Abstract: The microstructure of the charge/orbital ordering Ruddleden-Popper phase PrCa2Mn2O7 was studied by transmission electron microscopy along both the [001] and the [110] orientation. Three coexisting charge/orbital ordering phases CO1, CO2, and CO3 were observed along the [001] orientation at room temperature. Different from the one-dimensional modulation in the CO1 and CO2 phase, the CO3 phase is characterized by two sets of mutually perpendicular structural modulations. From [110] high angle annular dark field-scanning transmission electron microscopy, we found that the Pr atoms locate in-between the bilayer MnO6 octahedra, which is different from the previous reports.

Abstract: Recently discovered series of high Tc superconductors, characterized by the existence of two types of cations within the same layer, are presented. The first family concerns the mercury based cuprates, Hg(1-x)M(x)A(2)Ca(m-1)Cu(m)O(2m+2+delta), with A = Ba and/or Sr, which exhibit structures closely related to that of the thallium cuprates TlBa2Cam-1CumO2m+3. They differ from the thallium cuprates by a high oxygen deficiency at the level of the mercury layer. It is shown that cations such as M = Cu, Pb, Tl, Bi, Ce, Pr, Cr, V, Mo, W, Ti, Sr, Ca,... can partially substitute for mercury ions, stabilizing the structures. The cationic composition of the layer depends indeed on the nature of the M cation but also on that of the alkaline earth A. For given A and M cations, the a: value remains unchanged even when the number of copper layers varies. M and Hg cations are either statistically distributed over the same site or ordered. Different types of ordering have been detected. Another way of generating mixed layers is to shear periodically the structure, leading to the formation of the so called ''collapsed phase''. In the collapsed bismuth cuprates, bismuth and copper segments, a few octahedra long, alternate in strongly waving layers. In the collapsed oxycarbonates, carbonate groups and M cations are ordered within the intermediate layer so that they can be simply described from a partial and ordered substitution of carbon for Hg,TI, Bi and other M cations building the intermediate layer. The oxycarbonitrates (Y1-xCax)(n)Ba2nCu3n-1(C,N)O3O7n-3 can also be described as an ordered substitution of carbon for copper in the 123 matrix. The different families of superconducting materials which are generated by such mechanisms are described as well as the way the different species are distributed within the mixed layers. Their influence on the physical properties are discussed.

Abstract: Synchrotron small angle X-ray scattering (SAXS) was used to characterize silicalite-1 zeolite crystallization from TEOS/TPAOH/water clear sol. SAXS patterns were recorded over a broad range of length scales, enabling the simultaneous monitoring of nanoparticles and crystals occurring at various stages of the synthesis. A simple two-population model accurately described the patterns. Nanoparticles were modeled by polydisperse coreshell spheres and crystals by monodisperse oblate ellipsoids. These models were consistent with TEM images. The SAXS results, in conjunction with in situ light scattering, showed that nucleation of crystals occurred in a short period of time. Crystals were uniform in size and shape and became increasingly anisotropic during growth. In the presence of nanoparticles, crystal growth was fast. During crystal growth, the number of nanoparticles decreased gradually but their size was constant. These observations suggested that the nanoparticles were growth units in an aggregative crystal growth mechanism. Crystals grown in the presence of nanoparticles developed a faceted habit and intergrowths. In the final stages of growth, nanoparticles were depleted. Concurrently, the crystal growth rate decreased significantly.

Abstract: Mesoporous strontium hydroxyapatite (SrHAp) nanorods (NRs) have been successfully synthesized using a simple and efficient chemical route, i.e. the hydrothermal method. Structural and morphological characterization of the as-synthesized SrHAp NRs have been performed by transmission electron microscopy (TEM) and high angle annular dark field scanning transmission electron microscopy (HAADF-STEM). TEM and HAADF-STEM measurements of the NRs reveal the coexistence of longer and shorter particles with the length ranging from 50 nm to 400 nm and a diameter of about 20-40 nm. Electron tomography measurements of the NRs allow us to better visualize the mesopores and their facets. Two model drugs, hydrophobic risperidone and hydrophilic pramipexole, were loaded into the SrHAp NRs. These nanorods were coated using a modified chitosan (CS) with poly(2-hydroxyethyl methacrylate) (PHEMA), in order to encapsulate the drug-loaded SrHAp nanoparticles and reduce the cytotoxicity of the loaded materials. The drug release from neat and encapsulated SrHAp NRs mainly depends on the drug hydrophilicity. Importantly, although neat SrHAp nanorods exhibit some cytotoxicity against Caco-2 cells, the Cs-g-PHEMA-SrHAp drug-loaded nanorods show an acceptable cytocompatibility.

