铜基催化剂的结构、物性及其对混合碳四选择加氢反应的催化性能

 用XRD，XPS，SEM和H2－TPR等手段研究了铜基负载型催化剂的结\r\n构和物性及其对混合碳四加氢脱炔的催化性能．结果表明，在负载铜催\r\n化剂中加入一定量的Co可提高催化剂的加氢脱炔活性，而Co含量较少时\r\n加入少量的Ce也能提高催化剂的活性和选择性．Cu和Co之间存在着相互\r\n协同作用，使得活性组分在催化剂表面偏析，CuO在催化剂表面呈非晶\r\n相分散状态，催化剂颗粒粒径变小，催化剂更容易被还原，从而改善了\r\n催化剂的催化性能．     

氢化硝基苯合成对氨基酚中活性炭负载铂催化剂的新制备方法研究

采用不同还原剂（甲醛、甲酸、硼氢化钾和氢气）,或于还原Pt(IV)过程中引入少量Pt/AC(AC：活性炭)催化剂“催化”氢气分子,制备了Pt/AC催化剂。其催化氢化硝基苯制对氢基酚的反应结果表明,制备催化剂时所用的还原剂对催化剂的活性影响很大,但对反应选择性影响较小。用甲醛、甲酸和硼氢化钾还原制成的催化剂的活性皆较高;以氢气还原制得的催化剂活性较差;采用“催化”氢气还原法,可大大提高Pt/AC催化剂的活性,与传统甲醛还原法相比,甲酸和“催化”氢气还原制备Pt/AC催化剂的方法较简便、有效。     

钼催化剂上甲醇直接气相羰基化活性与吸附的关系

 制备了一系列非负载的钼催化剂，考察了催化剂上甲醇直接气相\r\n羰化活性与反应物及产物吸附的关系．结果发现，催化剂的制备方法对\r\n甲醇直接气相羰化活性的影响很明显，以纯二硫化钼试剂制备的催化剂\r\n，甲醇转化率与羰化产物乙酸甲酯的选择性最低；以三氧化钼气相还原\r\n硫化制备的催化剂，其羰化活性较低；以钼酸铵溶液经硫化铵溶液或硫\r\n化氢气体硫化制得的催化剂，其性能明显优于前两种，尤以钼酸铵经硫\r\n化铵溶液硫化制得的催化剂的性能最佳．催化剂的羰化活性明显依赖于\r\n催化剂的吸附性能，羰化活性高的催化剂不仅吸附CO的量大，而且对甲\r\n醇和乙酸甲酯的吸附量也明显较大．     

制备方法对Pd催化剂上丙烯选择性还原NO反应性能的影响

 采用三种不同方法制备了氧化铝负载的Pd催化剂．比表面积测定\r\n结果表明,与浸渍法相比,溶胶－凝胶加浸渍法和溶胶－凝胶法制备的\r\nPd／Al2O3样品具有较大的比表面积,但抗烧结性能不佳．其中采用溶\r\n胶－凝胶法制备的样品中,由于Pd分散于体相中,表面的活性位相对较\r\n少,造成催化剂在NO选择性还原反应中的活性较差;而将Pd浸渍于溶胶\r\n－凝胶法制得的Al2O3载体上所获得的催化剂比表面积较大,活性较好\r\n．添加CeO2的样品活性总体上比Pd／Al2O3样品高．其中采用溶胶－凝\r\n胶法制备的样品比表面积不大,并且XRD数据表明Al2O3和CeO2是高度分\r\n散并均匀地搀杂在一起的,不象在浸渍法制备的样品中那样以大晶粒的\r\n形式存在,因而CeO2的助剂作用没有充分体现出来,催化剂的活性比浸\r\n渍法制备的样品差一些．     

氧化铝负载钌基氨合成催化剂的制备条件及载体改性

 利用等体积浸渍法制备了氧化铝负载钌基氨合成催化剂．考察了\r\n氢氧化铝的焙烧温度，催化剂的还原温度，助剂K、Ba和Sm的添加，以\r\n及用MgO和BaO改性氧化铝载体等对催化剂活性的影响．通过XRD，N2物\r\n理吸附和CO2化学吸附等方法表征了载体的物相结构、比表面积和表面\r\n碱性．研究结果表明，氧化铝表面碱性随着氢氧化铝焙烧温度的升高而\r\n增大是催化剂活性升高的主要原因，载体比表面积的降低对催化剂活性\r\n的影响相对较小．助剂K、Ba和Sm的加入显著地提高了催化剂的活性，\r\n同时助剂Ba和Sm还减弱了强吸附氢对氮吸附的抑制作用，明显提高了催\r\n化剂的高压活性．用MgO改性氧化铝载体降低了其比表面积，但是显著\r\n地提高了载体的表面碱性和催化剂的活性．BaO改性的氧化铝载体的比\r\n表面积、表面碱性及其负载的钌基催化剂的活性随着BaO含量的增加先\r\n升高后降低，当BaO摩尔含量为7．7％时，催化剂活性最高．     

