不同粒径氧化铜的制备及其氢还原动力学研究

以CuSO4.5H2O和NaOH为原料制备0.1mol·L-1CuSO4溶液和4mol·L-1NaOH溶液,采用沉淀法制备Cu(OH)2纳米粉末,然后分别在200℃,500℃,900℃温度下分解Cu(OH)2得到不同粒度的氧化铜粉体.在氢气中,以15℃.min-1升温速率,用SDT2960Simulta-neousDSC-TGA差热-热重分析仪测定TG-DTA曲线,并进行动力学计算.结果表明:氧化铜粉体的形貌近似为球形,粒径分别为50,150,400nm;DTA峰值温度分别为258.90℃,279.17℃,364.80℃,随粒径的增大而提高;表观活化能分别为173.39,461.54,534.80kJ·mol-1,随粒径的增大而增大;频率因子分别为1.15×1018,2.49×1045,2.54×1045,随粒径的增大而增大;反应级数分别为1.16,1.15,1.03,随粒径的增大而减少.     

粒度可调纳米CuO的制备及其表面硫化研究

用Cu(NO3)2.3H2O为原料,25%氨水为配位剂,用NaOH做沉淀剂,在不同醇-氨水体系中用配位沉淀法制备粒径可调的纳米CuO。通过热重差热分析法(TG-DTA)分析前驱体的组成并得到煅烧最佳温度。在制备前驱体过程中,探究了反应体系溶剂分别为乙醇、正丁醇、正辛醇时对产物粒径的影响,实验结果表明:随着醇溶剂中碳链的增长,得到纳米CuO的比表面积依次增大,粒度依次减小。将纳米CuO与硫单质混合,在通入氮气的管式炉中以200℃加热90 min,可以得到表面硫化的CuO(CuO/CuS),利用X-射线粉末衍射(XRD)和红外吸收光谱(FT-IR)对纳米CuO和CuO/CuS进行表征。最后将纳米CuO和CuO/CuS分别对乙基黄原酸钾进行吸附,结果表明CuO/CuS对乙基黄原酸钾吸附能力明显增强,进而证明氧化铜表面发生了硫化。     

粒度可调纳米CuO的制备及其表面硫化研究

用Cu(NO₃)₂·3H₂O为原料,25%氨水为配位剂,用NaOH做沉淀剂,在不同醇-氨水体系中用配位沉淀法制备粒径可调的纳米CuO。通过热重差热分析法(TG-DTA)分析前驱体的组成并得到煅烧最佳温度。在制备前驱体过程中,探究了反应体系溶剂分别为乙醇、正丁醇、正辛醇时对产物粒径的影响,实验结果表明:随着醇溶剂中碳链的增长,得到纳米CuO的比表面积依次增大,粒度依次减小。将纳米CuO与硫单质混合,在通入氮气的管式炉中以200 ℃加热90 min,可以得到表面硫化的CuO(CuO/CuS),利用X-射线粉末衍射(XRD)和红外吸收光谱(FT-IR)对纳米CuO和CuO/CuS进行表征。最后将纳米CuO和CuO/CuS分别对乙基黄原酸钾进行吸附,结果表明CuO/CuS对乙基黄原酸钾吸附能力明显增强,进而证明氧化铜表面发生了硫化。     

吸附法制备CuO-Ag/SiO2纳米复合物

利用吸附法原位制备CuO/SiO2、CuO-Ag/SiO2纳米复合物,研究了不同吸附质体系中预负载的纳米Ag粒子对CuO的影响。结果表明:Ag粒子对CuO的影响因吸附质的不同而不同。以Cu(Ac)2为吸附质,纳米Ag几乎没有影响;以NaOH为吸附质,纳米Ag使得CuO的晶粒粒径增大。这一结果与铜物种对Ag晶粒粒径的影响规律完全不同。通过比较不同吸附质的吸附行为,Cu(OH)2与硅胶表面的相互作用被认为是导致这一现象的原因。     

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.     

