Preparation and characterization of ordered intermetallic platinum phases for electrocatalytic applications

Ordered intermetallic phases of Pt with several transition metals have been prepared and their electrocatalytic properties studied. In light of these tests it is proposed that these catalysts could be used as electrodes in fuel cells, as they combine an excellent capacity to adsorb organic fuels at the Pt sites with low susceptibility to being poisoned by intermediates and reaction products at the transition-metal sites. An experimental procedure used to obtain the four intermetallic phases Pt-M (M = Mn, Pb, Sb and Sn) is described. The phases thus produced were characterized by X-ray diffraction, scanning electron microscopy with surface analysis by energy-dispersive X-ray spectrometry, scanning tunneling microscopy and X-ray photoelectron spectroscopy. The data thus obtained support the conclusion that the method described here is highly effective for the preparation of Pt-M phases featuring a range of structural and electronic modifications that will allow a useful relation to be established between their physicochemical properties and predicted electrocatalytic activity. (C) 2007 Elsevier Ltd. All rights reserved.

Preparation and characterization of ordered intermetallic platinum phases for electrocatalytic applications

Ordered intermetallic phases of Pt with several transition metals have been prepared and their electrocatalytic properties studied. In light of these tests it is proposed that these catalysts could be used as electrodes in fuel cells, as they combine an excellent capacity to adsorb organic fuels at the Pt sites with low susceptibility to being poisoned by intermediates and reaction products at the transition-metal sites. An experimental procedure used to obtain the four intermetallic phases Pt-M (M = Mn, Pb, Sb and Sn) is described. The phases thus produced were characterized by X-ray diffraction, scanning electron microscopy with surface analysis by energy-dispersive X-ray spectrometry, scanning tunneling microscopy and X-ray photoelectron spectroscopy. The data thus obtained support the conclusion that the method described here is highly effective for the preparation of Pt-M phases featuring a range of structural and electronic modifications that will allow a useful relation to be established between their physicochemical properties and predicted electrocatalytic activity. (C) 2007 Elsevier Ltd. All rights reserved.

Non-Zeeman splitting for a spin-resolved STM with a Kondo adatom in a spin-polarized two-dimensional electron gas

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Effect of thickness on the electrical and optical properties of Sb doped SnO2 (ATO) thin films

This work reports the preparation and characterization of (SnO2) thin films doped with 7 mol% Sb2O3. The films were prepared by the polymeric precursor method, and deposited by spin-coating, all of them were deposited on amorphous silica substrate. Then, we have studied the thickness effect on the microstrutural, optical and electric properties of these samples. The microstructural characterization was carried out by X-ray diffraction (XRD) and scanning tunneling microscopy (STM). The electrical resistivity measurements were obtained by the van der Pauw four-probe method. UV-visible spectroscopy and ellipsometry were carried out for the optical characterization. The films present nanometric grains in the order of 13 nm, and low roughness. The electrical resistivity decreased with the increase of the film thickness and the smallest measured value was 6.5 x 10(-3) Omega cm for the 988 nm thick film. The samples displayed a high transmittance value of 80% in the visible region. The obtained results show that the polymeric precursor method is effective for the TCOs manufacturing.

Active planar waveguides based on sol-gel Er3+-doped SiO2-ZrO2 for photonic applications: Morphological, structural and optical properties

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Evidence of defect-mediated magnetic coupling on hydrogenated Co-doped ZnO

Hydrogenated bulk Zn1-xCoxO samples were synthesized via standard solid-state reaction route with Co molar concentrations up to 15 at.%. Magnetic characterization demonstrates a room temperature ferromagnetic behavior associated to a paramagnetic Curie-Weiss component. Detailed microstructural analysis was carried out to exclude the presence of extrinsic sources of ferromagnetism. The magnetization increases linearly as a function of Co concentration. Hall measurements reveal an insulating character for the whole set of samples. In this context, the defect mediated magnetic coupling between the Co atoms under the scope of the bound magnetic polarons model is used to interpret the observed room temperature ferromagnetism. © 2012 Elsevier B.V. All rights reserved.

