用无机硅剂水热法合成纳米NiO/SiO2及其催化乙炔分解制备纳米碳管

以硅溶胶为硅源．水热法制备NiO／SiO2催化剂，用于化学气相沉积法(Chemical Vapor Deposition，CVD法)制备碳纳米管通过SEM表征，研究了催化剂原料及其配比，水热制备工艺条件对催化效果的影响．结果表明：用硅溶胶可替代正硅酸乙酯作为硅源；制备的最佳条件为：MSiO2：MNi（NO3）2=1：12～1：14，水热温度为180～200℃，压力为1．2～1．5MPa．保温时间为0．5～2h．     

负载型Sn2(OMe)4/SiO2催化剂的制备及其催化CO2和CH3OH直接合成碳酸二甲酯的性能

 采用表面改性法制备了负载型Sn2（OMe）4／SiO2双核桥联配合物催化剂，用IR，TPD和微反技术对催化剂的表面结构、化学吸附性质和催化活性进行了研究．结果表明，双核桥联Sn2（OMe）4／SiO2配合物中存在Sn－O－Si双齿配位形式，甲氧基以桥基形式联结两个Sn4＋离子；CO2在催化剂表面以桥式吸附态和甲氧碳酸酯基吸附态存在，而CH3OH只以分子吸附态存在．在反应温度413K，压力0．5MPa，反应空速1500h－1以及CH3OH与CO2的摩尔比为2～2．5的反应条件下，CO2和CH3OH在Sn2（OMe）4／SiO2催化剂上生成碳酸二甲酯的选择性达到近100％．根据实验结果，提出了CO2与CH3OH在Sn2（OMe）4／SiO2催化剂表面上的反应机理，反应物分子共吸附于催化剂表面同一活性位上及CO2的甲氧碳酸酯基吸附态的形成是反应顺利进行的关键因素．     

SiO2复合Pt-Cd0.53Zn0.47S固溶体的光催化性能

采用共沉淀法制备了Cd0.53Zn0.47S固溶体光催化剂,以光还原沉积法负载Pt,水解正硅酸乙酯负载SiO2,得到了负载Pt的SiO2复合光催化剂SiO2/Pt-Cd0.53Zn0.47S,并研究了水解pH值对其催化活性的影响.通过X射线衍射（XRD）、比表面（BET）、荧光光谱（PL）、紫外-可见漫反射光谱（UV-Vis DRS）和扫描电镜（SEM）等测试技术对催化剂进行了表征.结果表明,SiO2复合光催化剂有效地抑制了Pt-Cd0.53Zn0.47S光催化过程中发生的光腐蚀和粒子团聚,促使光生电子和空穴分离,从而使可见光制氢催化剂活性和稳定性大大提高.     

SiO／CNTs：新型锂离子电池负极材料

通过化学气相沉积方法原位制备了氧化硅／碳纳米管（SiO／CNTs）极材料．扫描电镜（SEM）测试结果表明,碳纳米管沉积在氧化硅表面,形成笼状结构,将氧化硅粒子紧密包裹．SiO／CNTs负极材料的初始充放电容量分别为1171和789mAh／g,经过80次充放电循环后,可逆容量为500mAh／g．在循环过程中,碳纳米管和氧化硅之间的紧密接触使得SiO／CNTs复合材料保持了稳定的导电网络,循环性能得以提高．     

铁助剂对Rh-Mn-Li/SiO2催化剂表面上的CO脱附和CO加氢行为的影响

 采用一氧化碳程序升温脱附（CO－TPD）和吸附的一氧化碳加氢程序升温表面反应（TPSR）考察了Fe助剂对Rh基催化剂上CO的脱附行为及吸附CO的加氢行为的影响．CO－TPD实验表明，在Rh／SiO2催化剂上CO有三个脱附峰．在Rh－Mn－Li／SiO2中加入0．05％Fe后，高温脱附CO比Rh／SiO2催化剂上相应的CO量大．增加Fe的负载量，CO的脱附量减少．TPSR实验中，CO加氢反应的主要产物是甲烷．不同组分的催化剂上甲烷的生成温度有如下顺序：Rh／SiO2（482K）＜Rh－Mn－Li／SiO2（489K）＜Rh－Fe／SiO2（494K）＜Rh－Mn－Li－Fe／SiO2（501K）．甲烷峰的产生伴随着CO（s）高温脱附峰的消失，说明甲烷是由强吸附的CO加氢生成的．     

