乙二胺功能化处理CNTs对NiB/CNTs催化剂性能的影响

用乙二胺功能化处理碳纳米管,增强其亲水性,有利于非晶态合金在碳纳米管负载.用化学还原法制备NiB/CNTs非晶态合金,以苯加氢探针为反应考察催化剂的活性,利用XRD、ICP、BET、TEM、TPR、TPD等方法对催化剂进行表征,结果表明乙二胺功能化处理,CNTs比表面积增大,镍的负载量增多,镍硼颗粒细化,从而提高了非晶态NiB/CNTs的催化活性,增强了其抗硫性.     

载体对非晶态NiB合金催化性能影响的比较

各种负载型非晶态NiB合金表现出优良的苯加氢催化活性.其活性与载体的表面积成正比关系,高比表面积的载体更有利于NiB合金的分散,使催化剂具有更多的活性位.TPR结果表明非晶态NiB合金负载在不同的载体上表现出不同的分散状态.与γ-Al2O3相比较,海泡石和膨润土有更高的催化活性和抗硫性能,作为催化剂载体,具有很好的应用前景.     

用原位红外光谱法研究NiB和NiP非晶态合金的还原和苯加氢反应过程

 用化学还原法制备了NiB和NiP非晶态合金催化剂,并用XRD,DSC,SEM和TEM鉴定了样品的非晶性,用ICP测定了样品的组成．在脉冲微反－色谱装置上考察了这两种催化剂催化苯加氢反应的活性．采用在线漫反射傅里叶变换红外光谱研究了这两种催化剂的还原及苯加氢反应过程．结果表明,所制备的NiB和NiP合金均为非晶态,且都是纳米尺度．NiB的粒度要比NiP小,晶化温度也比NiP低,表明Ni与B之间同Ni与P之间的相互作用不同．对苯加氢反应,NiB非晶态合金具有更大的优势,原位红外光谱结果证实催化剂的活性中心与还原态镍有关．     

碳纳米管对非晶态NiB合金催化剂性能的影响

采用化学还原法制备了非晶态NiB合金，用CNTs-1、CNTs-2、y-Al2O3作载体制备了负载型非晶态NiB合金催化剂．以乙炔选择性加氢为目标反应考察了催化活性和选择性，用TEM、TPD等方法对催化剂进行了表征．TEM结果表明，粒径为8～10nm的NiB粒子均匀分散在CNTs-1外表面，大部分粒径为12～14nm的NiB颗粒在CNTs-2内腔生长，而y-Al2O3载体未能有效提高NiB分散度．用CNTs-1将NiB负载化，明显提高了NiB催化剂乙炔加氢活性．CNTs-1、CNTs-2和y-Al2O3载体对比，CNTs-2作载体促进了催化剂对氢的吸附，减弱了乙炔的吸附，提高了加氢活性和乙烯选择性．     

非晶态合金催化剂NiB、NiB/TiO2的制备、表征及其环丁烯砜加氢催化活性的研究

分别采用化学还原法和浸渍还原法制备了系列NiB及NiB／TiO2非晶态合金催化剂，用XRD、ICP、SEM、SAED和DSC等技术对催化剂的物性进行了表征，并将其用于环丁烯砜加氢反应，研究了制备条件(镍硼摩尔比、滴加方式和金属离子浓度)对非晶态合金催化剂加氢活性的影响。结果表明，选择镍硼摩尔比为1：2，Ni^2 浓度为0．1mol／L，采用正滴加方式(将KBH4溶液滴加到Ni(NO3)2溶液中)所制得的NiB非晶态合金催化剂环丁烯砜加氢活性优于RaneyNi催化剂，对于NiB／TiO2负载型非晶态合金催化剂，镍的实际负载量达14．5％时，NiB／TiO2与NiB的环丁烯砜加氢催化活性相当。     

钐对非晶态NiB合金催化剂性能及表面性质的影响

本文采用脉冲技术以气相苯加氢为探针反应，首次研究了化学还原法制备的非晶态ＮｉＢ，ＮｉＢＳｍ合金催化剂的加氢及抗硫性能，用ＸＲＤ，ＤＳＣ和ＩＣＰ鉴定结构与组成，并用ＴＰＲ，ＴＰＤ和ＸＰＳ手段表征了钐的加入对非晶态ＮｉＢ合金催化剂表面性质的影响，结果表明，在此两种催化剂上气相苯加氢反应符合Ｌａｎｇｍｕｉｒ－Ｈｉｎｓｈｗｏｏｄ机理，活性中心位数为２，钐的加入可提高非晶态ＮｉＢ合金的热稳定性和抗硫性，其原     

