La掺杂Bi2O3的制备、表征与可见光催化活性

采用浸渍法制备了La掺杂Bi2O3(La-Bi2O3)光催化剂,利用X射线荧光光谱(XRF)、X射线衍射(XRD)、扫描电子显微镜(SEM)、傅立叶变换红外光谱(FT-IR)、X射线光电子能谱(XPS)、紫外-可见吸收光谱(UV-Vis)和光致发光谱(PL)等分析测试手段对样品的La掺杂量、晶体结构和光谱特征等进行了表征,并以2,4-二氯苯酚(2,4-DCP)水溶液的降解作为探针反应,考察了样品的可见光催化性能.结果表明,适量的La掺杂能有效抑制Bi2O3由四方相向单斜相转变,并将光吸收范围拓展到550 nm以上.掺杂的La可取代Bi2O3晶格中部分Bi,形成Bi—O—La键,并生成了少量镧铋复合氧化物(La0.176Bi0.824O1.5),它们的存在能有效抑制光生电子-空穴对的复合,从而提高光催化量子产率.可见光照射下2,4-DCP的光催化降解实验表明,La-Bi2O3具有良好的可见光催化性能,并且当La的掺杂量为3%(摩尔分数)时,催化剂的可见光催化效率最高.     

La对Ag-BaO薄膜荧光特性的影响

用真空沉积的方法制备了掺杂稀土La的Ag-BaO薄膜，与不掺稀土La的Ag-BaO薄膜相比较，光致荧光光谱的形状和峰位基本没有改变，但在整个观测波段（325－600nm)的荧光发射都有所增强，总体荧光发射约增强40％，且增强效应表现为“蓝强”的特点，即短波方向比长波方向要显著一些，分析表明，La与Ag-BaO薄膜中的Ag会形成银镧金属间化合物，其4f能级位于费米能级附近下方，部分局域化且与导带部分耦合，4f能级与导带能级之间的能量传递是荧光发射增强效应的来源，4f电子的光吸收截面随入射光子能量的增加而增大的特点是“蓝强”现象的原因。     

镧掺杂纳米TiO2覆膜陶瓷的光催化自洁净和抗菌性能

采用溶胶-凝胶法制备了掺镧纳米TiO2薄膜,并用浸渍提拉法覆膜在陶瓷表面.最佳工艺条件为:覆膜层数为3,焙烧温度为500℃,掺镧量为La3 /TiO2=0.003(摩尔比).用XRD、SEM等方法研究了薄膜的结构与形貌.陶瓷覆膜镧掺杂纳米TiO,具有良好的亲水性能,抗菌率高达99%.     

锰离子控制掺杂二氧化钛薄膜光催化活性增强的机理探讨

采用溶胶-凝胶法通过工艺控制制备了锰离子以不同形式掺杂TiO₂的光催化剂薄膜,并通过XPS和SEM对薄膜的结构进行表征.通过UV-Vis分光光度计及电化学工作站表征了薄膜的光吸收性能和光电化学性能,通过甲基橙溶液的光催化降解脱色率来表征催化剂薄膜的光催化活性.结果表明,以锰离子MT掺杂方式制备的TiO₂薄膜可明显增强TiO₂的光催化活性,而以MM掺杂方式制备的TiO₂薄膜反而降低了TiO₂的光催化活性;锰离子MT掺杂方式的最佳掺杂质量分数为0.8%.催化剂薄膜的电化学行为显示,薄膜具有p-n结的电容-电压特性,锰离子MT掺杂TiO₂薄膜的开路电位和瞬时光电流信号较强,说明其光生载流子易于生成并且分离效果较好.依据半导体的p-n结原理探讨了锰离子控制掺杂TiO₂的光催化活性机理.     

