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61.
(PdCl2—PVP)/Al2O3催化剂中Pd状态的探讨 总被引:3,自引:0,他引:3
氯化钯先锚定在聚乙烯吡咯烷酮上后进一步负载到Al_2O_3上所制的催化剂[简称(PdCl_2-PVP)/Al_2O_3]是一种活性、选择性高,稳定性好的烯烃、二烯烃和多烯烃加氢催化剂。本文结合加氢反应,使用XPS、FT-IR、电镜及用CO为探针的FT-IR,对这种催化剂进行了考察。实验说明,在这种催化剂中,钯的价态是在0—2之间。红外光谱在486cm~(-1)处有一微弱的小峰,说明存在Pd—N的配位键。催化剂中钯含量低时(0.2wt%)稳定性好,不吸附CO,活性中心是络合钯原子;当钯含量较高时(0.7wt%),催化剂的初活性虽不低,稳定性却较差,这种催化剂能吸附CO,IR谱图上仅在1919cm~(-1)处有CO桥式吸附态的伸缩振动。表明除络合钯原子外,还有聚集的钯金属存在。FT-IR尚表明,PVP在Al_2O_3上可能并非单纯的物理吸附。电镜结果表明,PVP在Al_2O_3上呈30—70(?)的微球状,(PdCl_2-PVP)/Al)_2O_3上的(PdCl_2-PVP)亦呈微球状,与前者无明显区别,这种催化剂中其活性中心是络合钯原子。 相似文献
62.
研究了第二过渡金属化合物对TiCl4/AleT1.46cL1.54催化丁二烯环化三聚的多金属协同效应。结果表明,极少量的第二过渡金属化合物,如Cr,(acac)3,Mn(acac)3,NiCl2,ZrCl4等加入TiCl4/AlEt1.46Cl1.54体系后不同程度地提高了丁二烯环化三聚的选择性,并改变了体系的最大速率和催化剂效率。 相似文献
63.
Zhuxing Tang Yun Zhou Yikun Zeng Shuliang Zang Pingang He Yuzhi Fang 《Chromatographia》2006,63(11-12):617-622
A method based on capillary electrophoresis with electrochemical detection has been developed for the separation and determination of epicatechin, isovanillic acid, vanillic acid and myricetin in Dioscorea bulbifera L. and its medicinal preparations. The effects of working electrode potential, pH and concentration of running buffer, separation voltage and injection time were investigated. Under optimum conditions, the analytes could be separated in a 40 mmol L?1 borate buffer (pH 8.7) within 15 min. A 300 μm diameter carbon disk electrode has a good response at + 0.95 V (vs. SCE) for all analytes. The response was linear over three orders of magnitude with detection limits (S/N = 3) ranging from 3.0 × 10?8 g mL?1 to 1.0 × 10?7 g mL?1. The method has been successfully applied to the analysis of real samples. 相似文献
64.
Semiconductor alpha-MoTe2 nanorods have been synthesized by annealing Te-seeded particles of an amorphous MoTe2 intermediate. This intermediate is prepared by a solution reaction between Mo(CO)6 and elemental Te in diphenylmethane. The as-synthesized products were characterized by structural, compositional, and morphological techniques of X-ray diffraction, selected area electron diffraction, selected area energy dispersive spectroscopy, energy dispersive X-ray analysis, X-ray photoelectron spectroscopy, transmission electron microscopy, and high-resolution transmission electron microscopy. The results of the annealing process are MoTe2 nanorods with diameters of 50-200 nm and lengths ranging from 0.1 to 3.0 microm. Here, the rodlike structure of MoTe2 is reported for the first time, and added to the list as one kind of new morphology of MoTe2 nanomaterials. A mechanism for the formation of the nanorods is proposed. The sandwich-layered structure of Te-Mo-Te and the similarity in the structure between hexagonal alpha-MoTe2 and hexagonal Te are responsible for the formation of nanorods of MoTe2. 相似文献
65.
CompoundsformedfromCu ,AgandAuwithdithio lateligands ,suchasthedialkyldithiocarbamate (DTC) ,mercaptothiazoline (HMT)anddialkyldithiophosphates(DDP) ,haveplayedanimportantroleintechnology .1Cu(I) Sclustersalsohavebeenimplicatedinbiologyasan ti oxidants .2Thecuban… 相似文献
66.
