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1.
Simen Gjelseth Antonsen Arne Joakim C. Bunkan Tomas Mikoviny Yngve Stenstrøm Armin Wisthaler 《Molecular physics》2020,118(15)
The kinetics of the O3, OH and NO3 radical reactions with diazomethane were studied in smog chamber experiments employing long-path FTIR and PTR-ToF-MS detection. The rate coefficients were determined to be k CH2NN+O3?=?(3.2?±?0.4)?×?10?17 and k CH2NN+OH?=?(1.68?±?0.12)?×?10?10 cm3 molecule?1 s?1 at 295?±?3?K and 1013?±?30 hPa, whereas the CH2NN?+?NO3 reaction was too fast to be determined in the static smog chamber experiments. Formaldehyde was the sole product observed in all the reactions. The experimental results are supported by CCSD(T*)-F12a/aug-cc-pVTZ//M062X/aug-cc-pVTZ calculations showing the reactions to proceed exclusively via addition to the carbon atom. The atmospheric fate of diazomethane is discussed. 相似文献
2.
DFT mechanistic study of the H2‐assisted chain transfer copolymerization of propylene and p‐methylstyrene catalyzed by zirconocene complex 下载免费PDF全文
Cheng‐Gen Zhang Shu‐Yuan Yu Liaoyun Zhang Huayi Li Zhi‐Xiang Wang 《Journal of polymer science. Part A, Polymer chemistry》2015,53(4):576-585
DFT computations have been performed to investigate the mechanism of H2‐assisted chain transfer strategy to functionalize polypropylene via Zr‐catalyzed copolymerization of propylene and p‐methylstyrene (pMS). The study unveils the following: (i) propylene prefers 1,2‐insertion over 2,1‐insertion both kinetically and thermodynamically, explaining the observed 1,2‐insertion regioselectivity for propylene insertion. (ii) The 2,1‐inserion of pMS is kinetically less favorable but thermodynamically more favorable than 1,2‐insertion. The observation of 2,1‐insertion pMS at the end of polymer chain is due to thermodynamic control and that the barrier difference between the two insertion modes become smaller as the chain length becomes longer. (iii) The pMS insertion results in much higher barriers for subsequent either propylene or pMS insertion, which causes deactivation of the catalytic system. (iv) Small H2 can react with the deactivated [Zr]?pMS?PPn facilely, which displace functionalized pMS?PPn chain and regenerate [Zr]? H active catalyst to continue copolymerization. The effects of counterions are also discussed. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 576–585 相似文献
3.
《Comptes Rendus Chimie》2015,18(9):993-1000
The electrochemical oxidation of N-acetyl-p-aminophenol (PAR) was investigated at a Pt electrode with the application of cyclic (CV) and differential pulse (DPV) voltammetry methods. An effect of scan rate, substrate concentration and pH on electrode reactions was determined. The parameters of substrate electro-oxidation, i.e. heterogeneous rate constant, charge transfer coefficient, and diffusion coefficient, were calculated. Our investigation's results prove the exchange of two electrons and one proton in the first step, followed by a chemical reaction. PAR electro-oxidation occurs according to an EC mechanism. 相似文献
4.
采用密度泛函理论B3LYP方法,研究了锡苯和铅苯的[2+2],[4+2]及[4+4]二聚反应的微观机理和势能剖面,考察了Sn(Pb)原子上的2,4,6-三甲基苯基(Mes)取代基对反应势能剖面的影响.研究结果表明,所有反应均为协同过程,且大多数情况下,2个C—Sn(Pb)键同步形成.[2+2]和[4+2]反应在热力学和动力学上均比相应的[4+4]反应容易进行,而[4+2]反应在动力学上比相应的[2+2]反应有利.Sn(Pb)原子上的Mes取代基在热力学和动力学上均不利于反应的进行.铅苯的动力学稳定性与锡苯相当,但其热力学稳定性高于锡苯. 相似文献
5.
