联二脲氧化生成偶氮二甲酰胺反应的钒催化机理

在钒催伦剂存在下，用氯酸钠氧化联二脲制成偶氮二甲酰胺，从钒催化剂的单晶培养和结构解析入手，通过反应动力学研究，用ＥＳＲ检测反应过程中四价钒的生成，用分光光度法（分别以钛钛试剂和硫氰酸铵为显色剂）确定了反应过程中三价钒的生成和变化情况，从而提出了可能的催化机理，还利用量化计算从热力学角度证实了所提出的包括四价钒铬离子歧化过程在内的钒催化机理的合理性。     

ZnO超微粒子光催化氧化降解n-C7H16的研究

利用ZnO光催化氧化技术对气相n-C7H16进行了降解研究，考察了氧气、水燕气体积分数等因素对n-C7H16光催化氧化的影响，利用气相色谱－质谱联用仪和气相色谱仪对气相光催化反应过程中的气体组成进行了定性分析，并对主要中间产物丙醛进行了定量分析，结果发现，ZnO超微粒子光催化氧化n-C7H16的降解率较高，n-C7H16绝大部分被完全氧化成CO2，探讨了n-C7H16光催化氧化反尖的动力学行为及机理。     

La2Zr2O7催化剂结构相变对甲烷氧化偶联反应性能的影响

采用共沉淀法并通过改变焙烧温度制备了一系列具有不同晶相结构的La₂Zr₂O₇催化剂，在微型固定床反应器上评价其甲烷氧化偶联反应性能，并利用XRD、Raman、CO₂-TPD、XPS等表征手段，探究催化剂的物相结构、表面碱性以及表面氧物种的变化规律。结果表明，随着焙烧温度从700℃逐渐升高到1200℃，La₂Zr₂O₇催化剂结晶度不断提高，晶相发生明显变化，从无定形结构逐渐向缺陷萤石结构过渡，最终转变成烧绿石结构。焙烧温度提高促使La₂Zr₂O₇晶相转变过程中，催化剂表面的碱性强度减弱，中等碱性位数量以及具有催化活性的表面氧物种O₂^2-和O₂^-的相对含量不断减少，致使催化剂的CH₄转化率和C₂₊选择性不断降低。其中，无定形LZO-CP-700催化剂表现出最佳的甲烷氧化偶联反应性能。     

六钨酸四丁基铵盐和异丙醇体系的催化氧化反应的ESR研究Ⅰ.

本文研究了六钨酸四丁基铵盐在紫外光辐照的条件下催化氧化异丙醇为丙酮的反应。采用自旋捕捉技术与电子自旋共振相结合的方法,在位检测到氧化反应过程中有活泼自由基中间体产生,并观察到光电流产生。文中对六钨酸四丁基铵盐的催化反应机理进行了讨论。     

Oxidation and Reduction Processes During NO x Removal with Corona-Induced Nonthermal Plasma

In this paper, the NO-to-NO ₂ conversion in various gaseous mixtures is experimentally investigated. Streamer coronas are produced with a dc-superimposed high-frequency ac power supply (10–60 kHz). According to NO _x removal experiments in N ₂ +NO _x and N ₂ +O ₂ +NO _x gaseous mixtures, it is supposed that the reverse reaction NO ₂ +ONO+O ₂ may not only limit NO ₂ production in N ₂ +NO _x mixtures, but also increase the energy cost for NO removal. Oxygen could significantly suppress reduction reactions and enhance oxidation processes. The reduction reactions, such as N+NON ₂ +O, induce negligible NO removal provided the O ₂ concentration is larger than 3.6%. With adding H ₂ O into the reactor, the produced NO ₂ per unit removed NO can be significantly reduced due to NO ₂ oxidation. NH ₃ injection could also significantly decrease the produced NO ₂ via NH and NH ₂ - related reduction reactions. Almost 100% of NO ₂ can be removed in gaseous mixtures of N ₂ +O ₂ +H ₂ O+NO ₂ with negligible NO production.     

Propane oxidation over Pd/LaFe0.8Co0.2O3 catalyst

Pd/LaFe_0.8Co_0.2O₃ was found to be more active than the Pd/Al₂O₃ catalyst in propane oxidation. Activity and the oxidation state of palladium were strongly affected by the redox ratio (S) of reactants. Higher propane conversion could be obtained under rich conditions at higher temperatures, contributing to steam reforming. The presence of excess steam would bring about inhibition and oscillation.     

Influence of the conditions of manufacture of nanomeric zirconium dioxide,stabilized with yttrium oxide,on its catalytic properties in the oxidation of CO

The morphological and catalytic properties of samples of nanomeric zirconium dioxide, stabilized with yttrium oxide, manufactured via the effect of a UHF field during the process of drying precipitated zirconium hydroxide and calcination at temperatures from 300 to 1000 °C, were studied. It was shown that the highest activity in the oxidation of CO occurred with 40 nm particles of zirconium dioxide prepared at 1000 °C. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 43, No. 2, pp. 96–101, March–April, 2007.     

高碲酸合铜（Ⅱ,Ⅲ）配合物的合成和性质

在Ｈ６ＴｅＯ６／ＫＯＨ水溶液中以臭氧为氧化剂，将二价铜化合物氧化成三价铜化合物，并获得一个新的三价铜化合物Ｂａ４Ｋ［Ｃｕ（Ｈ２ＴｅＯ６）２］（ＯＨ）４．６Ｈ２Ｏ；描述了碱性溶液中“Ｃｕ（Ⅲ）／Ｃｕ（Ⅲ）”循环伏安图。对铜（Ⅲ）化合物，Ｎａ４Ｈ［Ｈ２ＴｅＯ６）２］．１７Ｈ２Ｏ以及相应的铜（Ⅱ）配合物的电子光谱和Ｃｕ２ｐＸＰＳ进行了研究，给出了其配位场场强参数和Ｃｕ２ＰＸＰＸ的电子结合能。由于价态升高     

助剂对Cu/Cr催化剂上甲醇部分氧化制氢的活性影响

曾研究了Cu/Cr二元催化剂上甲醇部分氧化制氢的反应，发现当Cu/Cr比为6：4时，催化剂的Cu^0比表面积最大，呈现出较好的活性。在Cu/Cr（6：4）催化剂中添加Fe,Zn,Al等8种助剂，考察其对甲醇部分氧化制氢催化性能的影响，并着重研究了Zn助剂的作用。实验结果表明，Zn的引入，有利于催化剂活性的提高。当Zn含量为10％时，催化剂活性最好。XRD表征结果表明，Cu/Cr催化剂的失活与其表面上的Cu物种烧结有关，Zn的引入可明显增强Cu/Cr（6：4）催化剂的热稳定性，提高其寿命。