The oxidation of alcohols to aldehydes with O2 in place of stoichiometric oxygen donors is a crucial process for the synthesis of fine chemicals. However, the catalysts that have been identified so far are relatively inactive with primary alkyl alcohols. We showed that Au/Pd-TiO2 catalysts give very high turnover frequencies (up to 270,000 turnovers per hour) for the oxidation of alcohols, including primary alkyl alcohols. The addition of Au to Pd nanocrystals improved the overall selectivity and, using scanning transmission electron microscopy combined with x-ray photoelectron spectroscopy, we showed that the Au-Pd nanocrystals were made up of a Au-rich core with a Pd-rich shell, indicating that the Au electronically influences the catalytic properties of Pd.

No abstract

The optical response from metal nanoparticles and nanostructures is dominated by surface plasmon generation and is critically dependent on the local structure and geometry. Electron energy-loss spectroscopy (EELS), combined with recent developments in spectrum imaging and data processing, has been used to observe the energy and distribution of surface plasmons excited by fast electrons. The energy of the plasmon responses is consistent with the optical response and with calculations. For gold and silver rods and ellipsoids, longitudinal, transverse and distinct cluster modes were readily identified and mapped. The spatial resolution of the presented maps is one order of magnitude better than that achievable with scanning near-field optical microscopy (SNOM)-based techniques.

No abstract

SummaryA new quantitative thin-film X-ray analysis procedure termed the ζ -factor method is proposed. This new ζ -factor method overcomes the two major limitations of the conventional CliffLorimer method for quantification: (1) use of pure-element rather than multielement, thin-specimen standards and (2) built-in X-ray absorption correction with simultaneous thickness determination. Combined with a universal, standard, thin specimen, a series of ζ -factors covering a significant fraction of the periodic table can be estimated. This ζ -factor estimation can also provide information about both the detector efficiency and the microscope-detector interface system. Light-element analysis can also be performed more easily because of the built-in absorption correction. Additionally, the new ζ -factor method has several advantages over the Cliff-Lorimer ratio method because information on the specimen thickness at the individual analysis points is produced simultaneously with compositions, thus permitting concurrent determination of the spatial resolution and the analytical sensitivity. In this work, details of the ζ -factor method and how it improves on the Cliff-Lorimer approach are demonstrated, along with several applications.

The ability of electron microscopes to analyze all the atoms in individual nanostructures is limited by lens aberrations. However, recent advances in aberration-correcting electron optics have led to greatly enhanced instrument performance and new techniques of electron microscopy. The development of an ultrastable electron microscope with aberration-correcting optics and a monochromated high-brightness source has significantly improved instrument resolution and contrast. In the present work, we report information transfer beyond 50 pm and show images of single gold atoms with a signal-to-noise ratio as large as 10. The instrument's new capabilities were exploited to detect a buried Sigma3 {112} grain boundary and observe the dynamic arrangements of single atoms and atom pairs with sub-angstrom resolution. These results mark an important step toward meeting the challenge of determining the three-dimensional atomic-scale structure of nanomaterials.

No abstract

No abstract