CeO2 samples doped with 10, 1.0, and 0.1 mol% Y2O3 and undoped CeO2 samples of high purity were studied by impedance spectroscopy at temperatures <800°C and under various oxygen partial pressures. According to microstructural investigations by SEM and analytical STEM (equipped with EDXS), the grain boundaries were free of any second phase, providing direct grain‐to‐grain contacts. An amorphous siliceous phase was detected at only a few triple junctions, if at all; as a result, its contribution to the grain‐boundary resistance was negligible. Nevertheless, the specific grain‐boundary conductivities were still 2–7 orders of magnitude lower than the bulk conductivities, depending on dopant concentration, temperature, and oxygen partial pressure. The charge carrier transport across the grain boundaries occurred only through the grain‐to‐grain contacts, whose properties were then determined by the space‐charge layer. The space‐charge potential in acceptor‐doped CeO2 was positive, causing the simultaneous depletion of oxygen vacancies and accumulation of electrons in the space‐charge layer. The very low grain‐boundary conductivities can be accounted for by the oxygen‐vacancy depletion; the accumulation of electrons became evident in weakly doped and undoped CeO2 at high temperatures and under low oxygen partial pressures.

We present an electron energy loss study using energy filtered TEM of spatially resolved surface plasmon excitations on a silver nanorod of aspect ratio 14.2 resting on a 30 nm thick silicon nitride membrane. Our results show that the excitation is quantized as resonant modes whose intensity maxima vary along the nanorod's length and whose wavelength becomes compressed towards the ends of the nanorod. Theoretical calculations modelling the surface plasmon response of the silver nanorodsilicon nitride system show the importance of including retardation and substrate effects in order to describe accurately the energy dispersion of the resonant modes.

Using energy-filtered transmission electron microscopy we measured surface-plasmon resonances of gold nanoplatelets with different shapes and edge lengths at high spatial resolution. We find equidistant maxima of the energy-loss probability along the platelet edges. The plasmon dispersion of the different geometries is very similar, i.e., hardly dependent on specimen shape. The experimental results are verified by means of finite-difference time-domain calculations which reveal the presence of wedge-plasmon polaritons propagating along the platelet edges. At platelet corners, apart from radiative losses, wedge-plasmon polaritons are partially reflected or transmitted to neighboring edges. The interference of all these contributions leads to the observed plasmon resonance modes. This is an essential step towards a thorough understanding of plasmon eigenmodes in prismatic nanoplatelets.

Low-dimensional nanostructures offer a host of intriguing properties which are distinct from those of the bulk material, owing to size-confinement effects and amplified surface areas. Here, we report on the scalable, bottom-up synthesis of ultrathin coordination polymer nanosheets via surfactant-mediated synthesis and subsequent exfoliation. Layers of a two-dimensional (2D) zinc coordination polymer are self-assembled in the interlamellar space of a reverse microemulsion mesophase into stacks of nanosheets interleaved with cethyltrimethylammonium bromide (CTAB) at regular intervals, thus giving rise to a lamellar hybrid mesostructure with a lattice period of ~8 nm and an underlying highly crystalline substructure. The basic structural motif is composed of 2D acetato-benzimidazolato-zinc layers of tetrahedrally coordinated zinc joined together by anionic acetate and benzimidazolate ligands. The hierarchical structure was studied by PXRD, TEM, EDX, EELS, AFM, and solid-state NMR spectroscopy, revealing a high level of order on both the atomic and mesoscale, suggesting fairly strong interactions along the organic-inorganic hybrid interface. Exfoliation of the hybrid material in organic solvents such as THF and chloroform yields sheet- and belt-like nanostructures with lateral sizes between 10's and 100's of nanometers and a height of about 10 nm measured by AFM, which precisely maps the basal spacing of the lamellar mesostructure; further exfoliation results in nanobelts with minimum sizes around 4 nm. Finally, the sheetlike nanostructures behave as morphological chameleons, transforming into highly regular multiwalled coordination polymer nanotubes upon treatment with organic solvents.

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