反应物的相间分配对吸附相技术制备纳米CuO过程的影响

以SiO2表面的富水吸附层为纳米反应器制备CuO纳米粒子. 不同水量下的吸附量测定、溶剂置换和反应后吸附对比实验结果表明, SiO2表面存在吸附水层, 并且该吸附水层是反应的主要场所. 根据吸附数据, 认为Cu2+在体系中具有三区域浓度分布特点, 体系中水浓度和氢氧化钠浓度的增加均会使得Cu2+向吸附层区域迁移. XRD分析结果表明, 反应温度的升高和NaOH浓度的增大有利于生成更小的CuO晶粒, 其中温度的升高使吸附层厚度减小, 限制了晶粒生长; NaOH浓度的增大则会增大层内溶质过饱和度, 导致晶核形成速率加快.     

纳米CuO的制备及对NH4ClO4热分解的催化性能

研究了快速液相沉淀条件对纳米CuO结构和形貌的影响。并用热分析法考察了不同形貌的纳米CuO对高氯酸铵(AP)分解的催化作用。结果表明,当反应物Cu(NO₃)₂和NaOH的浓度均增大到1.00mol·L^-1或者反应介质乙醇和水的体积比增大到3∶1时,纳米CuO(111)晶面的XRD峰强度弱于其(111)晶面的XRD峰强度;用Na₂CO₃作沉淀剂可获得平均粒径11nm的球形CuO,但团聚严重,添加聚乙二醇(PEG)可改善其分散性。不同形貌的纳米CuO均能强烈催化AP的分解,其中分散性良好的球形纳米CuO,催化活性最强,可使AP的高温分解温度降低99.13℃,分解放热量由590.12J·g^-1增至1380J·g^-1。     

氢氧化镁纳米片的合成及其润滑性能的研究

以硫酸镁和氢氧化钠为原料,油酸为表面修饰剂,采用原位合成的方法制备出了疏水性的Mg(OH2)纳米片.研究了反应温度、反应物浓度等因素对氢氧化镁纳米片平均粒径的影响.用X-射线粉末衍射(XRD)、红外(IR)和热重(DTA-TGA)及扫描电子显微镜(SEM),对制备出的Mg(OH)2纳米片的结构和形貌进行了表征,证实制备出的Mg(OH)2纳米片具有良好分散性,纳米片尺度为200～300nm,厚度10nm.摩擦实验证明Mg(OH2)纳米片可以作为润滑油中的添加剂来应用.     

叶状Cu（OH）2的合成及其向带有纳米孔的CuO的转化

通过乳液界面反应法,用以Span80(sorbitan monooleate)作为稳定剂的乳液体系控制合成了叶状Cu(OH)2单晶.通过热处理,可以得到表面有纳米孔的CuO,且保持了原有的叶状形貌.通过X射线衍射(XRD)、Fourier红外光谱(FTIR)、扫描电镜(SEM)和透射电镜(TEM)观测了其形貌和结构特征.实验结果表明,叶状Cu(OH)2为单晶,且沿[111]晶面定向生长.孔的形成是由于相转变过程中Cu(OH)2失去H2O分子所致.通过观测不同反应时间产物的形貌,深入探讨了叶状Cu(OH)2纳米结构的组装机理.整个组装过程是由能量高的颗粒状纳米粒子通过端部取向连接定向生长而得到能量相对较低的叶状结构.并且得到的CuO的紫外光谱相对于其块体材料发生了蓝移,显示出比较大的禁带宽度.     

叶状Cu(OH)2的合成及其向带有纳米孔的CuO的转化

通过乳液界面反应法, 利用以Span80(sorbitan monooleate)作为稳定剂的乳液体系控制合成了叶状Cu(OH)2单晶. 通过热处理, 可以得到表面有纳米孔的CuO, 且保持了原有的叶状形貌. 通过X射线衍射(XRD)、Fourier红外光谱(FTIR)、扫描电镜(SEM)和透射电镜(TEM)观测了其形貌和结构特征. 实验结果表明, 叶状Cu(OH)2为单晶, 且沿[111]晶面定向生长. 孔的形成是由于相转变过程中Cu(OH)2失去H2O分子所致. 通过观测不同反应时间产物的形貌, 深入探讨了叶状Cu(OH)2纳米结构的组装机理. 整个组装过程是由能量高的颗粒状纳米粒子通过端部取向连接定向生长而得到能量相对较低的叶状结构. 并且得到的CuO的紫外光谱相对于其块体材料发生了蓝移, 显示出比较大的禁带宽度.     

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.