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151.
We report on a molecular simulation study of the homogeneous nucleation of CO2 in the supercooled liquid at low pressure (P = 5 MPa) and for degrees of supercooling ranging from 32% to 60%. In all cases, regardless of the degree of supercooling, the structure of the crystal nuclei is that of the Pa3 phase, the thermodynamically stable phase. For the more moderate degree of supercooling of 32%, the nucleation is an activated process and requires a method to sample states of high free energy. In this work, we apply a series of bias potentials, which promote the ordering of the centers of mass of the molecules and allow us to gradually grow crystal nuclei. The reliability of the results so obtained is assessed by studying the evolution of the nuclei in the absence of any bias potential, and by determining their probability of growth. We estimate that the size of the critical nucleus, for which the probability of growth is 0.5, is approximately 240 molecules. Throughout the nucleation process, the crystal nuclei clearly exhibit a Pa3 structure, in apparent contradiction with Ostwald's rule of stages. The other polymorphs have a much larger free energy. This makes their formation highly unlikely and accounts for the fact that the nucleation of CO2 proceeds directly in the stable Pa3 structure. 相似文献
152.
Jäntti introduced a method to reduce the time required for the stepwise measurement of adsorption isotherms (Jäntti et al., Progress in Vacuum Microbalance Techniques, Vol. 1, Heyden, London, pp. 345–353, 1972). After a pressure change he measured the adsorbed mass three times and calculated its equilibrium value for the new pressure. In the present paper we discuss the applicability of this method in a broader scope (without starting from a single combination of gas and solid adsorbent) and also discuss the influence of measurement inaccuracies. It is shown that the method can serve as an early warning system, which decides whether an improvement of the adsorption model is necessary. 相似文献
153.
Sihem Khaddar-Zine Abdelhamid Ghorbel Claude Naccache 《Journal of Sol-Gel Science and Technology》2000,19(1-3):637-641
Alumina or silica supported chromium oxide catalysts prepared by sol-gel technique have been investigated by X-ray diffraction, BET analysis, combined diffuse reflectance spectroscopy, EPR and reduction-extraction by ethane 1,2 diol. The results reveal the presence of Cr3+, Cr5+ and Cr6+ ions. Chromium species Cr6+ are isolated and atomically dispersed on the alumina support as free chromate CrO
4
2–
while on silica, dichromate or polychromate species like Cr2O
7
2–
or Cr3O
10
2–
predominate. Chromium oxide exhibits a better catalytic properties for paraxylene partial oxidation, when it is supported on alumina. The difference of oxidation states and degree of oligomerisation of chromium on the two supports affects the catalytic properties. 相似文献
154.
Jia Xi Wang Aswini K. Dash Jean Claude Berthet Michel Ephritikhine Moris S. Eisen 《Journal of organometallic chemistry》2000,610(1-2):49-57
Dehydrocoupling reactions of primary amines RNH2 with PhSiH3 were catalyzed by [(Et2N)3U][BPh4] to give the corresponding aminosilanes PhSiH3−n(NHR)n (n=1–3), the relative yields of the products were found to be dependent on the experimental conditions and on the nature of R. For a primary silane (PhSiH3), the reactivity of RNH2 follows the order primary>secondary>tertiary. Similar dehydrocoupling reactions using secondary amines with secondary silanes were found to be less reactive. Homodehydrocoupling of the silane was found not to be a competing reaction at room temperature. The hydride [(RNH)2UH][BPh4], which is plausibly formed in the reaction of [(RNH)3U][BPh4] with PhSiH3 is a likely intermediate in the catalytic cycle. 相似文献
155.
156.
157.
158.
Falk Bernsmann Dr. Ovidiu Ersen Dr. Jean‐Claude Voegel Edward Jan Prof. Nicholas A. Kotov Prof. Vincent Ball 《Chemphyschem》2010,11(15):3299-3305
Films formed by oxidation of dopamine are of interest for functionalisation of solid–liquid interfaces owing to their versatility. However, the ability to modulate the properties of such films, for example, permeability to ionic species and the absorption coefficient, is urgently needed. Indeed, melanin films produced by oxidation of dopamine absorb strongly over the whole UV/Vis part of the electromagnetic spectrum and are impermeable to anions even for a film thickness as low as a few nanometers. Herein we combine oxidation of dopamine to produce a solution containing dopamine–melanin particles and their alternating deposition with poly(diallyldimethylammonium chloride) to produce films which have nearly the same morphology as pure dopamine–melanin films but are less compact, more transparent and more permeable to ferrocyanide anions. 相似文献
159.
160.
Atsuo Yamada Kazuyuki Saka Makiko Uehara Sou Taminato Ryoji Kanno Fabrice Mauvy Claude Grenier 《Electrochemistry communications》2010,12(12):1690-1693
Electrode–electrolyte hetero-epitaxial systems for solid oxide fuel cells (SOFCs) with two different configuration of Nd2NiO4 + δ(110)//YSZ(100) and Nd2NiO4 + δ(100)//YSZ(110) were successfully fabricated by pulsed laser deposition. Thin films of Nd2NiO4 + δ approximately 20 nm thick were grown on a commercial single crystal of YSZ. The preferred two-dimensional diffusion paths of the oxide ions were perpendicular to the substrate for both configurations and showed oxygen reduction capability different from each other. This opens up new research direction focusing on the details of anisotropic catalytic activity of SOFC cathode depending on the crystalline surface. 相似文献