In situ FT-IR spectroscopy was exploited to study the adsorption of CO2 and CO on commercially available yttria-stabilized ZrO2 (8 mol % Y, YSZ-8), Y2O3, and ZrO2. All three oxides were pretreated at high temperatures (1173 K) in air, which leads to effective dehydroxylation of pure ZrO2. Both Y2O3 and YSZ-8 show a much higher reactivity toward CO and CO2 adsorption than ZrO2 because of more facile rehydroxylation of Y-containing phases. Several different carbonate species have been observed following CO2 adsorption on Y2O3 and YSZ-8, which are much more strongly bound on the former, due to formation of higher-coordinated polydentate carbonate species upon annealing. As the crucial factor governing the formation of carbonates, the presence of reactive (basic) surface hydroxyl groups on Y-centers was identified. Therefore, chemisorption of CO2 most likely includes insertion of the CO2 molecule into a reactive surface hydroxyl group and the subsequent formation of a bicarbonate species. Formate formation following CO adsorption has been observed on all three oxides but is less pronounced on ZrO2 due to effective dehydroxylation of the surface during high-temperature treatment. The latter generally causes suppression of the surface reactivity of ZrO2 samples regarding reactions involving CO or CO2 as reaction intermediates.

Carbon deposition following thermal methane decomposition under dry and steam reforming conditions has been studied on yttria-stabilized zirconia (YSZ), Y2O3, and ZrO2 by a range of different chemical, structural, and spectroscopic characterization techniques, including aberration-corrected electron microscopy, Raman spectroscopy, electric impedance spectroscopy, and volumetric adsorption techniques. Concordantly, all experimental techniques reveal the formation of a conducting layer of disordered nanocrystalline graphite covering the individual grains of the respective pure oxides after treatment in dry methane at temperatures T ≥ 1000 K. In addition, treatment under moist methane conditions causes additional formation of carbon-nanotube-like architectures by partial detachment of the graphite layers. All experiments show that during carbon growth, no substantial reduction of any of the oxides takes place. Our results, therefore, indicate that these pure oxides can act as efficient nonmetallic substrates for methane-induced growth of different carbon species with potentially important implications regarding their use in solid oxide fuel cells. Moreover, by comparing the three oxides, we could elucidate differences in the methane reactivities of the respective SOFC-relevant purely oxidic surfaces under typical SOFC operation conditions without the presence of metallic constituents.

Neurons are highly specialized cells in which the integration and processing of electrical signals critically depends on the precise localization of ion channels. For large-conductance Ca(2+)- activated K(+) (BK) channels, targeting to presynaptic membranes in hippocampal pyramidal cells was reported; however, functional evidence also suggests a somatodendritic localization. Therefore we re-examined the subcellular distribution of BK channels in mouse hippocampus using a panel of independent antibodies in a combined approach of conventional immunocytochemistry on cultured neurons, pre- and postembedding electron microscopy and immunoprecipitation. In cultured murine hippocampal neurons, the colocalization of BK channels with both pre- and postsynaptic marker proteins was observed. Electron microscopy confirmed targeting of BK channels to axonal as well as dendritic membranes of glutamatergic synapses in hippocampus. A postsynaptic localization of BK channels was also supported by the finding that the channel coimmunoprecipitated with PSD95, a protein solely expressed in the postsynaptic compartment. These results thus demonstrate that BK channels reside in both post- and presynaptic compartments of hippocampal pyramidal neurons.

A combination of operando Fourier transform infrared spectroscopy, operando electrochemical-impedance spectroscopy, and moisture-sorption measurements has been exploited to study the adsorption and conduction behavior of H2O and D2O on the technologically important ceramic oxides YSZ (8 mol % Y2O3), ZrO2, and Y2O3. Because the characterization of the chemisorbed and physisorbed water layers is imperative to a full understanding of (electro-)catalytically active doped oxide surfaces and their application in technology, the presented data provide the specific reactivity of these oxides toward water over a pressure-and-temperature parameter range extending up to, e.g., solid-oxide fuel cell (SOFC)-relevant conditions. The characteristic changes of the related infrared bands could directly be linked to the associated conductivity and moisture-sorption data. For YSZ, a sequential dissociative water ("ice-like" layer) and polymeric chained water ("liquid-like") water-adsorption model for isothermal and isobaric conditions over a pressure range of 10(-5) to 24 mbar and a temperature range from room temperature up to 1173 K could be experimentally verified. On pure monoclinic ZrO2, in contrast to highly hydroxylated YSZ and Y2O3, a high surface concentration of OH groups from water chemisorption is absent at any temperature and pressure. Thus, the ice-like and following molecular water layers exhibit no measurable protonic conduction. We show that the water layers, even under these rather extreme experimental conditions, play a key role in understanding the function of these materials. Furthermore, the reported data are supposed to provide an extended basis for the further investigation of close-to-real gas adsorption or catalyzed heterogeneous reactions.

The surface reactivity of Y2O3, YSZ, and ZrO2 polycrystalline powder samples toward H2 has been comparatively studied by a pool of complementary experimental techniques, comprising volumetric methods (temperature-programmed volumetric adsorption/oxidation and thermal desorption spectrometry), spectroscopic techniques (in situ electric impedance and in situ Fourier-transform infrared spectroscopy), and eventually structural characterization methods (X-ray diffraction and scanning electron microscopy). Reduction has been observed on all three oxides to most likely follow a surface or near-surface-limited mechanism involving removal of surface OH-groups and associated formation of water without formation of a significant number of anionic oxygen vacancies. Partly reversible adsorption of H2 was proven on the basis of molecular H2 desorption. Dictated by the specific hydrophilicity of the oxide, readsorption of water eventually takes place. The inference of this surface-restricted mechanism is further corroborated by the fact that no bulk structural and/or morphological changes were observed upon reduction even at the highest reduction temperatures (1173 K). We anticipate relevant implications for the use of especially YSZ in fuel cell research, since in particular the chemical state and structure of the surface under typical reducing high-temperature conditions affects the operation of the entire cell.