VPO/SiO_2催化对甲氧基甲苯氢氧化制备大茴香腈

VPO／SiO2催化对甲氧基甲苯（PMOT）氨氧化制备精细化学品大茴香腈（MOBN）．在内径为20mm的连续流动固定床反应器上进行工艺条件正交实验和单因素实验．研究了反应温度、空气比、氨气比以及空间速度对PMOT转化率、MOBN摩尔产率和选择性的影响,确定最适宜的反应条件为：温度603K,PMOT：NH3：Air=1：12：30,空间速度为564h－1．在此条件下,PMOT转化率为98％,MOBN产率63％,选择性达64．3％．经气相色谱分析,产品纯度高于99％．     

可见光还原水制氢ZnS-CdS/SiO2催化剂表面结构与性能的研究

以H2S和Na2S为硫源,通过共沉淀法制备了ZnS-CdS/SiO2复合光催化剂,利用高分辨透射电镜（HR-TEM）、X射线光电子能谱（XPS）、X射线衍射（XRD）等技术对催化剂进行了表征.研究了Na2S及H2S为硫源时催化剂表面结构和可见光下光催化还原水产氢的活性的变化.结果表明,与H2S相比,Na2S为硫源更有利...     

Cr2O3-Co3O4／SiO2对十八醇氧化生成十八酸反应的催化性能

 制备了一系列不同Cr／Co比例的Cr2O3－Co3O4／SiO2催化剂，并用XRD，FT－IR和BET等手段对催化剂进行了表征；考察了催化剂对十八醇氧化生成十八酸反应的催化性能，及反应条件（反应温度和反应时间）对催化性能的影响，确定了最佳反应条件．结果表明，金属硝酸盐在773K焙烧后转变成相应的氧化物并负载于二氧化硅上．Cr2O3－Co3O4／SiO2催化剂对十八醇氧化反应有很高的催化活性，十八酸选择性最高可达99．93％，收率可达52．44％．Cr2O3－Co3O4／SiO2催化剂的活性明显高于单一的Cr2O3／SiO2或Co3O4／SiO2催化剂     

新型球形纳米空心SiO2的模板合成方法研究

以纳米碳酸钙颗粒为新颖的无机模板剂,硅酸钠为无机硅源,通过溶胶-凝胶法形成CaCO3／SiO2的核壳结构;随后通过高温煅烧、酸溶和干燥处理,合成出了具有高比表面积的球形纳米空心二氧化硅粒子．然后,分别采用TEM,SEM,EDS,XRD,FTIR和TG等测试手段对样品进行了分析和表征,并考察了不同合成条件,如反应温度、反应pH值、煅烧温度和包覆反应时SiO2／CaCO3的配比对纳米空心二氧化硅粒子的比表面积变化．实验结果表明：较高的反应温度如60～80℃,pn值9左右、SiO2包覆量为碳酸钙质量的10％,以及煅烧温度为700℃,有利于形成空心形貌较好、比表面较大的球形纳米空心二氧化硅。     

CH3S自由基H迁移异构化及脱H2反应的直接动力学研究

采用密度泛函方法（MPW1PW91）在6．311G（d,p）基组水平上研究了CH3S自由基H迁移反应CH3S→CH2SH（R1）,脱H2反应CH3S→HCS＋H2（R2）以及脱H2产物HCS异构化反应HCS→CSH（R3）的微观动力学机理．在QCISD（t）／6．311＋＋G（d,p）／／MPW1PW91／6．311G（d,p）＋ZPE水平上进行了单点能校正．利用经典过渡态理论（TST）与变分过渡态理论（CVT）分别计算了各反应在200-2000K温度区间内的速率常数K^TST和k^CVT,同时获得了经小曲率隧道效应模型（SCT）校正后的速率常数萨k^CVT/SCT．结果表明,反应R1,R2和R3的势垒△E^≠分别为160．69,266．61和241．63kJ／mol。R1为反应的主通道．低温下CH3S比CH2SH稳定,高温时CH2SH比CH3S更稳定．另外,速率常数计算结果显示,量子力学隧道效应在低温段对速率常数的计算有显著影响,而变分效应在计算温度段内对速率常数的影响可以忽略．     

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。     

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.

     

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.     

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。