基于磁响应光子晶体与量子点的多重变色防伪研究

结合Fe₃O₄@SiO₂ (M)超顺磁胶体粒子动态连续的磁致变色和碲化镉量子点(CdTe QDs)瞬时发射的光致发光特性, 采用聚二甲基硅氧烷(PDMS)弹性体封装含有M胶体粒子和CdTe QDs的乙二醇(EG)微液滴, 制得了具有多重变色功能的M/QDs/EG/PDMS复合薄膜. 利用光学显微镜、光纤光谱仪、荧光光谱仪、数码相机、拉力试验机对复合薄膜的内部结构、光学性质及力学性能进行表征. 结果表明, 在外界磁场的诱导下, 复合薄膜瞬时呈现明亮的结构色, 且随着磁场强度的降低, 复合薄膜的衍射波长发生连续红移, 移动范围可达145 nm. 此外, 在紫外光的激发下, 复合薄膜可呈现特定波长的荧光发射, 具备良好的光致发光特性. 同时, 复合薄膜断裂伸长率可达132%, 表现出良好的弹性, 这为其附着在不同材料表面实现防伪应用提供了基础. 进一步地, 通过图案化设计, 可制得响应变色迅速、图案隐现可逆、颜色变化多样的防伪薄膜, 这有利于其在信息加密和高级别防伪领域中的应用.     

离子掺杂与载体类型交互效应对纳米TiO2薄膜光活性改性研究

采用溶胶-凝胶法在六种不同基体材料上制备了掺杂La3 的TiO2纳米复合材料.利用扫描电子显微镜(SEM),x射线衍射(XRD)及紫外-可见吸收光谱对其TiO2薄膜的TiO2颗粒形态和相组成进行了详细研究,并以甲基橙为模拟对象,研究了不同浓度的La3 掺杂对催化剂光活性的影响,结果表明:脱色率(η%)随载体、掺杂浓度不同而变.不锈钢载体掺杂浓度为0.604×1021/cm3La3 的二氧化钛薄膜对甲基橙有最高的降解效率,陶瓷载体掺杂0.604×1017/cm3La3 的降解效率最高,玻璃载体最佳La3 掺杂浓度为6.04×1017/cm3,而钛片载体最佳La3 掺杂浓度为0.604×1023/cm3.     

磁性荧光纳米材料的制备与性能

采用表面活性剂3-氨丙基三乙氧基硅烷(APTES)修饰Fe₃O₄磁性纳米粒子, 经质子化后, Fe₃O₄磁性纳米粒子表面披覆大量的正电荷, 与表面带负电荷的巯基丙酸(MPA)修饰的核壳CdSe/CdS/ZnS量子点(QDs)通过强烈的静电作用而发生组装, 得到兼具磁性和荧光性能的磁性荧光纳米材料. 利用透射电子显微镜(TEM)、傅里叶变换红外光谱仪(FTIR)、X射线衍射仪(XRD)、荧光分光光度计和振动样品磁强计(VSM)等测试手段对磁性荧光纳米材料进行表征. 研究表明, 由两种粒子组装的核壳结构复合粒子拥有良好的磁性能和荧光性能.     

掺杂镧的TiO2纳米粒子的光致发光及其光催化性能

采用溶胶-凝胶法制备了纯的和掺杂La的TiO2纳米粒子,并利用XRD,TEM,XPS和荧光光谱(FS)等对样品进行表征,主要考察焙烧温度和La含量对TiO2纳米粒子的性质以及光催化降解苯酚活性的影响,并探讨了La的掺杂对TiO2相变的作用机制以及FS光谱与光催化活性的关系.结果表明,适量La掺杂能够提高TiO2纳米粒子FS光谱强度,这是因为La掺杂能够使表面氧空位和缺陷的浓度增加;600℃热处理的掺杂不同量La的TiO2样品的光催化活性顺序是:1%＞1.5%＞3%＞0.5%＞5%＞0%,这与它们的FS光谱强度的顺序是一致的,即FS光谱强度越高,其光催化活性越高.这是因为在光致发光过程中,FS信号主要来源于表面氧空位和缺陷,而在光催化反应过程中,表面氧空位和缺陷能够有利于光生电子被捕获.     

铂非均匀掺杂二氧化钛薄膜的光催化性能

采用溶胶-凝胶法制备了铂非均匀掺杂的二氧化钛薄膜, 并用UV-vis分光光度计及电化学工作站表征了薄膜的光吸收性能和光电化学行为, 通过对甲基橙的光催化降解动力学来表征催化剂的光催化活性. 结果表明 Pt非均匀掺杂可以明显增强二氧化钛的光催化活性, 而均匀掺杂的效果较差; Pt非均匀掺杂的最佳量为0.3 mol%. 催化剂薄膜的电化学行为显示: Pt非均匀掺杂二氧化钛薄膜的开路电压高, 交流阻抗小. 并从半导体的PN结原理探讨了Pt非均匀掺杂二氧化钛的催化活性机理.     