Macrocyclic Schiff‐base ligand, bisacetylaceton‐ethylenediimine (BAE) and its transition metal complexes M(BAE) (M = Cu2+, Ni2+) were synthesized. The complexes having characteristics of aromatic systems and well‐defined one‐dimensional structures, reacted with p‐phthaloyl chloride, to obtain polymer complexes. The complexes were characterized by elemental analysis, inductively coupled plasma (ICP), FT‐IR, and thermal analysis and show good thermal stability. ESR spectra analysis discovered that there are free radicals in the chain of polymers, indicating that a weak magnetic spin‐exchange interaction operates between the metal ions and free radicals. It is found that, as the bridging p‐phthaloyl group is able to propagate the magnetic exchange interaction, the polymer complexes show paramagnetic properties by measurement of temperature dependence of the magnetic property, and obey Curie–Weiss law. Copyright © 2001 John Wiley & Sons, Ltd. 相似文献
67.
Shi Zhen CHEN Yun Peng BAI Zhao Long LI 《中国化学快报》2006,17(2):258-260
Fluorous-phase chemistry is currently a topic of considerable interest1-6. Since fluoroustriphasic reactions were first described by the Curran and co-workers7, this triphasicsystem has been widely used for detagging7,8 and phase-vanishing reactions9-11. … 相似文献
68.
The detailed reaction dynamics of CH(3)I photodissociation at 304 nm were studied by using high-resolution long time-delayed core-sampling photofragment translation spectroscopy. The vibrational state distributions of the photofragment, i.e., CH(3), are directly resolved due to the high kinetic resolution of this experiment for the first time. CH(3) radicals produced from I((3)Q(0+)), I((1)Q(1) <--( 3)Q(0+)), and I((3)Q(1)) channels are populated in different vibrational state distributions. The I((3)Q(0+)) and I((3)Q(1)) channels show only progressions in the nu2'(a2") umbrella bending mode, and the I((1)Q(1) <-- (3)Q(0+)) channel shows both progression in the nu2' umbrella bending mode and a small amount of excitation in the nu1'(a1') C-H stretching mode. The photodissociation processes from the vibrational hot band of CH(3)I (upsilon3 = 1, upsilon3 = 2) were also detected, primarily because of the absorption probability from the vibrational excited states, i.e., hot bands are relatively enhanced. Photofragments from the hot bands of CH(3)I show a cold vibrational distribution compared to that from the vibrational ground state of CH(3)I. The I* quantum yield and the curve crossing possibility were also studied for the ground vibrational state of CH(3)I. The potential energy at the curve crossing point was calculated to be 32 790 cm(-1) by using the one-dimensional Landau-Zener model. 相似文献
69.
Yun‐Yu Liu Guang‐Shan Zhu Guo‐Zhen Fan Shi‐Lun Qiu 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(4):m159-m160
In the title compound, poly[μ5‐pyrazine‐2,3‐dicarboxylato‐cadmium(II)], [Cd(C6H2N2O4)]n or [Cd(pdc)]n, where pdc is the pyrazine‐2,3‐dicarboxylate anion, the CdII atom is six‐coordinated by five carboxylate O atoms and one N atom from five different pdc ligands in a distorted octahedral CdO5N coordination geometry. Two CdII atoms are bridged by carboxylate groups of the pdc ligands to create a dimeric unit. The dimeric units are further connected by the pdc ligands to generate an interesting two‐dimensional structure. 相似文献
70.
The cationic ruthenium hydride complex [(PCy(3))(2)(CO)(CH(3)CN)(2)RuH](+)BF(4)(-) was found to be a highly effective catalyst for the C-H bond activation reaction of arylamines and terminal alkynes. The regioselective catalytic synthesis of substituted quinoline and quinoxaline derivatives was achieved from the ortho-C-H bond activation reaction of arylamines and terminal alkynes by using the catalyst Ru(3)(CO)(12)/HBF(4).OEt(2). The normal isotope effect (k(CH)/k(CD) = 2.5) was observed for the reaction of C(6)H(5)NH(2) and C(6)D(5)NH(2) with propyne. A highly negative Hammett value (rho = -4.4) was obtained from the correlation of the relative rates from a series of meta-substituted anilines, m-XC(6)H(4)NH(2), with sigma(p) in the presence of Ru(3)(CO)(12)/HBF(4).OEt(2) (3 mol % Ru, 1:3 molar ratio). The deuterium labeling studies from the reactions of both indoline and acyclic arylamines with DCCPh showed that the alkyne C-H bond activation step is reversible. The crossover experiment from the reaction of 1-(2-amino-1-phenyl)pyrrole with DCCPh and HCCC(6)H(4)-p-OMe led to preferential deuterium incorporation to the phenyl-substituted quinoline product. A mechanism involving rate-determining ortho-C-H bond activation and intramolecular C-N bond formation steps via an unsaturated cationic ruthenium acetylide complex has been proposed. 相似文献