Oxidation of supported PtRh partcles:size and morphology effects

2008/2009The chemical transformations of supported PtRh particles ranging in size from a few micrometers to a few nanometres, and nanocrystalline films have been studied under identical oxidizing conditions by means of different chemical and structural characterization techniques; in particular the main technique used has been the scanning photoemission spectromicroscopy (SPEM) available at the EscaMicroscopy beamline of the Elettra Synchrotron Light Source. This novel experimental technique allows sample’s chemical mapping with a spatial resolution of 100nm and the acquisition of photoemission spectra on regions with the same dimension, and allow us to determine the chemical state of single micro-particles. In particular we studied PtRh cluster deposited by PLD (pulsed laser deposition) on a tungsten single crystal (W(110)) covered by a thin magnesium oxide film (MgO). Significant variations of the Pt and Rh atoms reactivity have been revealed by comparing the oxidation states of particles with different dimensions and, for the micron-scale particles, also within the same island. It was demonstrated that a selected oxidation occurs: rhodium atoms undergo stronger and faster oxidation than platinum ones. Furthermore, the oxidation process is composed by many intermediate steps, in which metastable oxides are formed. Very small cluster’s oxidation (100nm). Some morphological and structural clusters’ modifications after long oxidation treatments were also investigated using a high resolution SEM (<2nm lateral resolution). Other measurements have been performed by using a Low Energy Electron Microscope (LEEM) that combines a high spatial resolution (<5nm) to a high sensitivity to surface structural modifications. In particular the behaviour of the clusters’ polycrystalline structure has been studied during oxidation-reduction treatments. It has been shown that the clusters’ surface is polycrystalline and that each nano crystals have different crystallographic orientation. After oxidation each nano-crystal undergoes a different oxidation rate. The diffraction pattern revealed that after a long oxidation the long range order of the particles’ surface is completely lost. A characterization of the reactivity of the PtRh particles towards oxidation after an “ageing” process based on the repetition of many redox cycles has revealed a change in the stability of the oxides. Other experiments have been realized with SEM and EDX for studying the clusters’ morphology at different annealing temperatures. The results have shown structural, chemical and morphology changes.XXII Ciclo197

7Be-recoil radiolabelling of industrially manufactured silica nanoparticles

Radiolabelling of industrially manufactured nanoparticles is useful for nanoparticle dosimetry in biodistribution or cellular uptake studies for hazard and risk assessment. Ideally for such purposes any chemical processing post production should be avoided as it may change the physico-chemical characteristics of the industrially manufactured species. In many cases proton irradiation of nanoparticles allows radiolabelling by transmutation of a tiny fraction of their constituent atoms into radionuclides. However, not all types of nanoparticles offer nuclear reactions leading to radionuclides with adequate radiotracer properties. We describe here a process whereby in such cases nanoparticles can be labelled with 7Be, which exhibits a physical halflife of 53.29 days and emits γ-rays of 478 keV energy and is suitable for most radiotracer studies. 7Be is produced via the proton-induced nuclear reaction 7Li(p,n)7Be in a fine-grained lithium compound with which the nanoparticles are mixed. The high recoil energy of 7Be-atoms gives them a range that allows the 7Be-recoils to be transferred from the lithium compound into the nanoparticles by recoil implantation. The nanoparticles can be recovered from the mixture by dissolving the lithium compound and subsequent filtration or centrifugation. The method has been applied to radiolabel industrially manufactured SiO2 nanoparticles. The process can be controlled in such a way that no alterations of the 7Be-labelled nanoparticles are detectable by dynamic light scattering, X-ray diffraction and electron microscopy. Moreover, cyclotrons with maximum proton energies of 17 to 18 MeV that are available in most medical research centres could be used for this purpose.JRC.I.4-Nanobioscience

Disentangling Vacancy Oxidation on Metallicity-Sorted Carbon Nanotubes

Pristine single-walled carbon nanotubes (SWCNTs) are rather inert to O$_2$ and N$_2$, which for low doses chemisorb only on defect sites or vacancies of the SWCNTs at the ppm level. However, very low doping has a major effect on the electronic properties and conductivity of the SWCNTs. Already at low O$_2$ doses (80 L), the X-ray photoelectron spectroscopy (XPS) O 1s signal becomes saturated, indicating nearly all the SWCNT's vacancies have been oxidized. As a result, probing vacancy oxidation on SWCNTs via XPS yields spectra with rather low signal-to-noise ratios, even for metallicity-sorted SWCNTs. We show that, even under these conditions, the first principles density functional theory calculated Kohn-Sham O 1s binding energies may be used to assign the XPS O 1s spectra for oxidized vacancies on SWCNTs into its individual components. This allows one to determine the specific functional groups or bonding environments measured. We find the XPS O 1s signal is mostly due to three O-containing functional groups on SWCNT vacancies: epoxy (C$_2$$>$O), carbonyl (C$_2$$>$C$=$O), and ketene (C$=$C$=$O), as ordered by abundance. Upon oxidation of nearly all the SWCNT's vacancies, the central peak's intensity for the metallic SWCNT sample is 60\% greater than for the semiconducting SWCNT sample. This suggests a greater abundance of O-containing defect structures on the metallic SWCNT sample. For both metallic and semiconducting SWCNTs, we find O$_2$ does not contribute to the measured XPS O~1s spectra

Graphene etching on SiC grains as a path to interstellar polycyclic aromatic hydrocarbons formation.

