焙烧温度对TiO2柱撑膨润土结构、吸附及光催化性能的影响

采用酸性溶胶法合成了TiO2柱撑膨润土(Ti-Na-MMT), 采用XRD, FTIR, TG-DTA, BET和DRS等技术, 研究了焙烧温度对Ti-Na-MMT结构和处理偶氮染料废水性能的影响. 结果表明, 所制备的Ti-Na-MMT具有较好的热稳定性, 经773 K热处理后, 其结构仍基本保持不变. 随着焙烧温度的升高, 晶面间距逐渐减少. Ti-Na-MMT的比表面积、孔体积、孔径分布等特征以及TiO2晶粒粒径与煅烧温度有关; 在473 K下, 焙烧制备的Ti-Na-MMT BET的比表面积和最大孔容最大, 平均孔径和TiO2粒径最小; 随着焙烧温度的进一步升高, TiO2粒子发生团聚, 粒径变大, 从而Ti-Na-MMT的比表面积和最大孔容减小, 而其平均孔径呈增大趋势. DRS结果表明, 在473 K下焙烧制备的Ti-Na-MMT对光的吸收能力最强. 焙烧温度对Ti-Na-MMT的吸附性能和光催化活性的影响规律一致, 这表明吸附和光催化过程存在一定的协同作用. 473 K时制备的Ti-Na-MMT表现出的吸附和光催化活性均最强.     

V^5＋离子掺杂纳米氧化铈的合成与表征

以硝酸铈、柠檬酸和偏钒酸铵为原料,采用溶胶-凝胶(sol-Gel)法制备了V5+离子掺杂纳米CeO2粉体.利用X射线粉晶衍射(XRD)和 扫描电镜(SEM)等方法研究了合成反应条件(焙烧温度、V5+掺入量等)对合成物的微观结构、物相组成以及性能的影响.XRD分析表明所合成的CeO2纳米晶粒具有空间群符号为Fm3m的立方晶体结构.随焙烧温度的升高,合成的CeO2晶粒结晶度增高.对甲基蓝的光催化降解试验表明,纳米CeO2对甲基蓝具有较好的光催化降解效果,焙烧温度对纳米CeO2的光催化活性有较大影响,适量V5+的掺入有利于提高纳米 CeO2的光催化降解效果,掺1%V5+离子的CeO2光催化降解甲基蓝6 h,其降解率可达89%以上.     

共沉淀-喷雾干燥法制备Sm2O3掺杂CeO2纳米粉体

以Sm（NO3）3.6H2O和Ce（NO3）3.6H2O为原料,用共沉淀-喷雾干燥法制备了Sm2O3掺杂CeO2（SDC）粉体。通过沉降实验、TG-DSC、XRD、BET、SEM和粒度分布对前驱体的分散性、稳定性及制得的SDC粉体性能进行表征,研究了洗涤方法、分散剂对前驱体及SDC粉体的影响。结果表明：无机陶瓷膜洗涤后前驱体分散性好,经500℃以上温度焙烧后的粉体为立方萤石型结构。加入分散剂后前驱体的分散性明显提高,制得的SDC粉体比表面积显著增加,最终获得了晶粒平均粒径为12.51 nm、团聚态颗粒为球形的SDC纳米粉体。     

低温燃烧合成Ce0.8Y0.2O1.9固溶体及烧结性能的研究

以硝酸盐做氧化剂,柠檬酸为燃料,采用低温燃烧法制备纳米级超细Ce0.8Y0.2O1.9 (YDC)固溶体.利用TG-DSC,XRD,SEM,FT-IR和BET等手段对凝胶前驱体的热分解行为、相转化过程和YDC粉体的性能进行表征.TG-DSC结果表明,柠檬酸-硝酸盐干凝胶的点火温度约为263.3℃;经XRD测试,粉体经600℃焙烧即形成了单相立方萤石型结构的固溶体,晶粒度为16 ～23nm.柠檬酸与硝酸盐摩尔比(CA/N)对粉体的微观形貌、比表面积和烧结活性有显著影响.当CA/N为1.5∶1时,粉体粒子间仅有微弱的软团聚,将素坯在1400℃烧结2h,得到相对密度为95.6％,平均粒径约为0.7 μm的陶瓷烧结体.     

CeO2掺杂的PdO纤维催化剂的甲烷催化燃烧活性研究

制备了2%Pd/CeO2/Al2O3-SiO2纤维催化剂,考察了CeO2对催化剂甲烷催化燃烧活性的影响.结果表明,当CeO2的掺杂量为2%时催化剂活性最好,其甲烷完全转化温度为400 ℃.比表面积测定(BET)结果显示,CeO2的加入提高了催化剂的比表面积;氧气程序升温脱附(O2-TPD)实验结果表明,适量CeO2的加入,提高了活性相PdO的分解温度,催化剂热稳定性提高.     

