Abstract: Nanostructured core−shell microspheres with a rough rutile core and a thin anatase shell are synthesized via a one-step heterogeneous templated hydrolysis process of TiCl4 vapor on the aerosol water−air interface. The rutile-in-anatase core−shell structure has been evidenced by different electron microscopy techniques, including electron energy-loss spectroscopy and 3D electron tomography. A new mechanism for the formation of a crystalline rutile core inside the anatase shell is proposed based on a statistical evaluation of a large number of electron microscopy data. We found that the control over the TiCl4 vapor pressure, the ratio between TiCl4 and H2O aerosol, and the reaction conditions plays a crucial role in the formation of the core−shell morphology and increases the yield of nanostructured microspheres.

Abstract: In the Mg4−xNixNb2O9 (0x4) system two ranges of solid solution have been found. One of the solid solutions has a corundum-related structure type (space group ); the second one adopts the II-Ni4Nb2O9 structure type (space group Pbcn). The unit cell constants and atomic positions have been determined and refined using neutron powder diffraction data. Electron diffraction and high-resolution transmission electron microscopy (HRTEM) from MgNi3Nb2O9 crystals identify the presence of planar defects and the intergrowth of several (structurally related) phases. The magnetic susceptibility of Mg3NiNb2O9, measured in the temperature range T=2300 K, shows no indications of magnetic ordering at low temperatures, while for MgNi3Nb2O9 there is a magnetic ordering at temperatures below 45.5 K.

Abstract: Transition metal L2,3 electron energy-loss spectra for a wide range of V-, Mn- and Fe-based oxides were recorded and carefully analyzed for their correlation with the formal oxidation states of the transition metal ions. Special attention is paid to obtain an accurate energy scale which provides absolute energy positions for all core-loss edges. The white-line ratio method, chemical shift method, ELNES fitting method, two-parameter method and other methods are compared and their validity is discussed. Both the ELNES fitting method and the chemical shift method have the advantage of a wide application range and good consistency but require special attention to accurately measure the core-loss edge position. The obtained conclusions are of fundamental importance, e.g., for obtaining atomic resolution oxidation state information in modern experiments.

Abstract: Using a combination of high-angle annular dark-field scanning transmission electron microscopy and atomically resolved electron energy-loss spectroscopy in an aberration-corrected transmission electron microscope we demonstrate the possibility of 2D atom by atom valence mapping in the mixed valence compound Mn3O4. The Mn L2,3 energy-loss near-edge structures from Mn2+ and Mn3+ cation sites are similar to those of MnO and Mn2O3 references. Comparison with simulations shows that even though a local interpretation is valid here, intermixing of the inelastic signal plays a significant role. This type of experiment should be applicable to challenging topics in materials science, such as the investigation of charge ordering or single atom column oxidation states in, e.g., dislocations.

Abstract: For the first time, the local structure and physical properties of Ru1222 based compounds (RuSr(2)Gd(1.4)Ce(0.6)Cu(2)O(10-delta) and RuSr(2)Gd(1.8-x)Y(0.2)CexCu(2)O(10) (x = 0.90-0.55)) have been investigated and analyzed together on the very same compounds. The Ru1222 superstructure was confirmed by TEM at a local scale and was suggested to have an orthorhombic symmetry with space group Aba2 and lattice parameters a(s) similar or equal to root 2a, b(s) similar or equal to root 2a and c(s) = c. This new Ru1222 superstructure distortion from tetragonal symmetry is proposed to have a positive correlation with the superconductivity variation of these compounds. The more the distortion towards orthorhombic symmetry, the higher the critical superconducting temperature these compounds can achieve. The T(c)(0) of RuSr(2)Gd(1.8-x)Y(0.2)Ce(x)Cu(2)O(10-delta) (x = 0.85-0.55) increases monotonically from 4 to 16 K when x decreases from 0.85 to 0.70, then RuSr(2)Gd(2)Cu(2)O(8) defects emerge and the T(c) decreases with decreasing x. Ru1212 defects are observed to intergrow epitaxially with the Ru1222 structure as lamellas along the c-axis in RuSr(2)Gd(1.4)Ce(0.6)Cu(2)O(10-delta). Although Ru1212 is a superconductor, the intergrowth severely restrains its superconductivity.

Abstract: YBa2Cu3O7-x artificial grain boundary Josephson junctions have been fabricated, employing a recently implemented biepitaxial technique. The grain boundaries can be obtained by controlling the orientation of the MgO seed layer and are characterized by a misalignment of the c-axes (45 degrees a-axis tilt or 45 degrees a-axis twist). These types of grain boundaries are still mostly unexplored. We carried out a complete characterization of their transport properties and microstructure. Junctions and de SQUIDs associated with these grain boundaries exhibit an excellent Josephson phenomenology and high values of the ICRN product and of the magnetic flux-to-voltage transfer parameter respectively. Remarkable differences in the transport parameters of tilt and twist junctions have been observed, which can be of interest for several applications. A maximum speed of Josephson vortices as calculated from the voltage step values of the order of 2 x 10(6) m s(-1) is obtained. These devices could also have some impact on experiments designed to study the symmetry of the order parameter, exploiting their microstructure and anisotropic properties. High-resolution electron microscopy showed the presence of perfect basal plane faced boundaries in the cross sections of tilt boundaries.

