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31.
Direct demonstration of enhanced diffusion in mesoporous ZSM-5 zeolite obtained via controlled desilication 总被引:2,自引:0,他引:2
Groen JC Zhu W Brouwer S Huynink SJ Kapteijn F Moulijn JA Pérez-Ramírez J 《Journal of the American Chemical Society》2007,129(2):355-360
A 2 orders of magnitude gas transport improvement in a medium pore ZSM-5 zeolite has been achieved upon introduction of intracrystalline mesoporosity in gradient-free crystals by desilication post-treatment in alkaline medium. 相似文献
32.
Groen JC Hamminga GM Moulijn JA Pérez-Ramírez J 《Physical chemistry chemical physics : PCCP》2007,9(34):4822-4830
In situ pH and Attenuated Total Reflection (ATR) infrared techniques have been successfully applied in order to gain insights into the dissolution process connected to mesopore formation occurring upon alkaline treatment of ZSM-5 zeolites. Online pH measurements reveal a similar consumption of OH(-) ions in the initial stage of the reaction independent of the Si/Al ratio of the zeolite. In view of the greatly different mesoporosity development, the extraction of polymeric silica entities is anticipated, its structure depending on the framework Si/Al ratio. In agreement, ATR-IR experiments have confirmed dissolution of polymeric silicon-containing species that in the course of the alkaline treatment disintegrate into smaller entities. A direct relation between the type of porosity developed and the process of silicon extraction as measured in the liquid phase cannot be drawn. 相似文献
33.
The structures, energetic, and vibrational properties of MDyX(4) (M = Li, Na, K, Rb, Cs; X = F, Cl, Br, I) mixed alkali halide/dysprosium halide complexes have been investigated by a joint computational and experimental, matrix-isolation Fourier-transform infrared spectroscopic (MI-IR), study. According to our DFT computations for the complexes with heavier halides and alkali metals the ground-state structure is the tridentate isomer; while at high temperatures the bidentate structural isomer dominates. The survey of various dissociation processes revealed the preference of the dissociation to neutral MX and DyX(3) fragments over ionic and radical dissociation products. Cationic complexes are considerably less stable at 1000 K than the neutral complexes, and they prefer to dissociate to M(+) + DyX(4)(?) fragments. The vapor species of selected mixtures of NaBr and CsBr with DyBr(3) and of CsI with DyI(3) in the temperature range 900-1000 K have been isolated in krypton and xenon matrices and investigated by infrared spectroscopy. Besides the characteristic vibrational frequencies of the monomeric and dimeric alkali halide species and of the dysprosium trihalide molecules, certain signals indicated the formation of MDyX(4) (M = Na, Cs; X = Br, I) mixed complexes. Comparison with the computed vibrational and thermodynamic characteristics of the relevant species lead to the conclusion that these complexes appear in the vapor predominantly as the C(2v)-symmetry bidentate isomer. This is the first time that this structure was identified in an experimental vibrational spectroscopic study. The signals appearing upon performing a thermal anneal cycle were tentatively assigned to the double complex M(2)DyX(5) (M = Na, Cs; X = Br, I). A structure in which one alkali atom is bound to dysprosium by three and the other by two bridges is proposed for these double complexes. 相似文献
34.
35.
K.M. Diederix H.A. Algra J.P. Groen T.O. Klaassen N.J. Poulis R.L. Carlin 《Physics letters. A》1977,60(3):247-249
A magnetic phase transition to a long range ordered state is observed in Ni(C5H5NO)6(ClO4)2 in external fields 26.4 kOe< H < 71.0 kOe applied parallel to the threefold axis and below temperatures of 0.80 K. 相似文献
36.
37.
A liquid chromatographic column-switching system for the automated determination of flucycloxuron, a benzoylphenylurea pesticide, in crop and environmental matrices is described. The system consists of an internal surface reversed-phase (ISRP) column, a phenyl-bonded precolumn and an analytical reversed-phase (RP) C18 column. Sample extracts are evaporated to dryness and dissolved in the mobile phase of the ISRP column. An aliquot of this solution is injected into the column-switching system. Clean-up, with regard to removal of large molecules, is performed on the ISRP column. The flucycloxuron fraction from the ISRP column is concentrated on the phenyl-bonded precolumn. Additional clean-up can be performed by washing the precolumn. Finally, the compound is desorbed from the precolumn and separation and determination of the Z- and E-isomers of flucycloxuron are performed with the analytical RP-C18 column using UV detection at 254 nm. The total analysis time required is 40 min. The reproducibility of the method obtained with the column-switching system, expressed as relative standard deviation, varies between 3.7 and 10% for apple, strawberry, citrus and soil samples for flucycloxuron levels between 0.04 and 0.33 mg/kg. The system showed no loss of analytical performance after more than 300 analyses. 相似文献
38.
Theoretical study of mixed LiLnX4 (Ln = La, Dy; X = F, Cl, Br, I) rare earth/alkali halide complexes
The structure, bonding and vibrational properties of the mixed LiLnX4 (Ln = La, Dy; X = F, Cl, Br, I) rare earth/alkali halide complexes were studied using various quantum chemical methods (HF, MP2 and the Becke3-Lee-Yang-Parr exchange-correlation density functional) in conjunction with polarized triple-zeta valence basis sets and quasi-relativistic effective core potentials for the heavy atoms. Our comparative study indicated the superiority of MP2 theory while the HF and B3-LYP methods as well as less sophisticated basis sets failed for the correct energetic relations. In particular, f polarization functions on Li and X proved to be important for the Li...X interaction in the complexes. From the three characteristic structures of such complexes, possessing 1-(C3v), 2-(C2v), or 3-fold coordination (C3v) between the alkali metal and the bridging halide atoms, the bi- and tridentate forms are located considerably lower on the potential energy surface then the monodentate isomer. Therefore only the bi- and tridentate isomers have chemical relevance. The monodentate isomer is only a high-lying local minimum in the case of X = F. For X = Cl, Br, and I this structure is found to be a second-order saddle point. The bidentate structure was found to be the global minimum for the systems with X = F, Cl, and Br. However, the relative stability with respect to the tridentate structure is very small (1-5 kJ/mol) for the heavier halide derivatives and the relative order is reversed in the case of the iodides. The energy difference between the three structures and the dissociation energy decrease in the row F to I. The ionic bonding in the complexes was characterized by natural charges and a topological analysis of the electron density distribution according to Bader's theorem. Variation of the geometrical and bonding characteristics between the lanthanum and dysprosium complexes reflects the effect of "lanthanide contraction". The calculated vibrational data indicate that infrared spectroscopy may be an effective tool for experimental investigation and characterization of LiLnX4 molecules. 相似文献
39.
A glucose oxidase-based needle-type microsensor is described that is independent of the local oxygen concentration. The sensor consists of an enzyme-coated platinum microelectrode that is inserted in a glass capillary with a tip of 5–25 μm, and connected to the environment via an agar membrane. Oxygen is supplied to the enzyme coating from the shaft of the capillary. Depending on the electrode configuration, the sensor has a response time of 1–10 s, and the measuring range extends from 0.01 to 0.4 mmol l?1 or from 0.4 to 10 mmol l?1. The signal is not affected by stirring. 相似文献
40.
A total synthesis of the novel steroids DL-14α-methylestradiol () and DL-14α-methyl-19-nortestosterone () via cationic cyclization is described. Advantage was taken of the unusual stereoselectivity of Mo(CO)6/-BuOOH epoxidations. 相似文献