对叔丁基甲苯的直接电解氧化

由对叔丁基甲苯合成对叔丁基苯甲醛,主要有化学氧化法、空气(或氧气)催化氧化法和电化学氧化法。化学氧化法通常使用二氧化锰作氧化剂,在浓硫酸中氧化合成对叔丁基苯甲醛。此法的主要缺点是产生大量的硫酸锰,需回收处理。另外,浓硫酸介质腐蚀设备且对环境有一定影响。空气催化氧化     

烷基对蒽衍生物在水-乙腈中用硝酸铈铵氧化机理的影响

在水-乙腈混合溶剂中用(NH~4)~2Ce(NO~3)~6氧化烷基蒽. 甲基, 乙基和环丙基蒽经历氧化-水解-氧化-水解-消除-氧化-去质子历程, 得到蒽环氧化产物, 消除烷基(或氢原子)的可能顺序是:H＞CH~3＞C~2H~5. 当蒽环的1,9-位连着1,2-亚乙基桥时, 却经由氧化-去质子-氧化水解-氧化(或消除)历程, 得到侧链氧化产物. 烷基的本质对多核芳烃的氧化机理有显著的影响.     

Pt及其修饰电极上乙醇吸附和氧化的CV和EQCM研究

运用电化学循环伏安和石英晶体微天平研究了乙醇在Pt电极和以Sb,S吸附原子修饰的Pt(Pt/Sbad和Pt/Sad)电极上的吸附和氧化过程。结果表明乙醇的氧化与电极表面氧物种有着极其密切的关系。Pt电极表面Sb吸附原子能在较低的电位下吸附氧,可显著提高乙醇电催化氧化活性。相反,Pt电极表面S吸附原子的氧化会消耗表面氧物种,抑制了乙醇的电氧化。本文从表面质量变化提供了吸附原子电催化作用的新数据。     

Pt及其修饰电极上甲醇吸附和氧化的CV和EQCM研究

运用电化学循环伏安和石英晶体微天平 (EQCM )研究了 0 .1mol·L- 1H2 SO4 溶液中甲醇在Pt电极和以Sb ,S不可逆吸附原子修饰的Pt(Pt/Sbad和Pt/Sad)电极上的吸附和氧化过程 .结果表明甲醇的氧化与电极表面氧物种有着极其密切的关系 .Pt电极表面Sb吸附原子能在较低的电位下吸附氧 ,可显著提高甲醇电催化氧化活性 .与Pt电极相比较 ,Sb吸附原子修饰的Pt电极使甲醇氧化的峰电位负移了 0 .13V .相反 ,Pt电极表面S吸附原子的氧化会消耗表面氧物种 ,抑制了甲醇的电氧化 .本文从表面质量变化提供了吸附原子电催化作用的新数据     

Thermal oxidation of isotactic polypropylene synthesized with a metallocene catalyst

The mechanism and kinetics of thermal oxidation of metallocene PP are investigated. It is shown that the rate of oxidation of the samples synthesized at a high temperature (40–70°C) is higher than that of the samples synthesized at a low temperature (20 and 30°C). The composition of oxidation products of PP samples; the kinetics of the accumulation of these products; and changes in structural, thermal, and thermophysical parameters during oxidation are analyzed in detail. Our data indicate that the oxidation of low-temperature samples and the oxidation of high-temperature samples obey different mechanisms. The oxidation of low-temperature samples corresponds to the radical-chain process, in which the intramolecular transfer of kinetic chains prevails. High-temperature samples are characterized by the intermolecular transfer of oxidation kinetic chains, which leads to the degradation of macromolecules. It is inferred that the rate and mechanism of thermal oxidation are determined by the microstructure of polymer chains.     

Nanosecond redox equilibrium method for determining oxidation potentials in organic media

A general, nanosecond equilibrium method is described for determining thermodynamically meaningful oxidation potentials in organic media for compounds that form highly reactive cation radicals upon one-electron oxidation. The method provides oxidation potentials with unusually high precision and accuracy. Redox ladders have been constructed of appropriate reference compounds in dichloromethane and in acetonitrile that can be used to set up electron-transfer equilibria with compounds with unknown oxidation potentials. The method has been successfully applied to determining equilibrium oxidation potentials for a series of aryl-alkylcyclopropanes, whose oxidation potentials were imprecisely known previously. Structure-property trends for oxidation potentials of the cyclopropanes are discussed.     

