纳米Fe2O3的制备及其对高氯酸铵热分解的催化性能

 用两相体系方法制备了纳米Fe2O3，并用X射线衍射、红外光谱和粒度分析对其结构进行了表征．结果表明，当有机溶胶的pH＝6，油酸与Fe3＋的摩尔比为1∶3．5时，Fe（OH）3在油相中的萃取率可高达90％，将有机溶胶在120℃回流8h后可得到非晶态、窄粒度分布的纳米Fe2O3粒子，其粒径在12nm左右．分别采用恒容燃烧热和差热分析研究了纳米Fe2O3对高氯酸铵热分解的催化性能．结果表明，在模拟固体推进剂中分别加入4．7％微米Fe2O3和4．7％纳米Fe2O3后，恒容燃烧热分别提高了2350．84和5095．70J／g．在高氯酸铵中加入5％微米Fe2O3可使高氯酸铵两个放热峰的出现分别提前1．10和62．25℃，而加入5％纳米Fe2O3时分别提前61．89和118．82℃，这说明纳米Fe2O3的催化活性优于微米Fe2O3．     

纳米Fe2O3/高氯酸铵复合粒子的制备及其热分解性能研究

用溶剂-非溶剂法制备了纳米Fe2O3／高氯酸铵(AP)复合粒子，并用TEM，SEM，XRD和ICP对其进行了表征．为了研究纳米复合粒子中纳米Fe2O3对AP热分解的催化性能，将相同比例的微米Fe2O3和纳米Fe2O3与AP分别简单混合后作对比，并用DTA对三种样品进行了热分析．结果表明，三种样品中的Fe2O3粒子都能催化AP的热分解；但纳米Fe2O3粒子的催化性能优于微米Fe2O3粒子，纳米Fe2O3／AP复合粒子中纳米Fe2O3对AP的催化性能优于纳米Fe2O3与AP简单混合物．与纳米Fe2O3与AP简单混合的样品相比，纳米复合粒子中的AP高温分解峰温降低20．1℃，低温分解峰几乎消失，表观分解热由850．2J／g提高到1080．8J／g．证明纳米Fe2O3与AP的复合处理能显著提高纳米Fe2O3对AP热分解的催化性能．并用不同样品中AP热分解的动力学参数对所得结果进行了理论分析．     

纳米Cu2O的制备及其对高氯酸铵热分解的催化性能

 以Cu(NO3)2和NaOH为原料,以水合肼为还原剂,通过沉淀法在室温下制备了纳米Cu2O. 采用X射线衍射、透射电镜和X射线光电子能谱等手段对产物进行了表征,并用热分析法考察了不同形貌的纳米Cu2O对高氯酸铵热分解的催化作用. 结果表明,通过改变NaOH溶液的加入量可分别得到长针形和多边形的纳米Cu2O. 通过调节反应物浓度可以将纳米Cu2O粒径控制在19～68 nm. 不同形貌的纳米Cu2O均能强烈催化高氯酸铵的热分解,其中分散性良好的多边形纳米Cu2O的催化活性较高,添加2%的多边形纳米Cu2O可使高氯酸铵的高温分解温度降低103 ℃,分解放热量由590 J/g增至1350 J/g.     

草酸钴原位催化高氯酸铵热分解的DSC／TG-MS研究

采用差示扫描量热/热分析-质谱(DSC/TG-MS)联用技术研究了草酸钴对高氯酸铵的原位催化. 结果表明,草酸钴原位分解生成的钴氧化物对高氯酸铵有较强的催化作用,添加2%的草酸钴使高氯酸铵的分解温度降低104 ℃, 分解放热量从655 J/g增大到 1 469 J/g. 分解的气相产物主要有H2O, NH3,O2,HCl,Cl2,NO,N2O和NO2. 由于氧在新生态的纳米钴氧化物表面形成过氧化活性离子(O-2), 使氨氧化在钴氧化物的过氧化表面活性中心进行,加速了高氯酸铵的热分解,使其表观放热量大幅度增加.     

