Visualizing atomic-scale redox dynamics in vanadium oxide-based catalysts

Surface redox processes involving oxygen atom exchange are fundamental in catalytic reactions mediated by metal oxides. These processes are often difficult to uncover due to changes in the surface stoichiometry and atomic arrangement. Here we employ high-resolution transmission electron microscopy to study vanadium oxide supported on titanium dioxide, which is of relevance as a catalyst in, e.g., nitrogen oxide emission abatement for environmental protection. The observations reveal a reversible transformation of the vanadium oxide surface between an ordered and disordered state, concomitant with a reversible change in the vanadium oxidation state, when alternating between oxidizing and reducing conditions. The transformation depends on the anatase titanium dioxide surface termination and the vanadium oxide layer thickness, suggesting that the properties of vanadium oxide are sensitive to the supporting oxide. These atomic-resolution observations offer a basis for rationalizing previous reports on shape-sensitive catalytic properties

Detecting structural variances of Co_3O_4 catalysts by controlling beam-induced sample alterations in the vacuum of a transmission electron microscope

This article summarizes core aspects of beam-sample interactions in research that aims at exploiting the ability to detect single atoms at atomic resolution by mid-voltage transmission electron microscopy. Investigating the atomic structure of catalytic Co_3O_4 nanocrystals underscores how indispensable it is to rigorously control electron dose rates and total doses to understand native material properties on this scale. We apply in-line holography with variable dose rates to achieve this goal. Genuine object structures can be maintained if dose rates below ~100 e/Å^2s are used and the contrast required for detection of single atoms is generated by capturing large image series. Threshold doses for the detection of single atoms are estimated. An increase of electron dose rates and total doses to common values for high resolution imaging of solids stimulates object excitations that restructure surfaces, interfaces, and defects and cause grain reorientation or growth. We observe a variety of previously unknown atom configurations in surface proximity of the Co_3O_4 spinel structure. These are hidden behind broadened diffraction patterns in reciprocal space but become visible in real space by solving the phase problem. An exposure of the Co_3O_4 spinel structure to water vapor or other gases induces drastic structure alterations that can be captured in this manner

Atomic Structure of a Spinel-Like Transition Al2O3(100) Surface

We study a crystalline epitaxial alumina thin film with the characteristics of a spinel-type transition Al2O3(100)surface by using atom-resolved noncontact atomic force microscopy and density functional theory. It is shown that the films are terminated by an Al-O layer rich in Al vacancies, exhibiting a strong preference for surface hydroxyl group formation in two configurations. The transition alumina films are crystalline and perfectly stable in ambient atmospheres, a quality which is expected to open the door to new fundamental studies of the surfaces of transition aluminas.Peer reviewe

Recent Trends in Sociological Approach to Economy

The coarsening of supported palladiumnanoparticles in an oxidizing atmospherewas studied in situ by means of transmission electron microscopy (TEM). Specifically, the Pd nanoparticles were dispersed on a planar and amorphousAl2O3 support and were observed during the exposure to 10 mbar technical air at 650 \ub0C. Time-resolved TEM image series reveal that the Pd nanoparticles were immobile and that a few percent of the nanoparticles grew or shrank, indicating a coarsening process mediated by the Ostwald ripening mechanism. The TEM image contrast suggests that the largest nanoparticles tended to wet the Al2O3 support to a higher degree than the smaller nanoparticles and that the distribution of projected particle sizes consequently broadens by the appearance of an asymmetric tail toward the larger particle sizes. A comparison with computer simulations based on a simple mean-fieldmodel for the Ostwald ripening process indicates that the observed change in the particle size distribution can be accounted for by wetting of the Al2O3 support by the larger Pd nanoparticles