Selective oxidation on metallic carbon nanotubes by halogen oxoanions

Chlorine oxoanions with the chlorine atom at different oxidation states were introduced in an attempt to systematically tailor the electronic structures of single-walled carbon nanotubes (SWCNTs). The degree of selective oxidation was controlled systematically by the different oxidation state of the chlorine oxoanion. Selective suppression of the metallic SWCNTs with a minimal effect on the semiconducting SWCNTs was observed at a high oxidation state. The adsorption behavior and charge transfer at a low oxidation state were in contrast to that observed at a high oxidation state. Density functional calculations demonstrated the chemisorption of chloro oxoanions at the low oxidation state and their physisorption at high oxidation states. These results concurred with the experimental observations from X-ray photoelectron spectroscopy. The sheet resistance of the SWCNT film decreased significantly at high oxidation states, which was explained in terms of a p-doping phenomenon that is controlled by the oxidation state.     

The kinetics of oxidation of bilirubin and ascorbic acid in solution

The results of a comparative study of the oxidation of bilirubin, ascorbic acid, and their mixture in aqueous solutions under the action of air oxygen and hydrogen peroxide are presented. The observed and true rate constants for the oxidation reactions were determined. It was shown that the oxidation of tetrapyrrole pigment occurred under these conditions bypassing the stage of biliverdin formation to monopyrrole products. Simultaneous oxidation of bilirubin and ascorbic acid was shown to be accompanied by the inhibition of ascorbic acid oxidation by bilirubin, whereas ascorbic acid itself activated the oxidation of bilirubin.     

Pt和Sb、S吸附原子修饰的Pt电极上正丙醇氧化的CV和EQCM研究

运用电化学循环伏安法和石英晶体微天平研究了正丙醇在Pt电极和以Sb、S吸附原子修饰的Pt（Pt/Sbad和Pt/Sad）电极上的吸附和氧化过程.从电极表面质量变化角度指出正丙醇的氧化与电极表面氧物种有着极其密切的关系.Pt电极表面Sb吸附原子能在较低的电位下吸附氧，可显著提高正丙醇电催化氧化活性，与在Pt电极上相比较,正丙醇氧化的峰电位负移了0.29 V,峰电流增加了近2倍.相反,Pt电极表面S吸附原子的氧化会消耗表面氧物种，饱和吸附S原子的Pt电极上正丙醇的电氧化受到抑制.本文从表面质量变化提供了吸附原子电催化作用的新数据.     

A study of the oxidation of titanium hydride powder by measurements of its electrical resistance

The oxidation of titanium hydride powder by air oxygen and the influence of oxidation conditions on the degree of oxidation of hydride particles, specific gas content in the powder, and kinetics of its thermal decomposition were studied. The resistometry method was used to determine the effective activation energy of oxidation of titanium hydride by air oxygen. The content of the surface nonconducting phase formed by titanium oxide and oxohydride films under various oxidation conditions was estimated.     

Pt电极上Sb，S吸附原子对正丁醇电催化氧化性能的影响

运用电化学循环伏安和石英晶体微天平研究了0.1 mol/L H2SO4 溶液中正丁醇（1-BL）在Pt电极和以Sb，S吸附原子修饰的Pt（Pt/Sbad和Pt/Sad）电极上电催化氧化过程。从电极表面质量变化表明正丁醇的氧化与电极表面氧物种有着极其密切的关系。Pt电极表面Sb吸附原子能在较低的电位下吸附氧，可显著提高正丁醇电催化氧化活性。与Pt电极相比较，Sb吸附原子修饰的Pt电极使正丁醇氧化的峰电位负移了0.33 V，峰电流增大了近一倍。相反，Pt电极表面S吸附原子的氧化会消耗表面氧物种，抑制了正丁醇的电氧化。本文从表面质量变化提供了吸附原子电催化作用的新数据。     

Recent Progress in Direct Partial Oxidation of Methane to Methanol

The direct conversion of methane to methanol has attracted a great deal of attention for nearly a century since it was first found possible in 1902, and it is still a challenging task. This review article describes recent advancements in the direct partial oxidation of methane to methanol. The history of direct oxidation of methane and the difficulties encountered in the partial oxidation of methane to methanol are briefly summarized. Recently reported developments in gas-phase homogeneous oxidation, heterogeneous catalytic oxidation and liquid phase homogeneous catalytic oxidation of methane axe reviewed.     

Pt电极上吸附原子对仲丁醇电催化氧化性能的影响

运用电化学循环伏安和石英晶体微天平研究了HClO4溶液中仲丁醇在Pt电极及以Sb和S吸附原子修饰的Pt(Pt/Sbad和Pt/Sad)电极上的电催化氧化过程 .从电极表面质量变化可以看出 ,仲丁醇的氧化与电极表面的氧物种有着极其密切的关系 .Pt电极表面Sb吸附原子可在较低的电位下吸附氧 ,明显提高仲丁醇的氧化活性 .与Pt电极相比 ,Sb吸附原子修饰的Pt电极使仲丁醇氧化的峰电位负移约 10 0mV .相反 ,Pt电极表面S吸附原子的氧化会消耗表面氧物种 ,抑制仲丁醇的氧化 .从电极表面质量变化提供了吸附原子电催化作用的数据     