纳米LaCoO3的制备及其对高氯酸铵分解的催化性能

以硝酸镧和硝酸钴为原料,通过硬脂酸法制备了纳米LaCoO3。采用红外光谱、X射线衍射、透射电镜等测试手段对产物进行了表征,并用热分析法考察了不同含量的纳米LaCoO3对高氯酸铵热分解的催化作用。结果表明,在600℃下可获得结晶良好的钙钛矿型纳米LaCoO3,粒径约40-60 nm。纳米LaCoO3能强烈催化高氯酸铵的热分解,催化作用随着LaCoO3含量的增加而增强。添加5%的纳米LaCoO3可使高氯酸铵的高温分解温度下降116℃,分解放热量也由2%时的1390 J·g^-1增至1600 J·g^-1。     

SiO_2/Co_3O_4核壳催化剂对AP热分解的催化性能研究

采用改良的St觟ber法制备粒径约为200 nm的单分散球形SiO2颗粒,以此为内核,分别通过液相沉淀法和尿素均匀沉淀法制备包覆形式不同的新型SiO2/Co3O4核壳式纳米催化剂。采用X-射线衍射分析(XRD)、透射电子显微镜(TEM)、红外光谱分析(IR)、拉曼光谱分析(Raman)、BET比表面积测试等手段对产物进行表征,利用差式扫描量热仪(DSC)考察SiO2/Co3O4复合物对高氯酸铵(AP)热分解反应的催化作用,探讨不同包覆形式对其催化活性的影响。结果表明,两种方法制备得到的SiO2/Co3O4复合物分别为层包覆和粒子包覆,比表面积大,具有明显的核壳结构,且粒子包覆形式的SiO2/Co3O4对AP热分解反应的催化效果最好,使AP的高温分解温度降低了110℃,放热量增加了662 J·g-1。     

纳米Co-B非晶态合金对高氯酸铵分解的催化性能

 利用化学还原法制备了纳米 Co-B 非晶态合金,并用透射电镜、X射线衍射、差示扫描量热和N2吸附表面积测试等技术对样品进行了表征. 运用差热分析研究了纳米 Co-B 非晶态合金对高氯酸铵(AP)分解的催化性能. 结果表明,加入 Co-B 非晶态合金后AP的高低温放热峰相连,合并成一个高而大的放热峰,且峰温有很大程度的降低, 这说明纳米 Co-B 非晶态合金对AP热分解有很好的催化活性. 同时, Co-B 非晶态合金能使AP的表观分解热显著增大.     

Y2O3纳米粒子/碳纳米管复合体的制备及其催化高氯酸铵热分解

采用化学液相沉淀法制备Y2O3纳米粒子/碳纳米管复合体(Y2O3/CNTC),利用扫描电镜(SEM)和X 射线光电子能谱(XPS)对其结构和成分进行了表征. 结果表明, Y2O3纳米粒子能负载在碳纳米管上,且负载效果较好. 采用差热分析研究了Y2O3/CNTC 对高氯酸铵热分解的催化性能, 结果表明, Y2O3 /CNTC 可显著降低高氯酸铵(AP)的高温分解峰温,表现出对AP 高温分解良好的催化性能. 相同量的Y2O3/CNTC 和纯Y2O3纳米粒子进行对比, Y2O3 /CNTC表现出更强的催化性能.当Y2O3/CNTC的质量分数为4%时,使AP的高温分解峰温提前131.14C[deg].     

过渡金属二取代三元杂多酸盐的制备和表征

在水中由Na2 WO4 ·2H2 O ,Na2 MoO4 ·2H2 O和KH2 PO4 ·2H2 O反应生成具有半Dawson结构的钨钼混配杂多阴离子Na9PW6Mo3O34 ·1 0H2 O。以阴离子和过渡金属硝酸盐为原料在水溶液中合成了一系列过渡金属二取代的具有Keggin结构的杂多酸四丁基铵盐 [TBA]4 Hn[PW7Mo3M2 O38(H2 O) 2 ]·C3H6O(n =1 ,M =Fe3+;n =3,M =Mn2 +,Co2 +,Ni2 +,Cu2 +) ,用元素分析和波谱进行了表征。     

形貌可控的四氧化三钴溶剂热合成及反应机理

采用溶剂热法合成了纯相立方晶型四氧化三钴. 用聚乙二醇作分散剂, 调整溶剂正丁醇和水的比例, 可实现对纯相Co3O4的形貌和尺寸大小的控制. 采用IR, XRD, TG-DTA 和TEM 等方法跟踪反应过程, 对溶剂热法合成Co3O4的反应机理进行了研究. 实验表明合成Co3O4的反应机理分为两步: Co(OH)2-x ·(NO3)x被氧化为Co0.81IICo0.19III(OH)2.11(NO3)0.08·0.43H2O; 该氧化产物进而缓慢转化成Co3O4.     

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。     

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.     

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.     

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。     

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^-。     

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.     

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.     

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。     

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.