Atomic Resolution Imaging with a sub-50 pm Electron Probe

Using a highly coherent focused electron probe in a 5th order aberration-corrected transmission electron microscope, we report on resolving a crystal spacing less than 50 pm. Based on the geometrical source size and residual coherent and incoherent axial lens aberrations, an electron probe is calculated, which is theoretically capable of resolving an ideal 47 pm spacing with 29percent contrast. Our experimental data show the 47 pm spacing of a Ge 114 crystal imaged with 11-18percent contrast at a 60-95percent confidence level, providing the first direct evidence for sub 50-pm resolution in ADF STEM imaging

A general approach to fabricate fe3O4 nanoparticles decorated with Pd, Au, and Rh: Magnetically recoverable and reusable catalysts for Suzuki C-C cross-coupling reactions, hydrogenation, and sequential reactions

A facile strategy has been explored for loading noble metals onto the surface of ferrite nanoparticles with the assistance of phosphine-functionalized linkers. Palladium loading is shown to occur with participation of both the phosphine function and the surface hydroxyl groups. Hybrid nanoparticles containing simultaneously Pd and Au (or Rh) are obtained by successive loading of metals. Similarly, ferrite nanoparticles decorated with Pd, Au, and Rh have also been formed by using the same strategy. The catalytic properties of the new nanoparticles are evidenced in processes such as reduction of 4-nitrophenol or hydrogenation of styrene. Besides, the sequential process involving a cross-coupling reaction followed by reduction of 1-nitrobiphenyl has been successfully achieved by employing Pd/Au decorated nanoferrite particles. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.Postprint (published version

Atomic Resolution Imaging with a sub-50 pm Electron Probe

Using a highly coherent focused electron probe in a 5th order aberration-corrected transmission electron microscope, we report on resolving a crystal spacing less than 50 pm. Based on the geometrical source size and residual coherent and incoherent axial lens aberrations, an electron probe is calculated, which is theoretically capable of resolving an ideal 47 pm spacing with 29percent contrast. Our experimental data show the 47 pm spacing of a Ge 114 crystal imaged with 11-18percent contrast at a 60-95percent confidence level, providing the first direct evidence for sub 50-pm resolution in ADF STEM imaging

Transition metal trifluoroacetates (M = Fe, Co, Mn) as precursors for uniform colloidal metal difluoride and phosphide nanoparticles

We report a simple one-pot synthesis of uniform transition metal difluoride MF2 (M = Fe, Mn, Co) nanorods based on transition metal trifluoroacetates (TMTFAs) as single-source precursors. The synthesis of metal fluorides is based on the thermolysis of TMTFAs at 250–320 °C in trioctylphosphine/trioctylphosphine oxide solvent mixtures. The FeF2 nanorods were converted into FeF3 nanorods by reaction with gaseous fluorine. The TMTFA precursors are also found to be suitable for the synthesis of colloidal transition metal phosphides. Specifically, we report that the thermolysis of a cobalt trifluoroacetate complex in trioctylphosphine as both the solvent and the phosphorus source can yield 20 nm long cobalt phosphide nanorods or, 3 nm large cobalt phosphide nanoparticles. We also assess electrochemical lithiation/de-lithiation of the obtained FeF2 and FeF3 nanomaterials.ISSN:2045-232

Popcorn-Shaped FexO (Wüstite) Nanoparticles from a Single-Source Precursor: Colloidal Synthesis and Magnetic Properties

Colloidal nanoparticles (NPs) with myriads of compositions and morphologies have been synthesized and characterized in recent years. For wüstite FexO, however, obtaining phase-pure NPs with homogeneous morphologies have remained challenging. Herein, we report the colloidal synthesis of phase-pure FexO (x ≈ 0.94) popcorn-shaped NPs by decomposition of a single-source precursor, [Fe3(μ3-O)(CF3COO)(μ-CF3COO)6(H2O)2]·CF3COOH. The popcorn shape and multigrain structure had been reconstructed using high-angle annular dark-field scanning transmission electron micrograph (HAADF-STEM) tomography. This morphology offers a large surface area and internal channels and prevents further agglomeration and thermal tumbling of the subparticles. [Fe3(μ3-O)(CF3COO)(μ-CF3COO)6(H2O)2]·CF3COOH behaves as an antiferromagnetic triangle whose magnetic frustration is mitigated by the low symmetry of the complex. The popcorn-shaped FexO NPs show the typical wüstite antiferromagnetic transition at approximately 200 K, but behave very differently to their bulk counterpart below 200 K. The magnetization curves show a clear, unsymmetrical hysteresis, which arises from a combined effect of the superparamagnetic behavior and exchange bias.ISSN:0897-475

The ultrathin limit of improper ferroelectricity

The secondary nature of polarization in improper ferroelectrics promotes functional properties beyond those of conventional ferroelectrics. In technologically relevant ultrathin films, however, the improper ferroelectric behavior remains largely unexplored. Here, we probe the emergence of the coupled improper polarization and primary distortive order parameter in thin films of hexagonal YMnO3. Combining state-of-the-art in situ characterization techniques separately addressing the improper ferroelectric state and its distortive driving force, we reveal a pronounced thickness dependence of the improper polarization, which we show to originate from the strong modification of the primary order at epitaxial interfaces. Nanoscale confinement effects on the primary order parameter reduce the temperature of the phase transition, which we exploit to visualize its order-disorder character with atomic resolution. Our results advance the understanding of the evolution of improper ferroelectricity within the confinement of ultrathin films, which is essential for their successful implementation in nanoscale applications.ISSN:2041-172

Popcorn-Shaped Fe_<i>x</i>O (Wüstite) Nanoparticles from a Single-Source Precursor: Colloidal Synthesis and Magnetic Properties

Colloidal nanoparticles (NPs) with myriads of compositions and morphologies have been synthesized and characterized in recent years. For wüstite Fe_<i>x</i>O, however, obtaining phase-pure NPs with homogeneous morphologies have remained challenging. Herein, we report the colloidal synthesis of phase-pure Fe_<i>x</i>O (<i>x</i> ≈ 0.94) popcorn-shaped NPs by decomposition of a single-source precursor, [Fe₃(μ₃-O)­(CF₃COO)­(μ-CF₃COO)₆(H₂O)₂]·CF₃COOH. The popcorn shape and multigrain structure had been reconstructed using high-angle annular dark-field scanning transmission electron micrograph (HAADF-STEM) tomography. This morphology offers a large surface area and internal channels and prevents further agglomeration and thermal tumbling of the subparticles. [Fe₃(μ₃-O)­(CF₃COO)­(μ-CF₃COO)₆(H₂O)₂]·CF₃COOH behaves as an antiferromagnetic triangle whose magnetic frustration is mitigated by the low symmetry of the complex. The popcorn-shaped Fe_<i>x</i>O NPs show the typical wüstite antiferromagnetic transition at approximately 200 K, but behave very differently to their bulk counterpart below 200 K. The magnetization curves show a clear, unsymmetrical hysteresis, which arises from a combined effect of the superparamagnetic behavior and exchange bias

Functionalization of MWCNTs with atomic nitrogen

In this study of the changes induced by exposing MWCNTs to a nitrogen plasma, it was found by HRTEM that the atomic nitrogen exposure does not significantly etch the surface of the carbon nanotube (CNT). Nevertheless, the atomic nitrogen generated by a microwave plasma effectively grafts amine, nitrile, amide, and oxime groups onto the CNT surface, as observed by XPS, altering the density of valence electronic states, as seen in UPS