钙钛矿型氧化物负载纳米金属催化剂结构的动态调变及其催化氧化CO反应性能

研究了钛酸钡和钛酸钙担载的Ag和Pt纳米催化剂的表面结构随氧化-还原处理过程的动态变化及其对CO完全氧化反应性能的影响.发现氧化物担载的Ag催化剂在氧化处理后其催化活性较还原处理的高; X射线衍射(XRD)和X射线光电子能谱(XPS)表征结果表明,氧化处理能够提高载体表面Ag颗粒的分散度,而还原处理导致Ag颗粒的聚集,从而降低了催化氧化CO反应的活性.氧化-还原处理改变了担载Ag纳米粒子的尺寸并影响其CO氧化反应活性.与此相反,氧化物担载的Pt催化剂在还原处理后所表现出的CO氧化反应活性较氧化处理的高; 对比研究发现,氧化和还原处理后Pt纳米粒子的尺寸基本相同,但是氧化处理的样品中Pt表面物种以氧化态为主,而还原处理后Pt表面物种主要为金属态.Pt纳米粒子表面化学状态随氧化-还原处理的调变是导致表面催化活性差异的主要原因.     

超高相对分子质量聚丙烯腈基多孔中空氧化纤维的制备工艺研究

以超高相对分子质量聚丙烯腈基多孔中空纤维为原丝制备了多孔中空氧化纤维 ,研究了其制备工艺 .详细考察了氧化工艺条件 (温度、时间 )对多孔中空氧化纤维环化程度的影响 ,发现环化程度随氧化温度升高和氧化时间延长而提高 ;与以普通分子质量聚丙烯腈基实心纤维为原丝相比 ,氧化温度应较低 (<2 4 0℃ )、氧化时间应较短 (<2h) .     

A reasonable explanation for the mechanism of photo-promoted chemoselective aerobic oxidation of alcohols using (ON)Ru(salen) complex as catalyst

The mechanism of aerobic oxidation of alcohols using (ON)Ru(salen) complex as catalyst under photo-irradiation was examined through studies of kinetics of the oxidation, kinetic isotope effect in the oxidation, and effect of the ligand structure on the chemoselectivity of the oxidation of primary and secondary alcohols. It was demonstrated that the aerobic oxidation includes an intramolecular hydrogen atom transfer process that is attributed to realization of efficient differentiation of primary and secondary alcohols in the oxidation.     

卟啉类化合物对生物分子的光敏化氧化

本文就光敏化氧化反应、光敏剂、生物小分子的光敏化氧化机制以及生物大分子的光敏氧化与切割进行了系统的介绍与评述。同时, 介绍了国内外有关生命分子的光敏化氧化反应的最新研究成果以及它们潜在的应用前景。     

基于三维荧光光谱的乳制品脂氧化判别方法

为快速、无损判别乳制品脂氧化程度,提出了利用乳制品三维荧光光谱的氧化水平进行判别的方法。该方法用平行因子分析对荧光矩阵进行分解,用载荷向量组确定脂氧化过程中的光敏成分,用不同成分得分向量对样本进行聚类,并建立了不同氧化水平样本的偏最小二乘判别模型。实验采集不同存储环境下氧化程度各异的酸奶样本,找出了核黄素等荧光团在脂氧化过程中的变化规律,选取得分向量建立偏最小二乘判别模型对不同存储阶段氧化程度各异的样本判别分类,其特异度和灵敏度达88.9%以上,验证了该法对评判乳制品脂氧化水平的有效性。     

Boron doped diamond and glassy carbon electrodes comparative study of the oxidation behaviour of cysteine and methionine

The electrochemical oxidation behaviour at boron doped diamond and glassy carbon electrodes of the sulphur-containing amino acids cysteine and methionine, using cyclic and differential pulse voltammetry over a wide pH range, was compared. The oxidation reactions of these amino acids are irreversible, diffusion-controlled pH dependent processes, and occur in a complex cascade mechanism. The amino acid cysteine undergoes similar three consecutive oxidation reactions at both electrodes. The first step involves the oxidation of the sulfhydryl group with radical formation, that undergoes nucleophilic attack by water to give an intermediate species that is oxidized in the second step to cysteic acid. The oxidation of the sulfhydryl group leads to a disulfide bridge between two similar cysteine moieties forming cysteine. The subsequent oxidation of cystine occurs at a higher potential, due to the strong disulfide bridge covalent bond. The electro-oxidation of methionine at a glassy carbon electrode occurs in two steps, corresponding to the formation of sulfoxide and sulfone, involving the adsorption and protonation/deprotonation of the thiol group, followed by electrochemical oxidation. Methionine undergoes a one-step oxidation reaction at boron doped diamond electrodes due to the negligible adsorption, and the oxidation also leads to the formation of methionine sulfone.