Coexisting multi-states in catalytic hydrogen oxidation on rhodium.

Catalytic hydrogen oxidation on a polycrystalline rhodium foil used as a surface structure library is studied by scanning photoelectron microscopy (SPEM) in the 10-6 mbar pressure range, yielding spatially resolved X-ray photoemission spectroscopy (XPS) measurements. Here we report an observation of a previously unknown coexistence of four different states on adjacent differently oriented domains of the same Rh sample at the exactly same conditions. A catalytically active steady state, a catalytically inactive steady state and multifrequential oscillating states are simultaneously observed. Our results thus demonstrate the general possibility of multi-states in a catalytic reaction. This highly unusual behaviour is explained on the basis of peculiarities of the formation and depletion of subsurface oxygen on differently structured Rh surfaces. The experimental findings are supported by mean-field micro-kinetic modelling. The present observations raise the interdisciplinary question of how self-organising dynamic processes in a heterogeneous system are influenced by the permeability of the borders confining the adjacent regions.

How the anisotropy of surface oxide formation influences the transient activity of a surface reaction.

Scanning photoelectron microscopy (SPEM) and photoemission electron microscopy (PEEM) allow local surface analysis and visualising ongoing reactions on a µm-scale. These two spatio-temporal imaging methods are applied to polycrystalline Rh, representing a library of well-defined high-Miller-index surface structures. The combination of these techniques enables revealing the anisotropy of surface oxidation, as well as its effect on catalytic hydrogen oxidation. In the present work we observe, using locally-resolved SPEM, structure-sensitive surface oxide formation, which is summarised in an oxidation map and quantitatively explained by the novel step density (SDP) and step edge (SEP) parameters. In situ PEEM imaging of ongoing H2 oxidation allows a direct comparison of the local reactivity of metallic and oxidised Rh surfaces for the very same different stepped surface structures, demonstrating the effect of Rh surface oxides. Employing the velocity of propagating reaction fronts as indicator of surface reactivity, we observe a high transient activity of Rh surface oxide in H2 oxidation. The corresponding velocity map reveals the structure-dependence of such activity, representing a direct imaging of a structure-activity relation for plenty of well-defined surface structures within one sample.

Probing plasma fluorinated graphene via spectromicroscopy.

Plasma fluorination of graphene is studied using a combination of spectroscopy and microscopy techniques, giving insight into the yield and fluorination mechanism for functionalization of supported graphene with both CF4 and SF6 gas precursors. Ion acceleration during fluorination is used to probe the effect on grafting functionalities. Adatom clustering, which occurs with CF4 plasma treatment, is suppressed when higher kinetic energy is supplied to the ions. During SF6 plasma functionalization, the sulfur atoms tend to bond to bare copper areas instead of affecting the graphene chemistry, except when the kinetic energy of the ions is restricted. Using scanning photoelectron microscopy, with a 100 nm spatial resolution, the chemical bonding environment is evaluated in the fluorinated carbon network at selected regions and the functionalization homogeneity is controlled in individual graphene flakes.

Surface Effects on the Mott-Hubbard Transition in Archetypal V{2}O{3}.

We present an experimental and theoretical study exploring surface effects on the evolution of the metal-insulator transition in the model Mott-Hubbard compound Cr-doped V{2}O{3}. We find a microscopic domain formation that is clearly affected by the surface crystallographic orientation. Using scanning photoelectron microscopy and x-ray diffraction, we find that surface defects act as nucleation centers for the formation of domains at the temperature-induced isostructural transition and favor the formation of microscopic metallic regions. A density-functional theory plus dynamical mean-field theory study of different surface terminations shows that the surface reconstruction with excess vanadyl cations leads to doped, and hence more metallic, surface states, which explains our experimental observations.

Electrical properties of nanostructured tin oxide surfaces produced by thermal treatments.