负载型Ru基催化剂用于丙酮常压气相加氢

采用气相脉冲法，首次将非晶态Ru-B合金催化剂用于催化丙酮常压气相加氢反应．研究结果表明负载型Ru-B合金催化剂在较低的反应温度下表现出了很高的活性及生成异丙醇的选择性；负载在γ-Al2O3上的非晶态Ru-B合金与晶态的Ru相比，活性及异丙醇的产率都有很大提高；采用不同载体的非晶态Ru-B合金催化剂活性不同，在所选定的反应温度下，以膨润土为载体的Ru-B合金催化剂的活性与异丙醇的产率均高于以γ-Al2O3作载体的．用程序升温还原(TPR)，程序升温脱附(TPD)，等离子体发射光谱(ICP)等方法对催化剂表面性质及含量进行了表征．     

轻稀土氧化物对非晶态NiB合金催化剂的改性研究

采用脉冲技术以气相苯加氢为探针反应,首次研究了轻稀土元素Ｃｅ,Ｐｒ,Ｎｄ对化学还原法制备的非晶态ＮｉＢ合金催化剂遥加氢及抗硫性能的影响。用ＸＲＤ鉴定结构,用ＤＳＣ测定晶化温度;并用吸附ＣＯ,ＴＰＲ,ＴＰＤ等手段表征了轻稀土对非晶态ＮｉＢ合金催化剂表面性质的影响。     

载体γ-Al2O3和钐对非晶态NiB合金热稳定性的影响

用化学还原法制备了NiB、NiB/Al2O3和NiBSm/Al2O3三种催化剂，它们都呈非晶结构.用等离子耦合发射光谱仪(ICP)对催化剂组分进行了分析，采用差示扫描量热法（DSC）对三种催化剂进行了热稳定性分析.结果表明，载体的引入使非晶态NiB合金的体相组成中B的含量降低.将非晶态NiB合金负载到γ-Al2O3上,可以明显改善非晶态合金的热稳定性，少量Sm可以进一步提高晶化温度.晶化激活能数据亦表明了载体和Sm对非晶结构具有良好的稳定作用.载体和Sm可能通过不同的作用提高了非晶态合金的热稳定性.     

海泡石对非晶态NiB合金催化剂的改性研究

以常压气相苯加氢为探针反应,首次考察了酸性前后海泡石的加入对非晶态ＮｉＢ合金催化剂的加氢及抗硫性能的影响,用ＴＰＲ、ＴＰＤ表征了催化剂的表面性质,测定了酸改性前后海泡石的比表面及孔径分布,并与活性进行了关联。结果表明,加入海泡石显著地提高非晶态ＮｉＢ合金的催化活性和抗硫性;提高的幅度随制备方法的不同而异。其原因为ＮｉＢ与海泡石之间存在相互作用,改变了ＮｉＢ合金的还原性能和吸附性能,酸改性后脱镁率脱     

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.     

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。     

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.

     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

Summary of development of the theory of stability of colloids and thin films

In this review, the research of the author in the field of colloidal systems is summarized. The factors influencing colloidal stability are systematized and analyzed. Examples are presented to illustrate the practical utilization of the theory of stability of colloids and thin films.This review was prepared on the basis of the works of the author, which were awarded the State Premium for 1991 in the field of science and technology, chemistry section.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1708–1717, August, 1992.     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

氯氧化镁生成热的研究

用氧化镁氯化镁水溶液制备了8水合氯氧化镁[nMg(OH)2·MgCl2·8H2O], 并测定了其在盐酸中的溶解热, 实验结果表明, 氯氧化镁溶解热与n值呈线性关系, 根据溶解热求出5Mg(OH)2·MgCl2·8H2O和3Mg(OH)2·MgCl2·8H2O的生成热分别为-7727.1和5888.1kJ·mol^1^-。     

Thermodynamics of the formation of oxosulfides of rare-earth elements

The enthalpies of solution of several oxosulfides of rare-earth elements and the high-temperature enthalpies of oxosulfides and oxosulfates of lanthanum and yttrium were measured using solution calorimetry and high-temperature microcalorimetry techniques. Standard enthalpies of formation and some thermodynamic properties of oxosulfides and oxosulfates were calculated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2 pp. 294–297, February, 1997.     

恶臭嗅辨实验室建设探讨

针对恶臭测试的环境影响问题,提出了解决的实例方案,并对方案的要点及优缺点进行讨论,此方案在实际操作中具有较好的效果。