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91.
Changjiu Xia Long Ju Yi Zhao Hongyi Xu Bin Zhu Feifei Gao Min Lin Zhenyu Dai Xiaodong Zou Xingtian Shu 《催化学报》2015,(6):845-854
The reaction mechanism of the oxidation of cyclohexanone catalyzed by titanium silicate zeolite TS-1 using aqueous H2O2 as the oxidant was investigated by combining density function theory (DFT) calculations with experimental studies. DFT calculations showed that H2O2 was adsorbed and activated at the tetrahedral Ti sites. By taking into account the adsorption energy, molecular size, steric hindrance and structural information, a reaction mechanism of Baeyer-Villiger oxidation catalyzed by TS-1 that involves the activation of H2O2 was proposed. Experimental studies showed that the major products of cyclohexanone oxidation by H2O2 catalyzed by a hollow TS-1 zeolite wereε-carprolactone, 6-hydroxyhexanoic acid, and adipic acid. These products were analyzed by GC-MS and were in good agreement with the proposed mechanism. Our studies showed that the reaction mechanism on TS-1 zeolite was different from that on Sn-beta zeolite. 相似文献
92.
The polymerization of 1,3-butadiene was examined by using a novel halogen-free neodymium m-nitrobenzenesulfonate(Nd(3-NBSO3)3·donors)/alkylaluminum binary catalyst system. The catalyst showed fairly high activity and controllable selectivity. The microstructure of the resultant polymer was adjustable by variation of electron donor and/or the alkylaluminum. 13C-NMR and thermal analysis demonstrate that the produced polybutadienes have stereo-block chain structures of cis-1,4 and trans-1,4 segments with adjustable Tm and Tc. The neodymium sulfonate-based catalyst is believed to be significant in regulating the chain structure of polydienes and in exploring 1,3-diene polymerization mechanism. 相似文献
93.
Zhi-Qiang Hou Rui-Zhe Zhang Li-Gang Luo Jing Yang Chun-Ze Liu Yuan-Yuan Wang Li-Yi Dai 《Chemical Papers》2015,69(3):490-494
The reaction of phenylacetonitrile in supercritical methanol and ethanol in a system containing a small volume of water was studied. The effects of various operating conditions, such as reaction temperature, reaction time, the mole ratio of phenylacetonitrile/water/methanol or ethanol on the product yield were systematically investigated. The optimal yield of methyl phenylacetate for phenylacetonitrile in supercritical methanol in a system containing a small volume of water was 70 % at 583 K and 2.5 h. The optimal yield of ethyl phenylacetate for phenylacetonitrile in supercritical ethanol with a small volume of water was 80 % at 583 K and 1.0 h. At the same time, a feasible mechanism was proposed for phenylacetonitrile in supercritical methanol and ethanol in a system containing a small volume of water. 相似文献
94.
Dr. Toru Amaya Dai Hata Dr. Toshiyuki Moriuchi Prof. Dr. Toshikazu Hirao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(46):16427-16433
A reduced form of polyaniline has been shown to induce direct arylation of an arenediazonium salt with an arene (Gomberg–Bachmann reaction) to give the cross‐coupling product in moderate to good yields under mild conditions. Various arenediazonium salts and arenes, including heteroarenes such as furans, thiophenes, and pyrroles, are employed for the reaction. The most favorable combination of substrates is an electron‐poor arenediazonium salt with an electron‐rich heteroarene. Investigation of the mechanism by reactions with radical scavengers and experiments on kinetic isotope effects indicated the occurrence of a radical chain reaction initiated by one‐electron reduction of an arenediazonium salt by the polyaniline. Only 1 mol % (based on aniline tetramer) of the polyaniline is required for the cross‐coupling reaction to occur. This reaction proceeds under metal‐free conditions and with no need for photonic activation. 相似文献
95.
碱金属/液氨溶液具有很强还原性,在有机合成中有着广泛的运用。在高等教育出版社出版的由邢其毅、裴伟伟、徐瑞秋以及裴坚等人编著的《基础有机化学》(第3版)中描述了在碱金属/液氨作用条件下的两类还原反应:炔烃被还原为烯烃的反应和Birch还原反应。一般认为这两种反应均生成了自由基负离子中间体。本文结合近几年的文献报道,对它们的机理进行进一步的探讨。 相似文献
96.
97.
Synthesis of Nitrogen‐Doped Mesoporous Carbon Spheres with Extra‐Large Pores through Assembly of Diblock Copolymer Micelles 下载免费PDF全文
Jing Tang Dr. Jian Liu Dr. Cuiling Li Yunqi Li Prof. Moses O. Tade Prof. Sheng Dai Prof. Yusuke Yamauchi 《Angewandte Chemie (International ed. in English)》2015,54(2):588-593
The synthesis of highly nitrogen‐doped mesoporous carbon spheres (NMCS) is reported. The large pores of the NMCS were obtained through self‐polymerization of dopamine (DA) and spontaneous co‐assembly of diblock copolymer micelles. The resultant narrowly dispersed NMCS possess large mesopores (ca. 16 nm) and small particle sizes (ca. 200 nm). The large pores and small dimensions of the N‐heteroatom‐doped carbon spheres contribute to the mass transportation by reducing and smoothing the diffusion pathways, leading to high electrocatalytic activity. 相似文献
98.
Identification of tert‐Butyl Cations in Zeolite H‐ZSM‐5: Evidence from NMR Spectroscopy and DFT Calculations 下载免费PDF全文
Dr. Weili Dai Prof.Dr. Chuanming Wang Dr. Xianfeng Yi Prof. Dr. Anmin Zheng Prof. Dr. Landong Li Prof. Dr. Guangjun Wu Prof. Dr. Naijia Guan Prof. Dr. Zaiku Xie Dipl.‐Chem. Michael Dyballa Prof. Dr. Michael Hunger 《Angewandte Chemie (International ed. in English)》2015,54(30):8783-8786
Experimental evidence for the presence of tert‐butyl cations, which are important intermediates in acid‐catalyzed heterogeneous reactions, on solid acids has still not been provided to date. By combining density functional theory (DFT) calculations with 1H/13C magic‐angle‐spinning NMR spectroscopy, the tert‐butyl cation was successfully identified on zeolite H‐ZSM‐5 upon conversion of isobutene by capturing this intermediate with ammonia. 相似文献
99.
A new phenomenon of acoustic streaming 总被引:2,自引:0,他引:2
This paper describes a new phenomenon of acoustic streaming which takes place when a Helmholtz resonator is excited by an
inside sound source with resonant frequency, and takes the form of a strong turbulent jet. The flow visualizations, hot wire
and LDV measurements are combined to investigate the process of acoustic streaming. It is found that this kind of acoustic
streaming results from the contribution of Reynolds stress. 相似文献
100.
本文提出一种用高密度位相型闪耀光栅测取板的曲率和斜率的单光束错位云纹干涉法,由于这一方法具有高灵敏度。大量程和高反差的优点。可有效地用来求解板的弯曲问题。文中还给出了周边固定圆板和带缺口的方板两个应用实例。 相似文献