Sintering SnO2 powder in air or under an oxygen atmosphere at different temperatures, leads to polycrystalline samples with nanostructured surface as revealed by atomic force microscopy (AFM). The thermal treatments are also responsible for the variation of the surface electrical properties, as studied by scanning spreading resistance microscopy (SSRM) and scanning tunnelling microscopy and spectroscopy (STM-STS). The surface presents a p-conductance, contrary to the n-type characteristic of the bulk, and a band gap lower than the bulk band gap (3.6 eV). The electrical behaviour at the grain boundaries and the role of oxygen are discussed. X-ray photoelectron spectroscopy (XPS) results show a higher presence of oxygen at the boundaries, which generates a shift of the Fermi level position (E(F)-E(V)) towards lower energies.

Growth and luminescence of N doped TiO2 nanowires.

Titanium oxide nanowires have been grown by thermal treatment of pressed TiN powder under argon or N2 flow. It has been found that two-step treatments at two different temperatures, 400 degrees C and 800 degrees C, lead to the growth of nanowires all over the sample surface. The nanowires are of single crystalline rutile structure. Energy dispersive X-ray spectroscopy and photoelectron spectroscopy measurements show that the oxide nanostructures contain N from the starting nitride. The mechanism of N incorporation into the oxide and its possible effect on the luminescence are discussed.

Imaging with spectroscopic micro-analysis using synchrotron radiation.

Recent developments of element-specific microscopy techniques using synchrotron radiation are opening new opportunities for the analytical investigation of various heterogeneous materials. This article provides a general description of the operational principles of different microscopes allowing chemical and structural imaging combined with micro-spot spectroscopic analysis. Several selected examples are used to illustrate the potential of the synchrotron-based methods in terms of imaging and chemical sensitivity for identification of spatial variations in the composition of morphologically complex and nano-structured inorganic and organic materials, including biological samples.

Initial oxidation of a Rh(110) surface using atomic or molecular oxygen and reduction of the surface oxide by hydrogen.

The formation conditions, morphology, and reactivity of thin oxide films, grown on a Rh(110) surface in the ambient of atomic or molecular oxygen, have been studied by means of laterally resolved core level spectroscopy, scanning tunneling microscopy and low energy electron diffraction. Exposures of Rh(110) to atomic oxygen lead to subsurface incorporation of oxygen even at room temperature and facile formation of an ordered, laterally uniform surface oxide at approximately 520 K, with a quasi-hexagonal structure and stoichiometry close to that of RhO(2). In the intermediate oxidation stages, the surface oxide coexists with areas of high coverage adsorption phases. After a long induction period, the reduction of the Rh oxide film with H(2) is very rapid and independent of the coexisting adsorption phases. The growth of the oxide film by exposure of a Rh(110) surface to molecular oxygen requires higher pressures and temperatures. The important role of the O(2) dissociation step in the oxidation process is reflected by the complex morphology of the oxide films grown in O(2) ambient, consisting of microscopic patches of different Rh and oxygen atomic density.

A novel approach to the control of experimental environments: the ESCA microscopy data-acquisition system at ELETTRA.

An efficient control system is today one of the key points for the successful operation of a beamline at third-generation synchrotron radiation sources. The high cost of these ultra-bright light sources and the limited beam time requires effective instrument handling in order to reduce any waste of measurement time. The basic requirements for such control software are reliability, user-friendliness, modularity, upgradability, as well as the capability of integrating a horde of different instruments, commercial tools and independent pre-existing systems in a possibly distributed environment. A novel approach has been adopted to implement the data-acquisition system of the ESCA microscopy beamline at ELETTRA. The system is based on YASB, a software bus, i.e. an underlying control model to coordinate information exchanges and networking software to implement that model. This 'middleware' allows the developer to model applications as a set of interacting agents, i.e. independent software machines. Agents can be implemented using different programming languages and be executed on heterogeneous operating environments, which promotes an effective collaboration between software engineers and experimental physicists.

[Prevention of pulmonary embolism in surgery: analysis of 2 clinical cases]. / La prevenzione dell'embolia polmonare in chirurgia: analisi di due casi clinici.

After some short notices on the physiopathology of thrombosis, the AA. consider clinic, symptomatology and surgical therapy for prevention of pulmonary embolism. They outline that only a precocious operation and an exact diagnosis can help the patient who had had an embolism; in the end they report two cases, describing the operation and its indications.