Estudo da eletrocatálise da reação de oxidação de etanol sobre fases intermetálicas ordenadas Pt-M (M = Mn,Mo, Pb, Sb e Sn)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Bilayer graphene on h-BN substrate: investigating the breakdown voltage and tuning the bandgap by electric field

By performing density functional theory calculations we show that it is possible to make the electronic bandgap in bilayer graphene supported on hexagonal boron nitride (h-BN) substrates tunable. We also show that, under applied electric fields, it is possible to insert states from h-BN into the bandgap, which generate a conduction channel through the substrate making the system metallic. In addition, we verify that the breakdown voltage strongly depends on the number of h-BN layers. We also show that both the breakdown voltage and the bandgap tuning are independent of the h-BN stacking order.

Origin of Anomalous Activities for Electrocatalysts in Alkaline Electrolytes

Pt extended surfaces and nanoparticle electrodes are used to understand the origin of anomalous activities for electrocatalytic reactions in alkaline electrolytes as a function of cycling/time. Scanning tunneling microscopy (STM) of the surfaces before and after cycling in alkaline electrolytes was used to understand the morphology of the impurities and their impact on the catalytic sites. The nature of the contaminant species is identified as 3d-transition metal cations, and the formation of hydr(oxy)oxides of these elements is established as the main reason for the observed behavior. We find that, while for the oxygen reduction reaction (ORR) and the hydrogen oxidation reaction (HOR) the blocking of the sites by the undesired 3d-transition metal hydr(oxy)oxide species leads to deactivation of the reaction activities, the CO oxidation reaction and the hydrogen evolution reaction (HER) can have beneficial effects from the same impurities, the latter being dependent on the exact nature of the adsorbing species. These results show the significance of impurities present in real electrolytes and their impact on electrocatalysis.

Adsorption of NO on the Rh-13, Pd-13, Ir-13, and Pt-13 Clusters: A Density Functional Theory Investigation

The adsorption of NO on transition-metal (TM) surfaces has been widely studied by experimental and theoretical techniques; however, our atomistic understanding of the interaction of nitrogen monoxide (NO) with small TM clusters is far from satisfactory, which compromises a deep understanding of real catalyst devices. In this study, we report a density functional theory study of the adsorption properties of NO on the TM13 (TM = Rh, Pd, Ir, Pt) clusters employing the projected augmented wave method. We found that the interaction of NO with TM13 is much more complex than that for NO/TM(111). In particular, for low symmetry TM13 clusters, there is a strong rearrangement of the electronic charge density upon NO adsorption and, as a consequence, the adsorption energy shows a very complex dependence even for adsorption sites with the same local effective coordination. We found a strong enhancement of the binding energy of NO to the TM13 clusters compared with the TM(111) surfaces, as the antibonding NO states are not occupied for NO/TM13, and the general relationship based on the d-band model between adsorption energy and the center of gravity of the occupied d-states does not hold for the studied TM13 clusters, in particular, for clusters with low symmetry. In contrast with the adsorption energy trends, the geometric NO/TM13 parameters and the vibrational N-O frequencies for different coordination sites follow the same trend as for the respective TM(111) surfaces, while the changes in the frequencies between different surfaces and TM13 clusters reflect the strong NO-TM13 interaction.

Atomically resolved study of the morphology change of InAs/GaAs quantum dot layers induced by rapid thermal annealing

The optoelectronic properties of InAs/GaAs quantum dots can be tuned by rapid thermal annealing. In this study, the morphology change of InAs/GaAs quantum dots layers induced by rapid thermal annealing was investigated at the atomic-scale by cross-sectional scanning tunneling microscopy. Finite elements calculations that model the outward relaxation of the cleaved surface were used to determine the indium composition profile of the wetting layer and the quantum dots prior and post rapid thermal annealing. The results show that the wetting layer is broadened upon annealing. This broadening could be modeled by assuming a random walk of indium atoms. Furthermore, we show that the stronger strain gradient at the location of the quantum dots enhances the intermixing. Photoluminescence measurements show a blueshift and narrowing of the photoluminescence peak. Temperature dependent photoluminescence measurements show a lower activation energy for the annealed sample. These results are in agreement with the observed change in morphology. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4770371]