Polycyclic aromatic hydrocarbons as well as other organic molecules appear among the most abundant observed species in interstellar space and are key molecules to understanding the prebiotic roots of life. However, their existence and abundance in space remain a puzzle. Here we present a new top-down route to form polycyclic aromatic hydrocarbons in large quantities in space. We show that aromatic species can be efficiently formed on the graphitized surface of the abundant silicon carbide stardust on exposure to atomic hydrogen under pressure and temperature conditions analogous to those of the interstellar medium. To this aim, we mimic the circumstellar environment using ultra-high vacuum chambers and investigate the SiC surface by in situ advanced characterization techniques combined with first-principles molecular dynamics calculations. These results suggest that top-down routes are crucial to astrochemistry to explain the abundance of organic species and to uncover the origin of unidentified infrared emission features from advanced observations. © 2014 Macmillan Publishers Limited. All rights reserved

X-ray photoelectron spectroscopy analysis as a tool to assess factors influencing magnetic anisotropy type in Co/MgO system with gold interlayer

X-ray photoelectron spectroscopy (XPS) studies of Au/Co/Au(0.3 nm)/MgO and Au/Co/MgO systems were conducted in order to monitor the electronic structure modification at Co/MgO interface with/without gold interlayer. A detailed analysis of Co 2p states revealed that the amount of minor oxygen contribution at Co/MgO interface decreased after the Au interlayer was added. The obtained XPS results together with density functional theory (DFT) allowed explanation of the increase of surface anisotropy energy in the sample with the gold interlayer in terms of (i) noble and transitional metal d-d orbital hybridization; (ii) interfacial Co 3d and O 2p; and (iii) interface imperfectio

Transfer-free electrical insulation of epitaxial graphene from its metal substrate

High-quality, large-area epitaxial graphene can be grown on metal surfaces but its transport properties cannot be exploited because the electrical conduction is dominated by the substrate. Here we insulate epitaxial graphene on Ru(0001) by a step-wise intercalation of silicon and oxygen, and the eventual formation of a SiO$_2$ layer between the graphene and the metal. We follow the reaction steps by x-ray photoemission spectroscopy and demonstrate the electrical insulation using a nano-scale multipoint probe technique.Comment: Accepted for publication in Nano Letter

Synthesis of nitrogen-doped epitaxial graphene via plasma-assisted method: Role of the graphene-substrate interaction

Functionalization of graphene by substitution of carbon with nitrogen atoms is a promising way to tailor its electronic properties, but a good control over the heteroatomic configuration in the graphene network is most often a difficult task. In this paper, the synthesis of N-doped graphene by nitrogen plasma treatment of graphene/Ir(111) is presented. The formation of substitutional, pyrrolic and pyridinic nitrogen is analyzed by means of X-ray photoelectron spectroscopy (XPS) and X-ray photoelectron diffraction (XPD). The graphene\u2013Ir interaction is suggested to control the variation in the relative concentration of the nitrogen species. Annealing of the sample also leads to modifications of the nitrogen species incorporated in the graphene layer. Furthermore, the connection of the substitutional nitrogen arrangement with its corresponding spectroscopic fingerprint is unequivocally confirmed by XPD measurements, which give also a direct insight on the local geometry of the nitrogen atoms incorporated in the carbon network

Strategies for radiolabeling of commercial TiO2 nanopowder as a tool for sensitive nanoparticle detection in complex matrices

Detection and quantification of engineered nanoparticles (NPs) in complex environmental or biological media is a major challenge since NP concentrations are generally expected to be low compared to elemental background levels. This study presents three different options for radiolabeling of commercial titania NP (TiO2-NP, AEROXIDE® P25, Evonik Industries, mean diameter 21 nm) for particle detection, localization, and tracing under various experimental conditions. The radiolabeling procedures ensure stability and consistency of important particle properties such as size and morphology. With the presented radiolabeling methods, detection (and quantification) limits for TiO2-NPs in concentrations as low as 0.5 ng/L can be realized in complex systems without the necessity of intense sample purification or pretreatment.JRC.I.4-Nanobioscience

Chemical gating of epitaxial graphene through ultrathin oxide layers

We achieved a controllable chemical gating of epitaxial graphene grown on metal substrates by exploiting the electrostatic polarization of ultrathin SiO2 layers synthesized below it. Intercalated oxygen diffusing through the SiO2 layer modifies the metal\u2013oxide work function and hole dopes graphene. The graphene/oxide/metal heterostructure behaves as a gated plane capacitor with the in situ grown SiO2 layer acting as a homogeneous dielectric spacer, whose high capacity allows the Fermi level of graphene to be shifted by a few hundreds of meV when the oxygen coverage at the metal substrate is of the order of 0.5 monolayers. The hole doping can be finely tuned by controlling the amount of interfacial oxygen, as well as by adjusting the thickness of the oxide layer. After complete thermal desorption of oxygen the intrinsic doping of SiO2 supported graphene is evaluated in the absence of contaminants and adventitious adsorbates. The demonstration that the charge state of graphene can be changed by chemically modifying the buried oxide/metal interface hints at the possibility of tuning the level and sign of doping by the use of other intercalants capable of diffusing through the ultrathin porous dielectric and reach the interface with the metal