丙烯选择氧化铋钼铁复氧化物催化剂组成,结构及性能的研究

采用XRD、Raman、XPS及催化剂性能评价等手段,考察了Bi_3(FeO_4)(MoO_4)_2和Fe_2(MoO_4)_3分别存在及两者共存时对Bi-Mo复氧化物体系催化性能的影响.结果表明,这两种含Fe物种的存在都有助于改善Bi-Mo系复氧化物催化剂对丙烯选择氧化反应的催化性能.但两者在作用机理上有所不同.Fe_2(MoO_4)_3本身无催化活性,但在反应条件下可部分还原为FeMoO_4形成Fe~(3+)/Fe~(2+)氧化还原对;且其地结构上与α-Bi_2(MoO_4)_3相匹配,这些因素都有助于促进催化体系中电子和氧物种的传递及催化剂表面活性中心的再生,从而提高催化性能.Bi_3(FeO_4)(MoO_4)_2在反应条件下也可形成Fe~(3+)/Fe~(2+)氧化还原对,但由于其Fe~(3-)所处的化学环境与Fe_2(MoO_4)_3很不相同,且Fe的含量也不及Fe_2(MoO_4)_3,因此它在促进催化体系中电子和氧物种的传递及催化剂表面活性中心的再生等方面的性能较差,但它对提高催化剂表面的活性中心(Bi-Mo对)数目有贡献.     

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     

Aerobic oxidation assisted by ligand-free palladium catalysts

Aerobic oxidation of electron-rich benzylic and phenyl allylic alcohols was achieved with high yields with only 0.1 mol.% of Pd(OAc)2 catalyst in the absence of any ligand. This procedure was expected to be valuable for realistic industrial-scale applications from both economic as well as environmental points of view.     

Oxidation of thiol compounds by molecular oxygen in aqueous solutions

Side self-oxidation of thiols was studied. It was found that these reactions in neutral and alkaline solutions are induced by impurities of variable-valence metals. The ability of transition metals to catalyze oxidation of thiols changes in the order Cu > Mn > Fe > Ni Co. The plot of the self-oxidation rate vs. pH passes through a maximum whose position on the pH scale depends on both the nature of metal and the structure of the thiol oxidized. For thiols having different structures, the kinetic orders in reactions catalyzed by copper ions differently vary with pH, which is apparently associated with the formation of complexes possessing different catalytic activity.     

Cs-Fe-Co-Bi-Mn-Mo复合氧化物选择性催化氧化异丁烯

Mixed oxide catalyst Cs0.1 Fe2Co6BiMnMo12 Ox was prepared by the interprecipitation method, then the catalyst was calcined at different temperature. Selective oxidation of isobutene was carried out in a fixed-bed reactor. The results showed that the catalyst has high catalytic activity. Under the optimum reaction conditions ( n(-C4^= ) : n(O2) = 1:2-1:4, space velocity = 180h^-1, T = 360℃ ), the yield of methacmlein and methacrylic reached 80%, 8 %,respectively. The total yields of liquid products( methacrolein, methacrylic acid and acetic acid) reached about 90%.     

Synthesis of novel organoselenium as catalyst for Baeyer-Villiger oxidation with 30% H2O2

A novel diselenide was synthesized in good yield via only four steps from phenol, and was employed as the catalyst for the Baeyer-Villiger oxidation with 30% H₂O₂ to obtain lactones in good yields.     

SYNTHESIS AND CATALYTIC PROPERTY OF POLYSTYRENE SUPPORTED GLUTAMIC ACID SCHIFF BASE COMPLEX OF Mn（ Ⅱ ） IN AEROBIC OXIDATION OF CYCLOHEXENE

The polystyrene supported glutamic acid Schiff base complex of Mn （ Ⅱ ） （PS-Sal-Glue-Mn） was prepared with chloromethylated styrene polymer beads, 2,4-dihydroxybenzaldehyde, L-glutamic acid and manganese （ Ⅱ ） acetate tetrahyrate. The polymeric ligand and the complex were characterized by FT-IR, small area X-ray photoelectron spectroscopy （XPS） and 1CP-AES. In the presence of the manganese complex, cyclohexene （1） was effectively oxidized by molecular oxygen without reductant. The major products of the reaction were 2-cyclohexen-l-ol （2）, 2-cyclohexen-l-one （3） and 2-cyclohexen-1- hydroperoxide （4）, which was different with typical oxidation of cyclohexene. The influence of reaction temperature and additive for oxidation had been studied. The selectivity of 2-cyclohexen-1-hydroperoxide varied with reaction time and different additives. The mechanism of cyclohexene oxidation had also been discussed.     

离子液体［bmim］HSO4中合成的苯胺与环氧丙烷共聚物的电催化性能

 采用恒电流电解法,在1-丁基-3-甲基咪唑硫酸氢盐(［bmim］HSO4)离子液体中合成了苯胺与环氧丙烷共聚物(PAN-PPO). 扫描电镜观察表明, PAN-PPO由直径小于80 nm的纳米纤维组成. PAN-PPO对草酸氧化具有较好的电催化活性. 采用电化学原位红外光谱技术对草酸的电催化氧化进行了简单的分析.     

Application of thermal analysis to carbon black-elastomer systems

In this study a relationship between the surface and textural properties of carbon blacks and the gasification process induced thermally in air is noted. A temperature jump method was used to follow the gasification in air and to establish the relevant Arrhenius parameters. This can be associated with the activity of ‘basal’ plane carbon atoms as well as ‘edge’ carbon atoms at the surface. This is based on a model of carbon black structure consisting of the irregular packing of small graphite carbon structures. The carbon black surface was measured using a single measurement of adsorption based essentially on the BET volumetric method. The carbon black surface had a rate of oxidation per unit are which clearly indicated that the lower area carbon blacks had a predominately active area of ‘edge’ atoms at the surface while the surface of the higher area carbon blacks had a predominate amount of ‘basal’ plane graphite carbon atoms.     

选择性氧化含氰基的对硝基苯硫醚

选择性氧化含氰基的对硝基苯硫醚岳国仁，王建华，张正（南京大学化学系南京２１０００８）关键词含氰基硫醚，选择性氧化，四水合过硼酸钠据报道［１］对硝基苯磺酰基乙腈的合成，反应时间长，可采用四水合过硼酸钠（ＮａＢＯ３·４Ｈ２Ｏ）作为氧化剂，受到重视［２，３...