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M. Zakrzewski D. D. Klug J. A. Ripmeester 《Journal of inclusion phenomena and macrocyclic chemistry》1994,17(3):237-247
A high-pressure phase of the clathrate hydrate of tetrahydrofuran was prepared by freezing a liquid phase of overall composition THF · 7 H2O under a pressure of 3.0 kbar, or by pressurizing the solid structure II THF hydrate of 255K to 3.4 kbar. Unfortunately, the products recovered at 77K were always mixed phase materials as shown by X-ray powder diffraction. A number of diffraction lines could be indexed in terms of the cubic structure I hydrate with a slightly expanded lattice parameter, 12.08 Å, giving some support to Dyadin's idea that the high pressure phase transition involves a conversion of Structure II to Structure I. Other phases observed in the recovered product include Ice IX and amorphous materials. The reversion of the high pressure sample to the structure II hydrate was followed by differential scanning calorimetry. At ambient pressure, the high pressure sample converts slowly back to Structure II hydrate event at 77K.NRCC No. 35786. 相似文献
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Haque SA Palomares E Cho BM Green AN Hirata N Klug DR Durrant JR 《Journal of the American Chemical Society》2005,127(10):3456-3462
In this paper we focus upon the electron injection dynamics in complete dye-sensitized nanocrystalline metal oxide solar cells (DSSCs). Electron injection dynamics are studied by transient absorption and emission studies of DSSCs and correlated with device photovoltaic performance and charge recombination dynamics. We find that the electron injection dynamics are dependent upon the composition of the redox electrolyte employed in the device. In a device with an electrolyte composition yielding optimum photovoltaic device efficiency, electron injection kinetics exhibit a half time of 150 ps. This half time is 20 times slower than that for control dye-sensitized films covered in inert organic liquids. This retardation is shown to result from the influence of the electrolyte upon the conduction band energetics of the TiO2 electrode. We conclude that optimum DSSC device performance is obtained when the charge separation kinetics are just fast enough to compete successfully with the dye excited-state decay. These conditions allow a high injection yield while minimizing interfacial charge recombination losses, thereby minimizing "kinetic redundancy" in the device. We show furthermore that the nonexponential nature of the injection dynamics can be simulated by a simple inhomogeneous disorder model and discuss the relevance of our findings to the optimization of both dye-sensitized and polymer based photovoltaic devices. 相似文献
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Athos Bellomo und Otto Klug 《Fresenius' Journal of Analytical Chemistry》1965,207(2):93-98
Zusammenfassung Die Messung der Elektrolytkonzentration in fließenden Lösungen, auch bei solchen, die Niederschläge oder Suspensionen enthalten, wird auf Grund der Veränderung des Dielektrikums einer Zelle, welche von einem elektrischen Hochfrequenzstrom durchflossen wird, durchgeführt. Auf diesem Wege ist die quantitative Bestimmung der Konzentration der gelösten Substanz oder die der durchlaufenden Menge beträchtlich vereinfacht und automatisiert. Dabei werden subjektive und Manipulationsfehler weitgehend ausgeschlossen. Die untersuchte Probe erleidet keinerlei Veränderungen.
Summary The electrolyte concentration of flowing solutions and of suspensions or solutions containing precipitates can be measured by the variation of the dielectrics in a cell, which is coupled with a high-frequency circuit. By means of this method the quantitative determination of the concentration of solutions or the determination of the quantity of ions passed through the tube can be simplified. The method makes possible an automatization and it precludes the possibility of subjective and manipulation errors. During the measurement the sample remains unchanged.相似文献
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Proton NMR shielding constants and chemical shifts for hydrogen guests in small and large cages of structure II clathrates are calculated using density-functional theory and the gauge-invariant atomic-orbital method. Shielding constants are calculated at the B3LYP level with the 6-311++G(d,p) basis set. The calculated chemical shifts are corrected with a linear regression to reproduce the experimental chemical shifts of a set of standard molecules. The calculated chemical shifts of single hydrogen molecules in the small and large structure II cages are 4.94 and 4.84 ppm, respectively, which show that within the error range of the method the H2 guest molecules in the small and large cages cannot be distinguished. Chemical shifts are also calculated for double occupancy of the hydrogen guests in small cages, and double, triple, and quadruple occupancy in large cages. Multiple occupancy changes the chemical shift of the hydrogen guests by approximately 0.2 ppm. The relative effects of other guest molecules and the cage on the chemical shift are studied for the cages with multiple occupancies. 相似文献
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硅基材料是新一代高容量锂离子蓄电池负极材料的典型代表,近年来已成为理论研究和应用研究的热点.本文介绍了锂离子电池硅基负极材料的制备方法、电化学性能及其研究现状,分析了硅材料作为锂离子电池负极材料存在的问题;讨论了硅材料作为锂离子电池负极材料的研究前景.并指出若能克服目前存在问题,将有望成为新一代锂离子电池负极材料. 相似文献
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Manoj K. Kolel‐Veetil Kenan P. Fears Syed B. Qadri Christopher A. Klug Teddy M. Keller 《Journal of polymer science. Part A, Polymer chemistry》2012,50(15):3158-3170
A semicrystalline inorganic–organic hybrid crosslinked network containing polyhedral oligomeric silsesquioxane (POSS) cores was constructed by the unusual hydrosilylation of the terminal vinyl groups of an internal acetylene‐containing silane linker by a POSS monomer. Products from the thermal treatments of this network in either argon or air at 250, 550, and 1000 °C, respectively, were characterized by Fourier transform infrared, Solid‐state 13C and 29Si magic angle spinning NMR, X‐ray diffraction and XPS analyses. The highly symmetrically functionalized POSS silica clusters, in the fluorite silica phase, in the network were found to remain unchanged on thermal treatment possibly due to the shielding of the silica core by the functionalities and a cancellation of thermal stresses on the silica core. Stabilization of the metastable α‐cristobalite phase, which is typically formed on cooling by a β‐ to α‐transition of the β‐cristobalite phase formed above 1400 °C, was observed in the amorphous regions in the network sample treated only to 1000 °C in air. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献