In this work, we report the synthesis and characterization of highly ordered mesoporous CeO(2) thin films with crystalline walls. While this article focuses on electrochemical studies of CeO(2) with periodic nanoscale porosity, we also examine the mechanical properties of these films and show how pore flexing can be used to facilitate intercalation of lithium ions. Mesoporous samples were prepared by dip-coating using the large diblock copolymer KLE as the organic template. We establish that the films have a mesoporous network with a biaxially distorted cubic pore structure and are highly crystalline at the atomic scale when heated to temperatures above 500 degrees C. Following a previously reported approach, we were able to use the voltammetric sweep rate dependence to determine quantitatively the capacitive contribution to electrochemical charge storage. The net result is that mesoporous CeO(2) films exhibit reasonable levels of pseudocapacitive charge storage and much higher capacities than samples prepared without any polymer template. Part of this increased capacity stems from the fact that these films are able to expand normal to the substrate upon intercalation of lithium ions by flexing of the nanoscale pores. This flexing relieves stress from volume expansion that normally inhibits charge storage. Overall, the results described in this work provide fundamental insight into how nanoscale structure and mechanical flexibility can be used to increase charge storage capacity in metal oxides.
We describe in this account a general, yet facile strategy for the directed assembly of bioactive composite materials comprised of an erodible organic polymer such as polycaprolactone and physiologically-resorbable inorganic mesoporous silicon. This method exploits a combination of capillary forces and selective interfacial coupling chemistry to produce isolable macroscale (mm sized) structures possessing a diverse range of geometries through simple mixing rather than intricate molding processes. Furthermore, we demonstrate the ability of such constructs to dissociate into their individual building blocks, with the concomitant release of embedded model compounds in a sustained manner.
Two different types of erbium-doped silicon nanocrystals, along with undoped, oxide-capped Si dots, are employed to probe the impact of the impurity center location on phase transition pressure. Using a combination of high pressure optical absorption, micro-Raman, and x-ray diffraction measurements in a diamond anvil cell, it is demonstrated that the magnitude of this phase transition elevation is strongly dictated by the average spatial location of impurity centers introduced into the nanocrystal along with the interfacial quality of the surrounding oxide.
Femtosecond pump-probe absorption spectroscopy is used to investigate the role of Er(3+) dopants in the early relaxation pathways of photoexcited Si nanocrystals. The fate of photoexcited electrons in three different Si nanostructures was studied and correlated with the effect of Er-doping and the nature of the dopant architecture. In Si nanocrystals without Er(3+) dopant, a trapping component was identified to be a major electron relaxation mechanism. Addition of Er(3+) ions into the core or surface shell of the nanocrystals was found to open up additional nonradiative relaxation pathways, which is attributed to Er-induced trap states in the Si host. Analysis of the photodynamics of the Si nanocrystal samples reveals an electron trapping mechanism involving trap-to-trap hopping in the doped nanocrystals, whereby the density of deep traps seem to increase with the presence of erbium. To gain additional insights on the relative depths of the trapping sites on the investigated nanostructures, benzoquinone was used as a surface adsorbed electron acceptor to facilitate photoinduced electron transfer across the nanocrystal surface and subsequently assist in back electron transfer. The established reduction potential (-0.45 V versus SCE) of the electron acceptor helped reveal that the erbium-doped nanocrystal samples have deeper trapping sites than the undoped Si. Furthermore, the measurements indicate that internally Er-doped Si have relatively deeper trapping sites than the erbium surface-enriched nanocrystals. The electron-shuttling experiment also reveals that the back electron transfer seems not to recover completely to the ground state in the doped Si nanocrystals, which is explained by a mechanism whereby the electrons are captured by deep trapping sites induced by erbium addition in the Si lattice.
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