Keggin型钼钒磷杂多酸催化剂上丙烷选择氧化性能的研究

系统研究了不同数目V⁵⁺取代的钼钒磷杂多酸H_3+nPMo_12－nV_nO₄₀ (n＝0～4)催化剂上丙烷选择氧化反应性能. 通过BET, IR, TPR, 紫外-可见光谱等表征手段对催化剂的理化性质进行了考察, 并对催化剂的结构-性能关系进行了初步关联. 在杂多酸的一级结构中, V⁵⁺对Mo⁶⁺的取代不仅改变了杂多阴离子金属-氧桥的键强以及晶格氧的插入能力, 而且也相应地调变了样品的酸量. 催化剂活性随V⁵⁺取代数量的递增而增强; 适宜数量的V⁵⁺取代提高了含氧酸产物的选择性, 而过量的V⁵⁺取代则导致部分氧化产物的深度氧化. 考察了在Keggin型杂多酸二级结构上引入钒物种的影响, 也即将钒物种(VO)²⁺作为抗衡离子取代部分质子以调变催化剂的结构与性质. 实验表明, 处于一级结构和二级结构[(VO)²⁺抗衡离子]中的V在反应中均可离析出少量V₂O₅物种. 适宜量的(VO)²⁺物种以及离析出来的少量V₂O₅物种可能均对催化剂的性能有贡献. 显然, 钒在不同位置的价态变化以及形态的不同, 会导致催化性能的相应改变.     

The Study on Generalized Toda Mechanics System with Loop Algebra L(Dr)

In this paper,we generalize the Toda mechanics system with long range interaction to the case of Loop algebra l(D^r).by using a pair of ordered positive integer (X,y) to describe Toda chains,we extract the equation of motion and the hamiltonian structure of this system for (3,2) Toda chain.it turns out that both extra coordinates and standard Toda variables are Poisson non–commutative in the case of nontrivial generalization,and for some case,extra variables appear linearly on the right hand side of the Poisson bracket.     

[Pb2(TNR)2(CHZ)2(H2O)2]·4H2O的结构及热分解机理

用碳酰肼 (CHZ ,NH2 NHCONHNH2 )、硝酸铅和三硝基间苯二酚 (TNR ,斯蒂酚酸 )的水溶液制备 [Pb2 (TNR) 2 (CHZ) 2 (H2 O) 2 ]·4H2 O .采用单晶分析的方法测定它的分子结构 ,并用TG DTG、DSC和　IR相结合的技术研究它的热分解机理 .所得晶体属单斜晶系 ,P2 1/n空间群 .晶体学参数为 :a=0 .6470 0 ( 10 )nm ,b =1.60 74 ( 3)nm ,c=1.4 883( 3)nm ,β =97.4 2 ( 2 )° ,V =1.534 9( 5)n ,Z =2 ,DC=2 .572 g·cm- 3,μ(Mo ,Kα) =11.0 80cm- 1,F( 0 0 0 ) =112 8.最终偏离因子R =0 .0 4 2 2 ,Rw=0 .0 735.该配合物分子呈中心对称 ,两个羰基O原子形成两个氧桥 ,TNR2 - ,CHZ和H2 O同时参与了与中心离子的配位     

钒-5-溴水杨基荧光酮-氯酸盐体系极谱催化波的研究

在pH4.1的乙酸盐缓冲底液中,钒能与5-溴水杨基荧光酮形成络合物,并吸附在汞电极上,在氯酸盐存在下,在V(Ⅴ)的电极还原过程中形成催化波。用单扫二阶导数极谱法测定时,钒浓度在L.0×10-8～1.0×10-6mol·L-1范围内与峰高成正比关系,检出限为5.0×10-9mol·L-1。测得电活性络合物的组成为V(Ⅴ)5-Br-SAF＝11。平行催化反应的速率常数k=1.9×103(mol·L-1)-1·s-1。     

Demethoxylation and O-Demethylation of Pseudaconine and Isotalatizidine

Thenorditerpenoidalkaloidsnotonlyhaveimportantpharmacologicalactivities,butalsomaysetoffalotofinterestingchemicalreactionsl'2.Inthecourseofourstudiesonsearchforhighactivity,lowtoxicitycompoundsandconversionoftheskeletons,aseriesofmodificationsofthesealkaloidshavebeenreported'.Inthepresentpaper,wereportsomechemicalreactionsincludingthedemethoxylation,O-demethylationandoxidation,ofthenorditerpenoidalkaloidspseudaconine1andisotalatizidine7.Treatmentofthenorditerpenoidalkaloidscontainingmethoxylgr…     

Oxidation of the Norditerpenoid Alkaloids Isotalatisidine and 6-Epiforsticine

Inpreviousworksonmodificationsofnorditerpenoidalkaloids,wereportedsomeimportantreactionssuchasN-deethylationandpreparationsoftheimmesand7,17-secoderivatives'.NowwewishtorepoFtoxidationofthenorditerpenoidalkaloidsisotalatizidineand6-epiforsticine.Oxidationofnorditerpenoidalkalnidshavinganla-hydroxylgroupwithreagentssuchasKMnO.K,Fe(CN),,OsO.,Ag,OandNBSaffordedcompoundswithanO,Nmixedacetalsystems=.Thus,treatmentofisqtalatizidineIwithKMnO.inacetone-H,O(5;1)forIhgavetheknowncompoundnevade…     

New insight into the stability and dynamics of fluid-conveying supported pipes with small geometric imperfections

正Kun ZHOU1,2, Qiao NI1,2, Wei CHEN1,2, Huliang DAI1,2,3,Zerui PENG1,2,, Lin WANG1,2,     

Effect of Adsorption of ZrO2 in Catalysts on the Efficiency of Hydrolysisof Cellulose to Sugar in Aqueous System under Microwave Radiation

Five types of ZrO₂ are used to simply establish an effective aqueous catalytic system with sulfuric acid for the hydrolysis of cellulose to sugar, respectively. By adjusting surface roughness and particle size of ZrO₂, different adsorption is produced. Accordingly, following the thought to inhibit the self‐aggregation nature of cellulose, after the introduction of ZrO₂ with adsorption in catalysts, the efficiency of the hydrolysis of cellulose to sugar is improved. The results show different ZrO₂ can produce different effects during the hydrolysis of the cellulose with relatively low crystallinity. Under the optimal conditions, the conversion of cellulose and TRS yield reaches 95.5% and 93.6%, respectively. Through this research, it reveals the critical point to organize a feasible and useful way for the hydrolysis of cellulose to sugar with high efficiency in an aqueous system. An important theoretical and technical support is also provided for the conversion and utilization of cellulose in the future.     

Characteristics and properties of metal aluminum thin films prepared by electron cyclotron resonance plasma-assisted atomic layer deposition technology

Metal aluminum (Al) thin films are prepared by 2450 MHz electron cyclotron resonance plasma-assisted atomic layer deposition on glass and p-Si substrates using trimethylaluminum as the precursor and hydrogen as the reductive gas. We focus our attention on the plasma source for the thin-film preparation and annealing of the as-deposited films relative to the surface square resistivity. The square resistivity of as-deposited Al films is greatly reduced after annealing and almost reaches the value of bulk metal. Through chemical and structural analysis, we conclude that the square resistivity is determined by neither the contaminant concentration nor the surface morphology, but by both the crystallinity and crystal size in this process.