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981.
Abelló S Medina F Tichit D Pérez-Ramírez J Groen JC Sueiras JE Salagre P Cesteros Y 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(2):728-739
Two different rehydration procedures in the liquid or gas phase have been applied to reconstruct mixed oxides derived from calcined hydrotalcite-like materials to be used as catalysts for aldol condensation reactions. The as-synthesized hydrotalcite, its decomposition product, as well as the reconstructed solids upon rehydration were characterized by XRD, N(2) adsorption, He pycnometry, FTIR, SEM, TEM, (27)Al MAS-NMR and CO(2)-TPD (TPD=temperature-programmed desorption). Compared to the Mg-Al mixed oxide rehydrated in the gas phase (HT-rg), that rehydrated in the liquid phase (HT-rl) exhibits a superior catalytic performance with respect to the aldol condensation of citral with ketones to yield pseudoionones and in the self-aldolization of acetone. The textural properties of HT-rl and HT-rg differ strongly and determine the catalytic behavior. A memory effect led to a higher degree of reconstruction of the lamellar structure when the mixed oxide was rehydrated in the gas phase rather than in the liquid phase, although liquid-phase rehydration under fast stirring produced a surface area that was 26 times greater. This contrasts to typical statements in the literature claiming a higher degree of reconstruction in the presence of large amounts of water in the medium. CO(2)-TPD shows that the number of OH(-) groups and their nature are very similar in HT-rg and HT-rl, and cannot explain the markedly different catalytic behavior. Accordingly, only a small fraction of the available basic sites in the rehydrated samples is active in liquid-phase aldol condensations. Our results support the model in which only basic sites near the edges of the hydrotalcite platelets are partaking in aldol reactions. Based on this, reconstructed materials with small crystallites (produced by exfoliation during mechanical stirring), that is, possessing a high external surface area, are beneficial in the reactions compared to larger crystals with a high degree of intraplatelet porosity. 相似文献
982.
Shvartsburg AA Tang K Smith RD 《Journal of the American Society for Mass Spectrometry》2005,16(1):2-12
Field asymmetric waveform ion mobility spectrometry (FAIMS) holds significant promise for post-ionization separations in conjunction with mass-spectrometric analyses. However, a limited understanding of fundamentals of FAIMS analyzers has made their design and operation largely an empirical exercise. Recently, we developed an a priori simulation of FAIMS that accounts for both ion diffusion (including anisotropic components) and Coulomb repulsion, and validated it by extensive comparisons with FAIMS/MS data. Here it is corroborated further by FAIMS-only measurements, and applied to explore how key instrumental parameters (analytical gap width and length, waveform frequency and profile, the identity and flow speed of buffer gas) affect FAIMS response. We find that the trade-off between resolution and sensitivity can be managed by varying gap width, RF frequency, and (in certain cases) buffer gas, with equivalent outcome. In particular, the resolving power can be approximately doubled compared to "typical" conditions. Throughput may be increased by either accelerating the gas flow (preferable) or shortening the device, but below certain minimum residence times performance deteriorates. Bisinusoidal and clipped-sinusoidal waveforms have comparable merit, but switching to rectangular waveforms would improve resolution and/or sensitivity. For any waveform profile, the ratio of two between voltages in high and low portions of the cycle produces the best performance. 相似文献
983.
Characterization and electrochemical investigation of boron-doped mesocarbon microbead anode materials for lithium ion batteries 总被引:1,自引:0,他引:1
Mao-Hui Chen Guo-Tao Wu Guang-Ming Zhu Jin-Kua You Zu-Geng Lin 《Journal of Solid State Electrochemistry》2002,6(6):420-427
The structure and anodic performance of boron-doped and undoped mesocarbon microbeads (MCMBs) have been comparatively studied
and the results obtained by XPS, XRD, SEM, Raman spectroscopy and electrochemical measurements are discussed. It is found
that boron doping introduces a depressed d
002 spacing and the larger amount of "unorganized carbon", which induces vacancy formation in the graphite planes and leads to
a quite different morphology from that of the undoped material. Electrochemical charge/discharge cycle tests indicated that
after boron doping the lithium intercalation was carried through at a somewhat higher potential, being attended by greater
irreversible capacity loss.
Electronic Publication 相似文献
984.