铈掺杂TiO2光催化剂的制备及其催化性能

以TiCl4为原料、Ce(NO3)3·6H2O为稀土掺杂剂,制备了不同掺杂量的Ce/TiO2粉体,并进行了DTA-TG,XRD,SEM和TEM表征.实验主要考察铈掺杂对TiO2粉体的表面形状和光催化活性的影响.结果表明,掺铈能明显改善样品的团聚状态,有利于样品比表面积的增大.SEM和TEM对500℃的焙烧样品表征结果,掺杂样品二次颗粒的成孔性远好于没有掺杂的纯样品.掺杂量从m(CeO2)=0.5%增加到m(CeO2)=8%,样品的比表面积增加了74m2·g-1;活性评价结果表明,掺杂铈可有效提高催化剂的光催化活性,其中m(CeO2)=1%的样品活性最好.     

铈掺杂TiO2光催化剂的制备及其催化性能

以TiCl4为原料、Ce(NO3)3·6H2O为稀土掺杂剂,制备了不同掺杂量的Ce/TiO2粉体,并进行了DTA-TG,XRD,SEM和TEM表征.实验主要考察铈掺杂对TiO2粉体的表面形状和光催化活性的影响.结果表明,掺铈能明显改善样品的团聚状态,有利于样品比表面积的增大.SEM和TEM对500℃的焙烧样品表征结果,掺杂样品二次颗粒的成孔性远好于没有掺杂的纯样品.掺杂量从m(CeO2)=0.5%增加到m(CeO2)=8%,样品的比表面积增加了74m2·g-1;活性评价结果表明,掺杂铈可有效提高催化剂的光催化活性,其中m(CeO2)=1%的样品活性最好.     

Pd/Ce0.8Zr0.15La0.05Oδ整体催化剂甲苯催化燃烧性能的研究

采用一次浸渍法分别制备了 Pd/Ce0.8Zr0.15La0.05Oδ及Pd/Ce0.8Zr0.2O2整体式蜂窝陶瓷催化剂,考察了不同温度焙烧的两类整体催化剂甲苯催化燃烧性能.通过X射线粉末衍射(XRD)、比表面积、拉曼光谱(Raman)、程序升温还原(H2-TPR)、PdO分散度等表征结果与催化活性进行关联.结果表明,随着焙烧温度升高,催化剂比表面积下降,Raman图谱CeO2及PdO峰强度增加,H2-TPR中Ce4+还原峰向高温方向移动,同时PdO分散度下降,相应甲苯催化氧化活性下降.与CeO0.8Zr0.2O2涂层催化剂相比,La3+掺杂催化剂在高温焙烧时,其比表面积下降较小,Raman光谱表明其氧缺位比铈锆涂层催化剂多,H2TPR谱图中Ce4+还原峰低约60～80℃,PdO分散度亦比末掺杂催化剂高.1000℃焙烧下的甲苯氧化反应活性远高于未掺杂催化剂,说明镧的掺杂提高了铈锆涂层催化剂的高温反应活性及热稳定性.     

Redox property of Co3O4/CeO2 and the effect of reaction conditions on its performance in CO oxidation

采用沉淀氧化法制备了Co3O4/CeO2催化剂.运用XRD、BET和TPR表征手段,考察了不同钴铈比及焙烧温度对钴铈复合氧化物物理及化学性能的影响,并分别在干、湿条件下进行了一氧化碳氧化反应研究.结果表明,与纯的Co3O4相比,在不同比例的Co3O4/CeO2均经723 K焙烧的各种催化剂中,钴铈原子比为9∶1的复合氧化物粒径较小,比表面积较大,说明适当比例铈的添加能使Co3O4具有较小的粒径.此氧化物经538 K温度焙烧制得的钻铈比为9∶1的复合氧化物中Co3O4平均粒径为7.2nm,BET比表面积为167.6 m2/g.经TPR考察发现其具有最优的氧化还原性能.     

影响纳米CeO2沉淀法合成的工艺因素研究

以Ce(NO3)3·6H2O为铈源, (NH4)2CO3·H2O为沉淀剂, 加入少量表面活性剂作分散剂, 采用液相沉淀法成功合成了纳米CeO2. 研究了反应温度、反应时间、搅拌速率、表面活性剂种类及用量、焙烧温度和焙烧时间等因素对纳米CeO2晶粒尺寸和相对密度的影响, 得出优化工艺条件, 通过XRD, DTA/TG, TEM, BET比表面积、 N2等温吸附与脱附、 BJH脱附孔径分布及杂质含量分析等方法对合成产品性能进行了表征. 结果表明 采用浓度为0.1 mol·L-1的(NH4)2CO3·H2O溶液快速倒入浓度为0.1 mol·L-1 的Ce(NO3)3·6H2O溶液中以化学计量比进行反应, 同时加入0.4% (质量分数) PEG4000, 反应时间为10 min, 反应温度为40 ℃, 搅拌速率为800 r·min-1, 经水洗、醇洗、脱水和真空干燥后所得的前驱体于300 ℃的空气中焙烧1 h, 该条件下合成的CeO2属于立方晶系, 空间群为Fm3m, 原生晶粒粒径为5 nm左右, 颗粒粒径为20 nm以下, 比表面积达140.61 m2·g-1, 孔径分布为5～15 nm, 孔径峰值为9.3 nm, 纯度≥99.97%.     

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。     

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。     

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.     

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.     

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.     

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.

     

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。     

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。