Abstract: High-performing Fe-based electrodes for Li-based batteries are eagerly pursued because of the abundance and environmental benignity of iron, with especially great interest in polyanionic compounds because of their flexibility in tuning the Fe3+/Fe2+ redox potential. We report herein the synthesis and structure of a new Fe-based oxysulfate phase, Fe2O(SO4)(2), made at low temperature from abundant elements, which electrochemically reacts with nearly 1.6 Li atoms at an average voltage of 3.0 V versus Li+/Li, leading to a sustained reversible capacity of similar to 125 mAh/g. The Li insertiondeinsertion process, the first ever reported in any oxysulfate, entails complex phase transformations associated with the position of iron within the FeO6 octahedra. This finding opens a new path worth exploring in the quest for new positive electrode materials.

Abstract: As a size- and shape-selective catalyst, zeolites are widely used in petroleum and fine-chemicals processing. However, their small micropores severely hinder molecular diffusion and are sensitive to coke formation. Hierarchically porous zeolite single crystals with fully interconnected, ordered, and tunable multimodal porosity at macro-, meso-, and microlength scale, like in leaves, offer the ideal solution. However, their synthesis remains highly challenging. Here, we report a versatile confined zeolite crystallization process to achieve these superior properties. Such zeolite single crystals lead to significantly improved mass transport properties by shortening the diffusion length while maintaining shape-selective properties, endowing them with a high efficiency of zeolite crystals, enhanced catalytic activities and lifetime, highly reduced coke formation, and reduced deactivation rate in bulky-molecule reactions and methanol-to-olefins process. Their industrial utilization can lead to the design of innovative and intensified reactors and processes with highly enhanced efficiency and minimum energy consumption.

Abstract: The release of the lattice oxygen due to the thermal degradation of layered lithium transition metal oxides is one of the major safety concerns in Li-ion batteries. The oxygen release is generally attributed to the phase transitions from the layered structure to spinel and rocksalt structures that contain less lattice oxygen. Here, a different degradation pathway in LiCoO2 is found, through oxygen vacancy facilitated cation migration and reduction. This process leaves undercoordinated oxygen that gives rise to oxygen release while the structure integrity of the defect-free region is mostly preserved. This oxygen release mechanism can be called surface degradation due to the kinetic control of the cation migration but has a slow surface to bulk propagation with continuous loss of the surface cation ions. It is also strongly correlated with the high-voltage cycling defects that end up with a significant local oxygen release at low temperatures. This work unveils the thermal vulnerability of high-voltage Li-ion batteries and the critical role of the surface fraction as a general mitigating approach.

Abstract: Insulating and metallic stripes above and below the Curie temperature, T-C, respectively, were observed by a high-resolution scanning tunneling microscopy (STM) and/or spectroscopy (STS) in A-site ordered and macroscopically strain free epitaxial La0.75Ca0.25MnO3 film grown on MgO substrate. The “insulating” stripes were found to be incommensurable to the lattice and aligned along (110) direction. Metallic stripes were commensurable with periodicity 2a(p)similar to 0.8 nm and aligned parallel to the crystallographic a/b-axis. Formation of these stripes involves competing charge, orbital, and lattice orders and is an outcome of an overlapping of electron wave functions mediated by the local lattice-strain distribution, existed even in A-site ordered film due to the difference in cation radii of La and Ca. (C) 2007 Elsevier B.V. All rights reserved.

Abstract: X-ray photoelectron spectroscopy at 3.5 keV photon energy, in combination with high-resolution transmission electron microscopy, is used to follow the formation of the interface between rhodium and carbon nanotubes. Rh nucleates at defect sites, whether initially present or induced by oxygen-plasma treatment. More uniform Rh cluster dispersion is observed on plasma-treated CNTs. Experimental results are compared to DFT calculations of small Rh clusters on pristine and defective graphene. While Rh interacts as strongly with the carbon as Ti, it is less sensitive to the presence of oxygen, suggesting it as a good candidate for nanotube contacts.

Abstract: Site selective doping of aligned carbon nanostructures represents a promising approach for their implementation in actual devices. In the present work we report on alkali metals decoration on low density vertically aligned carbon nanotubes, disclosing the possibility of engineering site selective depositions of potassium atoms on the carbon systems. Photoemission measurements were combined with microscopy demonstrating the effective spatial control of alkali deposition. The changes of electronic structures of locally doped carbon regions were studied by exploiting the ability of the scanning photoemission microscopy technique. From the analysis of experimental data supported by theoretical calculations, we show the tuning of the charge transfer from potassium to carbon atoms belonging to neighboring nanotubes or along the same tube structure.