铂-氧化铈/聚苯胺/聚砜复合膜电极的制备及对甲醇的电催化氧化

采用电化学聚合法制备了掺杂CeO2纳米粒子的聚苯胺(PAN)/聚砜(PSF)复合膜电极,在其上电沉积铂粒子,制得了铂-氧化铈/聚苯胺/聚砜的复合膜修饰电极。 复合膜的形貌和化学组分通过冷场发射扫描电子显微镜（Cold FE-SEM）和能量散射X射线谱（EDS）进行了表征,用循环伏安法和电化学交流阻抗法考察了复合膜电极对甲醇的电催化氧化性能。 结果表明,复合膜的双层多孔结构使铂粒子与CeO2粒子在复合膜内层的多孔聚苯胺上均匀沉积,粒子平均尺寸约为80 nm;CeO2为铂质量的7%时,铂-氧化铈/聚苯胺/聚砜复合膜修饰电极对甲醇有很好的电催化氧化性能和高的稳定性。     

碱性介质中高择优取向（220）镍电极上乙醇的电氧化

碱性介质中高择优取向（220）镍电极上乙醇的电氧化;高择优取向镍电极;电沉积;乙醇;电氧化;现场红外反射光谱     

电沉积Ni/LaNiO3复合电极及其在碱性介质中的析氧性能

采用溶胶-凝胶法制备了钙钛矿型复合氧化物LaNiO3,然后将其加入瓦特镀镍液中进行复合电沉积,研究了镀液pH值和阴极电流密度对Ni/LaNiO3复合镀层组成的影响。运用扫描电镜(SEM)、能谱分析(EDS)和X射线衍射(XRD)等对复合镀层进行表征,结果表明:最佳电沉积工艺条件是镀液pH=5.8和阴极电流密度jk=90 mA.cm-2,所得的Ni/LaNiO3复合镀层中LaNiO3的质量含量约为60%。用循环伏安、稳态极化、恒电位阶跃、电化学阻抗谱等电化学技术评价了Ni/LaNiO3复合电极的析氧性能。结果表明:在5 mol.L-1的KOH溶液中,Ni/LaNiO3复合电极的起始析氧电位较镍电极负,表观活化自由能比镍电极降低约2/3,比表面积约为镍电极的55倍,析氧电催化性能得到大幅度提高。     

硫脲对镍电沉积的作用

应用循环伏安和阻抗＿电位法研究了硫脲(TU)对玻碳电极和镀镍玻碳电极上镍沉积过程的影响.结果表明,在玻碳电极上镍的电沉积呈现明显的电化学成核机理,而在镀镍玻碳电极上则无此特征.TU的存在虽阻碍了Ni晶核的形成,但却能加速晶粒的生长.     

金刚烷双席夫碱镍配合物/氧化石墨烯/玻碳电极检测胭脂红的研究

使用嵌入法和电沉积法制备了双席夫碱镍配合物/氧化石墨烯/玻碳电极,用于定量检测胭脂红含量. 通过循环伏安法、电流计时法和扫描电镜等技术对修饰电极的电化学性能和形貌进行表征,结果表明,金刚烷双席夫碱镍配合物/氧化石墨烯/玻碳电极对胭脂红氧化反应具有较高的电催化活性,提供了一种简便快捷、重现性好的检测胭脂红含量的新方法.     

CdSe/泡沫镍薄膜电极对结晶紫的光电催化降解

采用恒电位电沉积法,以泡沫镍为基底电极,制备了CdSe/泡沫镍薄膜电极,采用扫描电子显微镜、紫外可见漫反射光谱和能谱分析表征了CdSe薄膜的形貌及其组成。应用该电极研究结晶紫溶液在光电催化降解过程中的COD去除率。结果表明,以白炽灯(100 W,2只)为光源,采用电沉积30 min所得的CdSe/泡沫镍薄膜电极为工作电极,外加偏压为0.4 V(vs.SCE),0.01 mol/L NaCl为电解质,光电催化降解浓度为0.001 g/L的结晶紫溶液120 min,COD去除率达到84.3%。     

碱性介质中高择优取向（220）镍电极上丙醇的电氧化

对１．０ｍｏｌ／ＬＮｉＳＯ４和０．５ｍｏｌ／Ｌ Ｈ３ＢＯ３体系，控制电位为一１．２５Ｖ，沉积６０ｍｉｎ，制得高择优取向镍电极。该镍电极经Ｘ射线衍射测定其织构度ＴＣ２２０为９２％。采用循环伏安法研究了１ｍｏｌ／Ｌ ＮａＯＨ溶液中高择翁取向镍电极上丙醇的电催化氧化机理有活性，结果表明：高择优取向镍电极对正丙醇的电催化活性高，对异丙醇的电催化活性小；推导出正丙醇的电氧化动力学方程，运用稳态极经曲线测定了     

硼化镍氢电极催化剂研究

比较了各种后处理方法对湿法制备的硼化镍催化剂的化学、物理和电化学性能的影响,指出必须将硼化镍的制备过程与电极的制备过程统一起来考虑。在热处理过程中有控制地实现“冒烟”过程,可以得到能适应烧结式防水电极制备工艺的硼化镍。制得的电极电化学性能和工作寿命都比较好。     

用旋转圆盘电极制备碲化镉光电极

有关电沉积法制备碲化镉薄膜的报道中,碲化镉薄膜大多在静止的金属片上沉积.最近,我们用旋转圆盘电极(RDE)研究了电沉积碲化镉过程的动力学,发现在RDE上沉积的碲化镉具有更好的光电化学性能. 我们设计了一种可换盘的RDE.沉积基片为一镍盘(直径6mm,厚0.2mm),用导电银     

一个简单易行的物理化学综合型实验

介绍一个物理化学综合型实验,通过该实验可以了解用电沉积方法制备新材料的基本技术以及高耐蚀性材料的发展现状,掌握镍电极的制备方法及耐蚀性能;了解各种电化学测试技术在探索金属离子电沉积机理和考察金属镀层耐蚀性能上的应用。实验内容设置新颖且具有较强的探索性,有利于提高学生的综合素质和科研能力。     

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.     

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。