12-磷钨杂多酸受热相变的研究

在室温至４５０℃范围内，考察了Ｈ３ＰＷ１２Ｏ４０·２９Ｈ２Ｏ的受热相变情况．结果表明，杂多酸中所含沸石水和结晶水很容易失去，且失水程度与其所处环境有关．以ＩＲ、ＴＧ－ＤＴＡ、ＸＲＤ以及ＳＥＭ等表征了不同含水量的杂多酸，表明其晶体结构及外观均因失水而发生了相应的变化.

有机-无机自由基盐(DBTTF)_6PMo_(12)O_(40)·2H_2O的合成、性质和晶体结构

用电解法制备了有机－无机自由基盐（ＤＢＴＴＦ）６ＰＭｏ１２Ｏ４０·２Ｈ２Ｏ．用红外光谱、电子光谱和电子自旋共振谱进行了表征，测定了其磁化率、导电性和单晶的晶体结构．该晶体属三斜晶系，Ｐ１空间群．晶胞参数为ａ＝１．３７８７（７）ｎｍ，ｂ＝１．４２０４（２）ｎｍ，ｃ＝１．５７０２（２）ｎｍ，α＝１０４．５７０（８）°，β＝１０３．４１（２）°，γ＝９５．８０（２）°，Ｖ＝２．８５３（２）ｎｍ３，Ｚ＝１，Ｄｃ＝２．１４２Ｍｇ·ｍ－３，Ｒ＝０．０７２７．

层状复合氧化物La_2BaCu_(5-x)Mn_xO_(12)的表征及在催化消除NO中活性的研究

采用柠檬酸配合法合成了结构呈层状ABO_3的La_4BaCu_5O_(12)复合氧化物,并以它为基体合成了一系列Mn取代Cu的样品(La_4BaCu_(5-x)Mn_xO_(12),x=1～5。)并利用XRD,IR进行了结构表征,结果表明其均为5层的ABO_3结构.利用H_2-TPR考查了掺杂Mn以后样品的氧化还原性能的变化,发现由于Mn的掺杂使Cu明显的容易还原还考查了样品对NO+CO反应的催化活性,结果表明反应的活性中心是Cu离子,但加入适量的Mn离子可以使活性提高.

Study on the Property of Vitamin B-12-Modified Electrode and its Electrocatalysis for the Reduction of Oxygen

It was found that vitamin B-12 could be strongly adsorpted on the anodized glassy carbon electrode to form a vitamin Thy-modified glassy carbon electrode. The modified electrode is stable in a wide pH range. The electrochemical characteristics of the modified electrode were studied in details. In addition, it was found that the reduction of oxygen could be catalyzed by the modified electrode to form H2O2. An EC mechanism was suggested for the process, and the follow up chemical reaction might he the rate determined step.

Electrochemical studies on vitamin B-12 and its derivatives

The electrochemical studies on vitamin B-12 and its derivatives were reviewed in this paper. The importance of electrochemical studies for explaining the mechanism of B-12 coenzyme in body was discussed. The latest results of electrochemical studies on vitamin B-12 and its derivatives was reviewed. A prospect for the electrochemical studies in vitamin B-12 and its derivatives was suggested.

La_2O_3-Ni/SrAl_(12)O_(19)催化剂上甲烷与二氧化碳重整反应的研究

采用ＸＲＤ、ＵＶ－ＤＲＳ、Ｈ２－Ｏ２滴定、ＴＰＲ、吡啶吸附红外光谱等技术，研究了Ｌａ２Ｏ３助剂对Ｌａ２Ｏ３－Ｎｉ／ＳｒＡｌ１２Ｏ１９催化剂的还原性、表面酸性、金属镍的分散度和抗烧结能力，以及对催化甲烷与二氧化碳重整制取合成气反应性能的影响．结果表明，在负载型的镍催化剂中，添加Ｌａ２Ｏ３助剂，能够削弱金属组分与载体之间的相互作用，降低催化剂的还原性，提高金属镍在催化剂表面的分散度和在反应过程中的抗烧结能力，降低催化剂表面酸性．关联甲烷与二氧化碳重整反应活性的结果，发现影响负载型镍催化剂的反应活性、稳定性和积炭性质的主要因素是金属镍的分散状态，而不是催化剂表面酸性．Ｌａ２Ｏ３主要是通过改变镍的分散度来影响催化甲烷与二氧化碳重整反应活性的．