中孔分子筛HMS负载钴催化剂在费-托合成中的应用:载体HMS的孔径对钴基催化剂性能的影响

 用不同链长度的十二胺，十四胺，十六胺和十八胺等伯胺为模板\r\n剂合成了具有不同孔径大小的HMS中孔分子筛．XRD和低温氮吸附测定表\r\n明，HMS具有典型的中孔分子筛特征，且其孔径大小随HMS合成中所用模\r\n板剂链长度的增加而增加．以HMS为载体，采用孔体积浸渍法制备了负\r\n载量为7．5％的钴催化剂，在接近工业试验条件下（n（H2）／n（CO）\r\n＝2．1，GHSV＝500h－1，p＝2．0MPa，θ＝227℃）考察了载体孔径大\r\n小对费－托合成反应性能的影响．结果表明，与常规的SiO2载体相比，\r\nHMS负载钴催化剂具有更高的催化活性和C5＋选择性；而且，CO转化率\r\n，C5＋选择性及产物中的蜡油比均随着HMS载体孔径的增大而升高．以\r\n7．5％Co／HMS－18为催化剂，CO转化率为78．0％，C5＋选择性为80．\r\n8％，蜡油比为11．1．     

硫化物对Pd/树脂催化剂上异戊二烯选择加氢催化性能的影响

 在流体并流向上的气液固三相固定床反应器中考察了多种硫化物\r\n对负载Pd催化剂上异二戊烯加氢反应活性的影响．结果表明，在低温（\r\n60℃）和液相加氢条件下，硫化氢、二硫化碳、二甲基硫醚、二甲基二\r\n硫醚、硫醇及噻吩都能使强酸性树脂负载的Pd催化剂上异戊二烯加氢反\r\n应活性下降；随着硫化物含量的增加，异戊二烯加氢活性下降的程度增\r\n大．在硫的质量分数相同（8×10－6）的情况下，这些硫化物使催化剂\r\n失活程度的大小顺序为：二硫化碳＞硫化氢＞二甲基二硫醚≈乙硫醇＞\r\n二甲基硫醚＞噻吩．其中噻吩基本上不导致催化剂失活．     

沸石负载的钒络合物催化剂对烷烃氧化反应的催化性能

 将钒氧吡啶甲基络合物VO（pic）2负载于Y及ZSM－5沸石分子筛\r\n中，制备出沸石负载的钒络合物催化剂．用X射线衍射、电子自旋共振\r\n、红外光谱和元素分析等方法对催化剂进行了表征．结果表明，VO（p\r\nic）2络合物确实负载于分子筛孔道内，负载后的络合物仍保持着原来\r\n的结构．考察了催化剂对正己烷和环己烷氧化反应的催化性能，发现沸\r\n石分子筛负载的VO（pic）2络合物催化剂保留有络合物原有的催化性能\r\n，虽然催化活性有所下降，但显示出较好的形状选择性．与未负载的络\r\n合物相比，NaY和ZSM－5沸石负载的VO（pic）2络合物催化剂对正己烷\r\n氧化反应的伯醇选择性分别提高了2～3倍和5～6倍．     

制备条件对Al1P1.30Ti0.30Si0.17体系催化剂性能的影响

 从制备催化剂的原料、沉淀剂种类、铝沉淀物终点的pH值、水量\r\n及原料的加入顺序等方面考察了制备条件对AlP1．30－Ti0．30Si0．1\r\n7体系的结构及催化性能的影响．结果表明，以自制新鲜氢氧化铝为铝\r\n源，以硅溶胶为硅源，以钛酸丁酯为钛源，以氨水为沉淀剂，在pH＝6\r\n．2，c（Al3＋）＝0．64mol／L（V（H2O）＝200ml）的条件下，采用\r\n通常的沉淀方法可制备出性能优良的催化剂．催化剂的酸性是影响其催\r\n化性能的主要因素，主产物选择性与酸强度有关，酸强度高的催化剂具\r\n有较低的主产物选择性；催化剂的活性与其孔径及表面酸量有关；催化\r\n剂中的B酸中心是反应可能的活性中心．     

纳米二氧化锆催化剂上一氧化碳加氢合成异丁烯

 考察了纳米ZrO2的制备方法及Al2O3和KOH助剂的添加对ZrO2催化\r\nCO加氢合成异丁烯反应的影响．纳米ZrO2的制备方法对ZrO2的物理性质\r\n和催化性能有较大的影响．用超临界流体干燥法干燥并在流动N2气氛中\r\n焙烧制得的ZrO2催化剂对异丁烯具有较高的选择性．Al2O3和KOH助剂表\r\n现出非常优良的助剂效应，在大幅度提高催化剂对i－C4烃选择性的同\r\n时保持了和ZrO2同样高的催化活性．催化剂的酸碱性表征结果表明，酸\r\n碱性对催化剂的催化性能影响很大，催化剂上适宜的酸碱数量和酸碱比\r\n例是影响其催化CO加氢合成异丁烯性能的非常重要的因素．     

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.     

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.

     

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。     

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.     

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。     

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.     

解决能源问题的新途径——光解水制氢的研究

面对日益枯竭的能源危机,氢能是一种洁净、最有前景的替代能源。目前在各种制氢的方法中光催化分解水制氢的研究最多,光解水过程中催化剂最关键,本文对利用太阳能光解水的途径、提高光催化反应效率以及光催化剂的开发研究进行了综述。     

黄酮化合物的合成研究进展

黄酮化合物是一类具有多种生物活性的天然产物,其经典的合成方法主要为查耳酮路线和β-丙二酮路线.近年来出现了许多新技术、新方法.本文介绍了2'-羟基查尔酮的氧化关环法、黄烷酮氧化法、改进的Baker-Venkataraman法及其他合成黄酮化合物的方法.