A series of MCM22 zeolites exchanged with copper and cobalt are studied for the selective catalytic reduction (SCR) of NO
with C3H8 and the behavior compared with that of Cu and Co-beta and ZMS5 zeolites. The results show that Co and Cu-MCM22 samples are
stable SCR catalysts. These zeolites give the maximum activity at 450°C. Their behavior towards oxygen content in the reactant
phase and exchange level of the metal in the catalyst, is qualitatively similar to that of metal exchanged beta and ZSM5 zeolite,
but the yields obtained with this zeolite are lower in any case. The infrared studies of adsorbed NO show, contrary to what
is occurring in ZSM5 in which only Cu+ sites are observed at low NO partial pressure, that in this condition, Cu+ and Cu2+ species are formed on MCM22. The results indicate that in MCM22, the copper located in the 10 member ring (MR) circular channels
behaves similarly to that present in ZSM5, while the Cu present in the 12 MR cavities has a strong tendency to agglomerate
forming non active CuO clusters. 相似文献
985.
The chemical reactivity of the [1,2,3]triazolo[1,5-a]- and [1,5-c]-pyrimidinium salts towards morpholine, water and sodium methoxide have been studied. Among others, new 1-aza and 2-azabutadienes substituted by a [1,2,3]-triazole ring were obtained in the course of the opening of the positively charged pyrimidine ring. 相似文献
986.
M.Victoria Mart?&#x;nez-D?&#x;azSagrario Esperanza Andrés de la EscosuraMarinella Catellani Sami YunusSilvia Luzzati Tomás Torres 《Tetrahedron letters》2003,44(46):8475-8478
Two new donor-acceptor copolymers comprising a polythiophene backbone, and bearing phthalocyanine chromophores on the side chains have been prepared. Preliminary photophysical characterization of these materials by FTIR photoinduced absorption indicates that electron transfer from the polythiophene to the phthalocyanine units takes place. 相似文献
987.
Spectroscopic infrared ellipsometry was applied to determine the optical constants of thin metal layers deposited on dielectric substrates such as glass or CaF(2). The layers were produced by evaporating gold or silver in a vacuum, and the coverage, that is the deposited mass per area, was chosen in the range 80-1200 mg m(-2) for gold, which refers to thicknesses in the lower nanometer range; in the case of the specifically lighter silver, about half the coverage was applied. At low coverage a metal island structure is obtained, which gives rise to surface-enhanced infrared absorption (SEIRA). Depending on the coverage, the deposited films exhibit either dielectric or metallic optical properties. Atomic force microscopy and conductivity measurements complement the spectroscopic observation. 相似文献
988.
E. Krös L. Ladányi V. Friedrich Zs. Nagy Á. Kis 《Reaction Kinetics and Catalysis Letters》1974,1(4):455-460
The Ru(dipy)
3
2+
-bromate-malonic acid oscillating system was in vestigated. It has been established that at early stages of the reaction the period of oscillation is about 20 sec and the potential change is about 170 mV; chloride at concentrations hiherg than 10–3M is an inhibitor. The rates of both heat evolution and formation of bromomalonic acid are periodic. The activation energy of the oscillating (E) is 16.2 kcal mol–1. Ru(dipy)
3
2+
-- . , 20 , 170 ; , - 10–3 M, . . (E) 16,2 /. 相似文献
989.
Tomás Pérez-Ruiz Carmen Martínez-Lozano Virginia Tomás Antonio Sanz Jesús Martín 《Fresenius' Journal of Analytical Chemistry》1998,362(4):399-403
A flow-injection configuration is proposed for the fluorimetric determination of ethylenethiourea. The procedure is based
on the inhibitory effect of ethylenethiourea on the oxidation of thiamine to thiochrome by mercury(II). A linear calibration
graph was obtained between 0.1 and 2.0 μg mL–1, with a sampling rate of 40 samples per hour and a relative standard deviation of about 1.11%. The usefulness of the method
was tested for the determination of ethylenethiourea residues in water, milk, potatoes, pear, grape and apple.
Received: 26 January 1998 / Revised: 6 April 1998 / Accepted: 9 April 1998 相似文献
990.
Stuart D. R.?GallowayEmail author Elizabeth M.?Broad 《Monatshefte für Chemie / Chemical Monthly》2005,136(8):1391-1410
Summary. Oral L-carnitine supplementation is frequently reported to have beneficial effects on exercise capacity in clinical populations and has been considered as a potential ergogenic aid for endurance athletes. However, this latter view is largely unsubstantiated possibly due to many experimental studies being poorly controlled or difficult to compare. The potential for oral L-carnitine supplementation to influence skeletal muscle carnitine content has been questioned and there are several key factors identified that may explain variations between study outcomes. Recent more well controlled research suggests some potential for L-carnitine to act as a key regulator of cellular stress, possibly through an impact on the integration of carbohydrate and lipid metabolism, and this work should be followed up in future by well controlled studies in both athlete and clinical subject groups. 相似文献