维生素B_(12)修饰电极及其催化氧还原性质的研究

发现维生素B12能吸附在经阳极化处理的玻碳电极上，从而制成稳定的维生素B12修饰玻碳电极．详细研究了此电极的电化学性质．并发现此修饰电极能有效地催化分子氧的二电子还原.

YGa_(3-x)Cr_xB_4O_(12)的合成、发光与磁性

扩展了ＹＧａ３Ｂ４Ｏ１２的合成温度。研究了合成温度的改变及Ｃｒ３＋离子引入后发光性质的变化。合成ＹＧａ３－ｘＣｒｘＢ４Ｏ１２化合物后，对其磁学性质进行了表征。结果表明，高温合成该化合物有利于化合物荧光发射的增强，掺杂少量Ｃｒ３＋可以稳定该化合物的结构并改变其发光光谱。磁化率随Ｃｒ３＋含量的增加而增大。

4-羟基偶氮苯与6-氯-5,12-萘并萘醌反应产物的NMR分析

无水碳酸钾存在下6-氯-5,12-萘并萘醌与4-羟基偶氮苯在干燥DMF中反应的主要产物在某些反应条件下不是6[4-(苯基偶氮基)苯氧基]-5,12-萘并萘醌(1)。该未知反应产物2经核磁共振方法研究证实是6-(N,N-二甲氨基)-5,12-萘并萘醌。本文对化合物2的~1H-和~(13)C化学位移、偶合信息和结构作了详细归属,并推测其反应进程,实验结果表明,化合物2是由化合物1与溶剂DMF反应生成。

Studies on morphology and crystallization of polypropylene/polyamide 12 blends

Scanning electron microscopy (SEM) and an image analyser are used to study morphologies of the fractured surface, etched by hot phenol, of polypropylene/maleated polypropylene/polyamide 12 PP/PP-MA/PA12) = 65/10/25 blend and PP-MA/PA12 = 75/25 blend. The particle dimension and its distribution of PA12 dispersed phase in these blends are much lower and narrower than that of the PP/PA12. blends. Especially, most of the particles in the PP-MA/PA12 = 75/25 blend are smaller than 0.1 mu m. The effect of the morphology of PP/PA12 blends on their crystallization behaviour is studied using differential scanning calorimetry and SEM. PA12 dispersed phase coarsens during annealing in the PP/PP-MA/PA12 = 65/10/25 blend. The mechanism of coarsening of the PA12 dispersed phase is a coalescence process. The intense mixing between the PP component and the PA12 component through reaction of PP-MA and PA12 leads to a change of dynamic mechanical behaviour of the components. A separation method is used to separate the polyolefin parts (precipitated from hot phenol), from PA12 parts (hot phenol filtrate). Of PP/PP-MA/PA12 = 65/10/25 blend, infra-red measurements and elementary analysis show that the precipitate has a lower PA12 content than the feed, whereas the filtrate has a higher PA12 content. From PP-MA/PA12 = 75/25 blend, PA12 contents in the precipitate and the filtrate are the same as in the feed. This implies that all PA12 has reacted with all PP-MA in the latter case while not in the former case. Using the method of interface exposure, interfacial reaction of PP-MA with PA12 is studied by X-ray photoelectron spectrometry (X.p.s.). Copyright (C) 1996 Elsevier Science Ltd.

