Cu修饰的MCM—41的合成,表征及对芳烃羟化反应催化作？…

利用ＭＣＭ－４１形成过程中协同自组装特点,在合成过程中引入Ｃｕ（ＮＨ３）４＾２＋,制备出过渡金属表面修饰的纯硅介孔分子筛Ｃｕ－ＭＣＭ－４１,采用ＸＲＤ,ＩＣＰ,ＥＳＲ,Ｎ２吸附等手段确定Ｃｕ处于ＭＣＭ－４１的表面,取代了端羟基中氢的位置,与骨架桥氧和硅羟基中的氧配位,利用苯酚羟化反应为探针,考察了Ｃｕ－ＭＣＭ－４１的催化活性。结果表明,Ｃｕ－ＭＣＭ－４１具有很高的苯酚羟化活性,与ＴＳ－１分子筛的催     

CuZSM-5分子筛上苯酚羟化制苯二酚

在Ｎａ２Ｏ－ＳｉＯ２－ＣｕＯ－Ｈ２Ｏ体系中以１５％ＴＰＡＢｒ－８５％ＨＭＤＡ为模板剂合成了ＣｕＺＳＭ－５分子筛，并用ＸＲＤ，ＩＲ及ＳＥＭ等方法进行了表征，考察了ＣｕＺＳＭ－５分子筛催化苯酚与过氧化氢的羟化活性，研究了催化剂用量、反应温度、反应时间及ｎ（ＰｈＯＨ）／ｎ（Ｈ２Ｏ２）等对羟化活性的影响．     

CuZSM—5分子筛上苯酚羟化制苯二酚

在Ｎａ２Ｏ－ＳｉＯ２－ＣｕＯ－Ｈ２Ｏ体系中以１５％ＴＰＡＢｒ－８５％ＨＭＤＡ为模板剂合成了ＣｕＺＳＭ－５分子筛，并用ＸＲＤ，ＩＲ及ＳＥＭ等方法进行了表征，考察了ＣｕＺＳＭ－５分子筛催化苯酚与过氧化氢的羟化活性，研究了催化剂用量，反应温度，反应时间及ｎ（ＰｂＯＨ）／ｎ（Ｈ２Ｏ２）等对羟化活性的影响。     

八羟基喹啉铁(Ⅱ)/MCM-41对苯酚羟化的催化作用

利用ＭＣＭ－４１中孔分子筛为载体，制备了负载型八羟基喹啉铁（Ⅱ）／ＭＣＭ－４１（简记为Ｆｅ（Ⅱ）－Ｑｘ／ＭＣＭ－４１）催化剂．ＸＲＤ，ＩＲ证明八羟基喹啉铁（Ⅱ）配合物成功地负载于ＭＣＭ－４１分子筛中．考察了八羟基喹啉铁（Ⅱ）／ＭＣＭ－４１对苯酚羟化反应的催化作用，和未负载的配合物相比，苯酚的转化率、对苯二酚的选择性以及Ｈ２Ｏ２的利用率都有显著的提高．同时也探讨了温度、反应介质及介质ｐＨ值对苯酚羟化反应的影响．结果表明，随着温度的提高，苯酚的转化率增加，但温度太高，易导致副产物增多；有机溶剂不利于羟化反应的进行，水是实验条件下苯酚羟化反应的最佳反应介质；在一定程度上，ｐＨ值越低，越有利于反应活性的提高，若ｐＨ值太低，活性反而下降，ｐＨ值升高不利于苯酚羟化反应的进行．该催化剂也具有较高的稳定性．     

杂原子HMS介孔分子筛的催化脱氢和加氢脱硫性能

ＭＣＭ４１［１］和ＨＭＳ［２］等介孔分子筛对大分子的扩散阻力较小且具有良好的热稳定性,特别是在合成中可以直接将各种杂原子引入骨架,从而调变其催化性能,因此目前介孔分子筛在催化中的应用引起了各国研究者的广泛兴趣．Ｔｉ,Ｚｒ,Ｖ,Ｃｒ,Ｍｎ,Ｃｕ和Ｆｅ...     

八羟基喹啉铁（Ⅱ）／MCM—41对苯酚羟化的催化作用

利用ＭＣＭ－４１中孔分子筛为载体，制备了我载型八羟基喹啉铁／ＭＣＭ－４１催化剂。ＸＲＤ，ＩＲ证明八羟基喹吉林 铁配合物成功地负载于ＭＣＭ－４１分子筛中。考察了八羟基喹啉铁／ＭＣＭ－４１对苯酚羟化反应的催化作用，和未负载的配合物相比，苯酚的转化率，对苯二酚的选择以及Ｈ２Ｏ２的利用率都有显著的提高。     

超大孔Fe和V—Ti分子筛的合成

水热法合成了具有超大孔ＭＣＭ－４１分子筛结构的含Ｆｅ和Ｖ－Ｔｉ分子筛，通过ＸＲＤ，骨架ＩＲ，ＥＳＲ，＾２９ＳｉＭＡＳ ＮＭＲ，紫外漫反射等测试表征证实，Ｆｅ原子在ＦｅＭＣＭ－４１分子筛骨架上，Ｖ和Ｔｉ同是进入Ｖ－ＴｉＭＣＭ－４１分子筛骨架。     

内嵌型介孔分子筛的合成

用表面活性剂十六烷基三甲基氢氧化铵在溶液中形成的液晶相胶态分子团作为模板剂，同时在分子团憎水基团内部导入对乏燃料中钯离子有特效选择萃取效应的协萃剂ＴＯＰＯ－Ｐ２０４，通过表面活性剂亲水基团与易水解的有机硅酸盐阴离子之间的自组织过程，合成了内嵌型介孔分子筛固体吸附剂ＭＣＭ－ＴＰ，经ＴＥＭ，ＸＲＤ，２９Ｓｉ－ＭＡＳＮＭＲ测试，与ＭＣＭ－４１介孔分子筛有相似的孔道结构，但其晶胞参数有所增加，水热稳定性有明显的改善．用于提取乏燃料中的钯，饱和吸附Ｐｄ容量可达０．０１５ｍｍｏｌ／ｇ．     

