附活性.实验结果表明,5%Ce/ZrO₂样品室温时可吸附NO_x的最大值为34.5mg;100℃时为17.5mg;200℃时可达9.5mg.对比表明,同样条件下微乳液法制备的ZrO₂对NO_x的最大吸附量是一般沉淀法制备的ZrO₂样品的2.5倍.纳米级ZrO₂的特殊孔结构可能是导致微乳液法制备的ZrO₂样品吸附量较高的主要原因.     

制备条件对纳米级固体超强酸SO42- /ZrO2性能的影响

通过溶剂替代法制备了纳米级固体超强酸SO42-/ZrO2催化剂,用XRD、TEM、TG-DTA、IR、XPS等技术考察了制备条件对样品的粒径、晶化温度与结构的影响,并研究了它们对松油醇乙酰化反应的催化性能。实验结果表明,0·5mol/LH2SO4浸渍、500~550℃焙烧3h的纳米SO42-/ZrO2具有最高超强酸性和催化活性。其酸强度为-16·02≤H0≤-14·52,粒径在20~40nm,松油醇转化率达99·8%。