提出用溶胶粒子表面修饰方法,结合溶胶凝胶技术制备无机催化膜.该方法的基本原理是利用合适的金属配合物在胶粒表面的吸附作用,经溶胶凝胶过程,将活性组分结合到无机膜中.实验测定结果表明:(NiEDTA)2-,VO-3,MoO2-4,(Pd(NH3)4)2+,PdCl2-4,PtCl2-6和RhCl3-6可用来修饰AlOOH溶胶.以Pd/γAl2O3催化膜的制备为例,经三次溶胶凝胶过程,可制得无裂缺的厚度为9μm的Pd/γAl2O3催化膜,膜材料的平均孔直径为6nm,Pd被均匀地分布在膜的顶层,其平均粒径为23nm. 相似文献
6.
A new family of positive photosensitive polyimide (PPI) systems composed of solvent soluble polyimides (Pls) with cyclobutane (CBDA) structures and diazonaphthoquinone compounds (DNQ) has been prepared. Heat and catalytic imidizations were carried out to obtain CBDA Pls; the former was better than the latter in controlling the molecular weight of the Pl. The ? OH groups in the Pls were easily acetylated during catalytic imidization, so ? COOH groups were selected as weak acidic groups in the Pls. The ? COOH groups were also effective in giving the Pls an alkaline solubility. Therefore, Pls having ? COOH groups were superior to those having ? OH groups for PPI systems. The photosensitive properties of various PPl systems containing ? COOH were found to vary with the fraction of ? COOH groups in the Pls, the content of DNQ in the systems, and the molecular weight of the Pls. 相似文献
7.
《Electroanalysis》2006,18(6):595-604
The following two numerical models have been applied to zinc cations electroreduction in 1 M NaClO4 water solution: a classical EE model describing the concentration of involved species in solution (semi infinitive diffusion region), an extended EE model describing both: the concentration of involved species in solution and the concentration of metallic zinc inside mercury drop (in limited area of diffusion). In the latter model the inner part of mercury drop and surrounding solution were treated as dynamic interrelated system. Both models were applied to experimental cyclic voltammetric CV data in 1 M NaClO4, the results compared and discussed. The concentration profiles of all species including metallic zinc inside mercury drop were performed. The presented integrated model is essential for theoretical and analytical aspects of the electrochemistry of mercury soluble metal cations and amalgams. 相似文献
8.
Shufeng Zuo 《Applied Surface Science》2006,253(5):2508-2514
Al-pillared clays supported rare earths (RE/Al-PILC) are prepared and used as supports of palladium catalysts for deep oxidation of low concentrations of benzene (130-160 ppm). The supports and catalysts are characterized by X-ray powder diffraction (XRD), FT-IR, BET, transmission electron microscopy (TEM) and temperature-programmed reduction (H2-TPR). The results show that Al-pillaring results in a strong increase in the basal spacing (d0 0 1) from about 1.2 to 1.8 nm, and an increase in the BET surface area from 63.6 (±3.2) to 238.8 (±11.9) m2/g. Activity tests of deep oxidation of low concentration benzene show catalysts supported on Al-PILC and RE/Al-PILC are obviously more active than that on raw clay. Pd/6% Ce/Al-PILC, in particular, can catalyze the complete oxidation of low concentration benzene at a temperature as low as about 290 °C. 相似文献
9.
1 INTRODUCTION Carbon nanotubes have many potential applica- tions due to their unique structures and properties[1~4]. Physicists have been studying their electrical, me- chanical and other properties since their discove- ries[5, 6]. Recently, chemists are interested in carbon nanotubes because their properties can be altered by chemical functionalization[7~14], and these functiona- lized nanotubes can undergo further chemical trea- tment. So the potential application range of such na- … 相似文献
10.
Grishin D. F. Semyonycheva L. L. Telegina E. V. Smirnov A. S. Nevodchikov V. I. 《Russian Chemical Bulletin》2003,52(2):505-507
Organometallic compounds Cp2TiCl2, (EtC5H4)2NbCl2, and (PriC5H4)2WCl2 were assessed as additives that control polymer chain growth in the polymerization of methyl methacrylate. In the presence of compounds mentioned in amounts comparable with that of the initiator, a uniform process with no gel-effect occured and respective linear increase in the molecular weight of the polymer up to high degrees of the monomer conversion was observed. 相似文献