MCM－41中孔分子筛的合成及其性质

以十六烷基三甲基溴化铵（ＣＴＡＢ）作模板剂，研究了水热体系中中孔ＭＣＭ－４１分子筛的合成条件。在Ｈ_２Ｏ／Ｓｉ介于１２～１００，Ｓｉ／Ａｌ介于１０～∞，ＣＴＡＢ／Ｓｉ介于０．０８～０．２时，可以合成出ＭＣＭ－４１分子筛。在加入煤油等混合烃的合成体系中，可以合成出孔径大于４ｎｍ的ＭＣＭ－４１分子筛。用ＸＲＤ、ＳＥＭ、Ｎ_２吸附对合成样品加以表征，证明它们具有典型的中孔分子筛特性。探针反应证明它具有中强酸中心。     

Eu（TTA）3／MCM—41介孔复合体的溶胶—凝胶法组装

利用溶胶－凝胶法将稀土的Ｅｕ（ＴＴＡ）３组装到ＭＣＭ－４１介孔分子筛的孔道中,并初步认定客体分子Ｅｕ（ＴＴＡ）３是以加合物形式包裹于表面活性剂胶束中。该法制得的介孔复合体Ｅｕ（ＴＴＡ）３／ＭＣＭ－４１,用ＸＲＤ、ＨＲＴＥＭ技术证实有短程有序的,规整的六方介孔结构和大小分布均匀的纳米晶粒。对其光致发光和荧光寿命的研究发现,与乙醇溶液中相比,Ｅｕ＾３＋的荧光寿命没有发生改变,但Ｓｔｏｋｅｓ位移却明显增大;复合体中,能量是从主体ＭＣＭ－４１传递到客体Ｅｕ（ＴＴＡ）３上。     

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。     

Acid hydrolysis of carboxymethylcellulose of low degree of substitution

Cotton cellulose was swollen in a sodium hydroxide solution and carboxymethylated by a two-bath method for different periods of time for each process. The kinetics of acid hydrolysis and the crystallinity of the swollen and carboxymethylated samples were measured. The proportion of broken bonds, rate constants for hydrolysis, and permeability of cellulose to hydrolyzing agents were calculated. The susceptibility of glycosidic linkages to acid hydrolysis was improved by carboxymethylation more than by swelling in alkali. The increased accessibility of carboxymethylcellulose to acid was regarded as a consequence of increased intra-and intercrystalline swelling and of the glycosidic bonds' weakness caused by the electron-attracting carboxymethyl group on the C-6 position.     

Estimation of Kinetic Parameters of Thermal Oxidation of Ilmenite

The aim of the presented work was the investigation of thermal oxidation of ilmenite in static air atmosphere. The investigations were carried out by use of a derivatograph (MOM, Hungary). The changes of crystallographic structure of investigated samples were identified by X-ray diffractometry on Philips PW-1710 diffractometer. In temperature above 500°C appears structure of hematite Fe₂O₃. On the basis of the thermogravimetric measurements, the contracting area and contracting volume models were found as the best fitting experimental data. This revised version was published online in August 2006 with corrections to the Cover Date.     

Mechanism of action of base-catalyzed oxygenation of phenol derivatives

Cyclopropyl derivative of 2,6-di-tert-butylphenol is synthesized as a probe to investigate the mechanism of base-catalyzed autooxidation of phenol derivatives. Our study indicates that one electron reduction of molecular oxygen from phenolate gives phenoxyl radical 3, a key intermediate of autooxidation. The coupling of phenoxyl radical and superoxide radical gives peroxylate anion 4 and produces the final epoxy alcohol adduct 6.     

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^-。     

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.

     

化学计量中不确定度评定研究进展

测量不确定度是表征合理地赋予被测量之值的分散性的参数。本文针对化学计量不确定度评定基础模型仅适用于线性模型、概率分布为正态分布或缩放位移t分布等局限,介绍了近年来不确定度评定的研究热点:蒙特卡罗方法(Monte Carlo Method,MCM),不确定度评定的来源、评定概念、评估方法及其发展过程,扩大了测量不确定度评定与表示的适用范围。     

微量钙的测定方法研究进展

介绍了1995-2006年期间测定微量和痕量钙的方法,如电感耦合等离子体-原子发射光谱法、原子吸收光谱法以及离子色谱法等的工作原理和特点,并说明了其测定微量钙的应用领域。并对微量钙的测定技术进行了展望(引用文献55篇)。     

Stages of thermal decomposition of sodium oxo-salts of sulphur

Thermal behaviour of sodium oxo-salts of sulphur: Na₂SO₄, Na₂S₂O₇, Na₂S₂O₆, Na₂SO₃, Na₂S₂O₅, Na₂S₂O₄, Na₂S₂O₃, Na₂S₃O₆ and of sulphides Na₂S and Na₂S₂ was studied on heating up to 1000°C. The experiments were performed with anhydrous compounds obtained from commercial products by recrystallisation and dehydration. The stage mechanisms of decomposition of anionic sub-lattices of the salts have been proposed basing on the Górski’s morphological classification of simple species. The thermal stability and the stage decomposition mechanisms were correlated with the structure and the potential chemical properties of the salt anions. The thermal decomposition processes were studied by means of thermal analysis, and the decomposition products were identified by means of X-ray phase analysis.