Epitaxial crystallization in the sPP/nylon-12 semicrystalline polymer system

The epitaxial crystallization behaviour of syndiotactic polypropylene (sPP) on highly oriented nylon-12 substrates has been investigated by means of transmission electron microscopy. The results obtained from bright field electron microscopy and electron diffraction indicate that sPP crystals grow epitaxially on the oriented nylon-12 substrate with their c-axes +/- 37 degrees apart from the chain axis of the nylon-12 substrate. The contact planes of the sPP crystals are the (100) lattice planes. Moreover, the epitaxial crystallization of nylon-12 on highly oriented sPP substrates from a dilute solution in cyclohexanone has also been studied using optical microscopy. The results show that the nylon-12 crystals grow epitaxially on the oriented sPP substrate with the oriented nylon-12 lamellae forming large, anisotropic domains. Copyright (C) 1996 Elsevier Science Ltd.

Electrochemical study of isopoly- and heteropoly-oxometallates film modified microelectrodes .6. Preparation and redox properties of 12-molybdophosphoric acid and 12-molybdosilicic acid modified carbon fiber microelectrodes

The redox behaviours of 12-molybdophosphoric acid (12-MPA) and 12-molybdosilicic acid (12-MSA) in aqueous acid media are characterized at the carbon fiber (CF) microelectrode. The preparation of CF microelectrode modified with 12-MPA or 12-MSA monolayer and the oxidation-reduction properties of the modified electrode in aqueous acid media or 50% (v/v) water-organic media containing some inorganic acids are studied by cyclic voltammetry. 12-MPA or 12-MSA monolayer modified CF microelectrode with high stability and redox reversibility in aqueous acidic media can be prepared by simple dip coating. The cyclic voltammograms of 12-MPA and 12-MSA and their modified CF microelectrodes in aqueous acid solution exhibit three two-electron reversible waves with the same half-wave potentials, which defines that the species adsorbed on the CF electrode surface are 12-MPA and 12-MSA themselves. The acidity of electrolyte solution, the organic solvents in the electrolyte solution, and the scanning potential range strongly influence on the redox behaviours and stability of 12-MPA or 12-MSA monolayer modified electrodes. On the other hand, the catalytic effects of the 12-MPA and 12-MSA and chlorate anions in aqueous acidic solution on the electrode reaction processes of 12-MPA or 12-MSA are described.

12－硅钨酸与γ-Al_2O_3载体表面的相互作用

研究了不同溶剂中ＳｉＷ１２在γ－Ａｌ２Ｏ３表面的吸附和溶脱规律，以ＩＲ，ＸＲＤ以及酸催化模型探针反应对吸附于γ－Ａｌ２Ｏ３表面的ＳｉＷ１２的存在形态和酸性进行了表征．尽管ＳｉＷ１２碱降解稳定性在常见杂多酸中最强，但由水溶液中吸附在γ－Ａｌ２Ｏ３表面的ＳｉＷ１２仍有一部分被该载体的碱性所降解．此外，在γ－Ａｌ２Ｏ３表面上ＳｉＷ１２质子的活动性大大减弱，其阴离子的热稳定性也明显降低．可以认为，ＳｉＷ１２的质子和Ｋｅｇｇｉｎ阴离子与γ－Ａｌ２Ｏ３表面均有直接相互作用.

活性炭固载杂多酸催化剂（SiW_（12）／C）气相催化酯化反应动力学的研究

在固定床积分反应器中，于８５～１６０℃温度区间内，在活性炭固载的硅钨酸催化剂上研究了合成乙酸乙酯和乙酸丁酯的酯化反应动力学。实验结果表明，在总压保持１．０１３×１０５ｐａ的条件下，酯化反应速率与反应物以及稀释剂的分压有密切的关系，并且醇结构不同，其酯化反应的动力学也不同，在此基础上，提出了酯化反应在活性炭固载杂多酸催化剂上的反应机理。