Abstract: MFI zeolite nanosheets with thickness of 2 and 8 nm were synthesized, transformed into bifunctional catalysts by loading with platinum and tested in n-decane isomerization and hydrocracking. Detailed analysis of skeletal isomers and hydrocracked products revealed that the MFI nanosheets display transition-state shape-selectivity similar to bulk MFI zeolite crystals. The suppressed formation of bulky skeletal isomers and C5 cracking products are observed both in the nanosheets and the bulk crystals grown in three dimensions. This is typical for restricted transition-state shape-selectivity, characteristic for the MFI type pores. It is a first clear example of transition-state shape-selectivity inside a zeolitic nanosheet. Owing to the short diffusion path across the sheets, expression of diffusion-based discrimination of reaction products in the MFI nanosheets was limited. The 2-methylnonane formation among monobranched C10 isomers and 2,7-dimethyloctane among dibranched C10 isomers, which in MFI zeolite are favored by product diffusion, was much less favored on the nanosheets compared to the reference bulk ZSM-5 material.

Abstract: Galvanic replacement reactions on metal nanoparticles are often used for the preparation of hollow nanostructures with tunable porosity and chemical composition, leading to tailored optical and catalytic properties. However, the precise interplay between the three-dimensional (3D) morphology and chemical composition of nanostructures during galvanic replacement is not always well understood as the 3D chemical imaging of nanoscale materials is still challenging. It is especially far from straightforward to obtain detailed information from the inside of hollow nanostructures using electron microscopy techniques such as SEM or TEM. We demonstrate here that a combination of state-of-the-art EDX mapping with electron tomography results in the unambiguous determination of both morphology transformation and elemental composition of nanostructures in 3D, during galvanic replacement of Ag nanocubes. This work provides direct and unambiguous experimental evidence toward understanding the galvanic replacement reaction. In addition, the powerful approach presented here can be applied to a wide range of nanoscale transformation processes, which will undoubtedly guide the development of novel nanostructures.

Abstract: In this article, we report on the synthesis of thin, epitaxial films of the transparent conductive oxide Al:ZnO on (0001)-oriented synthetic sapphire substrates by DC sputtering from targets with a nominal 1 at.% Al substitution. The deposition was carried out at an unusually low substrate temperature of only 250 °C in argonoxygen mixtures as well as in pure argon. The impact of the processgas composition on the morphology was analysed by transmission electron microscopy, revealing epitaxial growth in all the cases with a minor impact of the process parameters on the resulting grain sizes. The transport properties resistivity, Hall effect and magnetoresistance were studied in the range from 10 to 300 K in DC and pulsed magnetic fields up to 45 T. While the carrier density and mobility are widely temperature independent, we identified a low fieldlow temperature regime in which the magnetoresistance shows an anomalous, negative behaviour. At higher fields and temperatures, the magnetoresistance exhibits a more conventional, positive curvature with increasing field strength. As a possible explanation, we propose carrier scattering at localised magnetic trace impurities and magnetic correlations.

Abstract: This work focuses on the use of tailored copper oxide nanoarchitectures as multi-functional materials for the sustainable production of hydrogen and its on-line detection. An innovative copper(II) precursor, Cu(hfa)2TMEDA, was adopted in the CVD of CuxO (x=1,2) nanosystems under both O2 and O2+H2O atmospheres on Si(100) and Al2O3 substrates. A multi-technique characterization indicates that both the phase composition (from Cu2O to CuO) and morphology (from continuous films to entangled quasi-1D nanosystems) can be tailored by varying the growth temperature and reaction atmosphere. The obtained CuxO nanodeposits are active in the photocatalytic H2 production from aqueous solutions under UV-Vis irradiation and display interesting gas sensing performances towards hydrogen detection even at moderate temperatures.