烯烃加氢催化剂—聚丙烯腈-钯络合物

近年来出现了用过渡金属化合物和具有官能团的高聚物络合的所谓高分子催化剂.这种催化剂在催化某些反应上具有活性高,选择性好,容易分离及反应条件温和等优点.因此引起人们的重视. 我们用聚丙烯腈为配位体与带结晶水的氯化钯制备了聚丙烯腈-钯络合物.该络合物在催化庚烯-1的加氢时显示良好的催化活性,并且催化活性明显地受到络合物中N/Pd     

高分子膦-钯络合催化剂的氢化催化活性和稳定性的考察

本文报道高分子膦-钯络合催化剂的合成及对催化剂催化加氢的活性、稳定性进行考察的结果。与文献对比表明,高分子膦-钯络合催化剂具有良好的稳定性和催化活性,膦化物不失为一类优良的配位体。     

含氨基酸侧链的有机硅高分子催化剂——Ⅸ.聚γ-(甘-色二肽基)丙基硅氧烷钯催化剂的合成、加氢活性及结构表征

本文报道了不同N/Pd摩尔比的聚γ-(甘-色二肽基)丙基硅氧烷钯催化剂的合成及对烯烃和硝基苯的加氢活性.催化剂的结构表征说明,其活性中心的组成可能是氨基酸配体的羧基与PdCl_2的络合.这种催化剂对丙烯腈和苯乙烯有较高的加氢活性,而对硝基苯的氢化没有催化活性.并研究了溶剂和温度对加氢活性的影响.     

硅胶负载聚乙烯吡啶-聚[苯乙烯-顺丁烯二酸]-钯催化剂的结构研究

利用X-光电子能谱、紫外-可见光谱、电子显微镜等技术研究了硅胶负载的聚乙烯吡啶-聚[苯乙烯-顺丁烯二酸]-钯催化剂的结构.发现催化剂中活性组分除钯(0)外,还存在少量钯(Ⅱ).第二种高分子的存在可以影响钯(Ⅱ)的相对含量.催化剂中钯以很小的粒子均匀分布在载体上,因此具有良好的催化加氢性能.     

硅胶负载的双高分子-钯催化剂的研究——Ⅰ.硅胶负载的聚[4(2)-乙烯吡啶]-聚[苯乙烯-顺丁烯二酸]-钯催化剂的合成及其催化加氢性能

 合成了硅胶负载的聚(4-乙烯吡啶)或聚(2-乙烯吡啶)-聚(苯乙烯-顺丁烯二酸)-钯催化剂(P4VP-PSM-Pd/SiO₂和P2VP-PSM-Pd/SiO₂),研究了合成条件、组成等对其催化性能的影响及对丙烯酸甲酯的催化加氢性能。发现,同时含两种高分子的催化剂比只含一种高分子的催化剂具有较高的催化活性,催化剂在常温常压下对丙烯酸甲酯的氢化反应具有很高的催化活性和选择性,且能重复使用,表现出良好的稳定性。同时还研究了其它因素对催化剂性能的影响。     

聚苯乙烯邻氨基苯甲酸负载钯催化剂的加氢性能研究

含有双配位基的聚苯乙烯邻氨基苯甲酸与钯络合物反应制得螫合的配位高分子钯催化剂。用甲醇-水(pH=12)还原可得晶粒分布均匀的胶态钯催化剂,它们对烯烃的加氢具有良好的催化作用。研究表明,钯络合物上原有配体的给予性常数(E_n)与负载后络合催化剂的加氢活性具有良好的线性关系,金属粒径为40—50A的催化剂对己烯-1的加氢活性最高。本文还研究了溶剂极性,载体孔结构及底物对催化剂活性的影响。     

聚γ—（乙二胺基）丙基硅氧烷负载的钯,镍双金属催化剂研究

本工作制取了聚γ-(乙二胺基)丙基硅氧烷〔SiO_2 Si-O-Si-(CH_2)_3NHCH_2CH_2NH_2〕负载的钯、镍双金属催化剂及相应的单金属催化剂。XPS测定表明,载体中的N与Pd~0、PdCl_2、NiCl_2之间产生络合。文中比较了双金属催化剂对癸烯-1、丙烯酸、环己烯、苯乙烯和硝基苯的加氢活性,研究了双金属催化剂,单金属催化剂及混合催化剂对环己烯的加氢活性,讨论了温度对双金属催化剂催化活性的影响。     

树枝状钯纳米结构的控制合成及硝基苯加氢反应的催化活性

以氯钯酸为前驱体, 苯甲醇为还原剂和溶剂, 十六烷基吡咯烷酮(PVP)为稳定剂, 在微波辐射下制备了分散均匀、形貌均一的树枝状钯纳米结构. 产物用透射电子显微镜(TEM), X射线粉末衍射(XRD), X射线光电子能谱(XPS)进行了表征, 表明所制备的Pd纳米颗粒呈树枝状, 形貌单一, 分散均匀, 是由许多近似圆形的小颗粒自组装而成的二级结构. 对树枝状钯催化硝基苯加氢反应进行探究, 表明树枝状钯的催化活性比市售的钯碳催化剂的催化活性高.     

聚苯胺对钯催化甲酸电氧化反应的促进作用

钯基纳米材料是甲酸电氧化反应的优良催化剂.本工作制备了两个系列钯基催化剂,并考察了聚苯胺对钯上甲酸电氧化反应的助催化作用.一种是以聚苯胺为基底,在其表面电沉积钯纳米粒子,制得nPANI/Pd催化剂(n表示聚合苯胺的循环数);另一种是直接在商业Pd/C催化剂表面电聚合苯胺,制得Pd/C/nPANI催化剂.结果显示,聚苯胺单独存在时对甲酸电氧化反应没有催化活性,但其可对钯上甲酸电氧化反应呈现明显的促进作用,且促进作用与聚苯胺的厚度(聚合循环数)密切相关.在两个系列催化剂中,15PANI/Pd和Pd/C/20PANI显示出最高的催化性能.15PANI/Pd中钯的质量比催化活性是纯钯催化剂的7.5倍; Pd/C/20PANI中钯的质量比催化活性和本征催化活性分别是商业Pd/C催化剂的2.3和3.3倍.钯催化性能的提升与聚苯胺和钯纳米粒子间的电子效应有关.     

胶原纤维接枝多酚负载纳米钯的制备及其对硝基苯加氢的催化特性

以胶原纤维(CF)接枝表棓儿茶素棓酸脂(EGCG)为载体,制备了新型非均相钯(Pd)纳米催化剂(CF-EGCG-Pd).EGCG作为"桥分子"不仅对Pd纳米颗粒具有锚定作用,而且能控制Pd纳米颗粒的大小及分布.通过SEM、TEM、XRD、XPS对该催化剂的形貌和物理特性能进行了表征,发现该催化剂具有规整的纤维结构,在胶原纤维的外表面形成了高分散的平均粒径在3.8 nm的Pd纳米颗粒.将该催化剂用于硝基苯液相催化加氢反应,结果表明在308 K和1.0 MPa氢压下,硝基苯转化速率(TOF)达到34.13 mol·mol-1·min-1,苯胺选择性为100%,催化剂重复使用3次其催化活性基本不变.     

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.     

探究“铁的锈蚀条件”实验创新设计

设计了铁的锈蚀实验,说明了铁钉的处理方法,增加了温度、酸、碱的影响条件,实现了铁跟蒸馏水及空气中氧气快速反应而生锈,使实验在5 min左右就能够得到准确的结果。