镧钼热阴极表面活性层中的镧超微粒子

为了研究镧钼阴极表面发射机制, 利用新型阴极研究装置研究阴极发射性能与表面元素La, O比例的关系, 发现表面层中La/O比例越高, 阴极的发射性能越好. 在实验基础上提出了金属La超微粒子埋藏于La2O3晶体中的热阴极表面发射模型, 模型认为活性层中的超额镧以镧超微粒子形式存在, La超微粒子中的电子在热激发下越过肖特基势垒进入La2O3晶体的导带进而克服表面电子亲和势逸出到真空, 提供了电子发射的丰富源泉. 由于肖特基势垒远小于La2O3的禁带宽度, 并且超微粒子可以使耗尽层厚度变薄, 极大降低了电子发射到真空的阈值.     

利用手持技术改进测定乙醇分子结构实验

利用压强传感器代替排水集气法,改进测定乙醇分子结构实验的仪器装置,并探索最佳反应条件。另外,设计两个空白实验,结合压强变化曲线对实验误差进行相关讨论。     

Neutral diterpenoids of oleoresins of five species of conifers of Transcarpathia

The compositions of the neutral diterpenoids of the oleoresins of five species of conifers growing in the Transcarpathia have been studied. It has been found that the oleoresins ofAbies alba M.,Larix decidua M., andPicea excelsa L. contain more than 50% of neutral diterpenoids. The group and qualitative compositions of the oxygen-containing diterpenoids have been determined. In the oleoresins ofAbies alba,Picea excelsa, andPicea abies tertiary alcohols — cis-abienol and isocembrol — predominate, while inLarix decidua the main component is the hydroxy ester larixyl acetate. Primary alcohols related to the resin acids have been found in all the oleoresins investigated. Features of the distribution of diterpenoids according to the species of conifers have been revealed. The results obtained are necessary for the chemotaxonomy of conifers of the family Pinceae.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodynkh Soedinenii, No. 6, pp. 812–816, November–December, 1988.     

光谱仪测试范围的扩展

由于石化行业的生产需要，其材质的使用具有多样性和广泛性，经常会出现顾客委托的测试样品的一个或几个元素跨越光谱仪现有测试程序测量范围的情况。本法通过对光谱仪测试原理的认识，根据光谱仪的测试能力及标样的采集，实现了一个或几个元素测量范围的扩展，并对其测量的影响因素进行了研究。     

Influence of viscosity of medium on processes of oxygen quenching of excited states of mesoporphyrin

The oxygen quenching rate constants for singlet and triplet excited states of the dimethyl ester of mesoporphyrin IX increase with decreasing viscosity of the medium and reach a maximum at a viscosity of approximately 0.4 mPa·sec, after which the rate constants begin to decrease. The drop in rate constant with increasing fluidity of the medium may be related to a nonequilibrium character of the elementary act in the interaction of the reactants in the solvent cage. In viscous media such as isopropyl alcohol, isobutyl alcohol, and isoamyl alcohol, the reaction radius is greater than the sum of the radii of the reacting particles. The long-range character of these processes is due to the relatively weak dependence of the quenching probability on distance.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 2, pp. 161–167, March–April, 1989.     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

物质分配系数的测定实验改进

实验教学目的是从解决实际问题出发,以实验技术训练和实验设计思想培养为目标。介绍了将单一的物质分配系数测定实验改进为综合实验,提高了实验效果及实验资源利用率。     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

Calculation of enthalpies of hydrogenation of hydrocarbons

Sets of hydrogen molecule equivalents have been developed which permit the calculation of hydrogenation of different types of carbon-carbon bonds from ab initio total energies (3-21G and 6-31G* basis sets, and, to a more limited extent, for MP2/6-31G* data) of reactants and products. The calculated enthalpies of hydrogenation are in good agreement with experiment for unstrained molecules, with average errors on the order of 2 kcal/mol. The 6-31G* equivalents allow the enthalpies for strained molecules to be calculated accurately, but the 3-21G equivalents do not. The equivalents for both basis sets have been tested by calculating the enthalpies of hydrogenation of carbon-carbon bonds in nitrogen- and oxygen-containing organic molecules, free radicals, and classical carbocations. The results are in good agreement with experiment in most cases.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。