Wasserstoffbrücken-gebundene Netzwerke

Die supramolekularen Organisationen von 5-n-Alkoxyisophthaläuren und 2,5-Di-n-alkoxyterephthalsäuren bilden durch sekundäre Wechselwirkungen in Form van der Waals-Kräften und Wasserstoffbrückenbindungen hochgeordnete lamellare Strukturen, die sowohl mittels Röntgen-kristallgraphie als auch durch Rastertunnelmikroskopie (STM) visualisierbar sind. Diese Art der Aggregationsmuster ermöglicht den potentiell reaktiven Gruppen (Diacetylene, Zimtsäuren) in der Alkoxykette, einen optimalen Abstand und geometrische Orientierungen im Kristall einzunehmen, um lichtinduzierte Reaktionen im Festkörper durchzuführen. Einführung einer Amidgruppe an die Alkoxykette erweitert dieses Konzept, durch Erhalt einer zusätzlichen Wasserstoffbrückenbindung im hydrophoben Bereich der Organisation.Die Stabilität solche supramolekularer Aggregate kann durch Einführung semifluorierter Alkoxyketten stark beeinflußt werden, da die Inkompatibilität der pefluorierten Gruppen durch viele organische Verbindungen das Gleichgewicht nicht-kovalenter Wechselwirkung drastisch verändert. Diese Eigenschaft der semifluorierten 5-n-Alkoxyisopthalsäuren und 2,5-Di-n-alkoxyterephthalsäuren zeigt sich erstaunlicherweise jedoch nur bei einem großen Anteil des perfluorierten Alkylteils als der des nicht-perfluorierten. Da sich dann die perfluorierten Alkylteile untereinander organisieren können, erscheint die Änderung der Assoziationsstruktur von interdigitiert-lamellar zu nicht-interdigitiert-lamellar plausibel.Das gezielte Design eines neuen Organisationsmusters der 5-n-Alkoxyisophthalsäuren gelang durch Brechung der Symmetrie dieses Bausteins. Die Einführung zweier Alkoxyketten ließ die zweidimensionale Anordnung der wasserstoffbrückengebundenen Aromate unverändert, resultierte aber mit Ausbruch einer Alkoxykette aus dieser Ebene.

Synthetical engineering of supramolecular properties of large polycyclic aromatic hydrocarbons

An important property for devices is the charge-carrier mobility values for discotic organic materials like hexa-peri-hexabenzocoronenes. A close relation exists between the degree of their columnar self-arrangement of the molecules and their mobilities. Within this first step an induction of a higher order via hydrogen-bonding was considered, which mainly pointed towards the improvement of the intracolumnar stacking of the materials. For the analytics a broad range of methods was used including differential scanning calorimetry (DSC), wide-angle X-ray diffractometry (WAXS), solid-state NMR spectroscopy and scanning tunneling microscopy (STM). Indeed, a specific influence of the hydrogen-bonds could be identified, although in several cases by the cost of a severe reduction of solubility and processability. This effect was dampened by the addition of a long alkyl chain next to the hydrogen-bond exerting functional group, which resulted in an improved columnar arrangement by retention of processability. In contrast to the before mentioned example of inducing a higher intracolumnar order by hydrogen-bonding, the focus was also be set upon larger aromatic systems. The charge-carrier mobility is also in close relation to the size of the aromatic core and larger π-areas are expected to lead to improved mobilities. For photovoltaic applications a high extinction coefficient over a broad range of the spectrum is favorable, which can also be achieved by enlarging the aromatic core component. In addition the stronger π-interactions between the aromatic core components should yield an improved columnar stability and order. However the strengthening of the π-interactions between the aromatic core components led to a reduction of the solubility and the processability due to the stronger aggregation of the molecules. This required the introduction of efficiently solubilizing features in terms of long alkyl chains in the corona of the aromatic entity, in combination of a distortion of the aromatic core moiety by bulky tert-butyl groups. By this approach not only the processing and cleaning of the materials with standard laboratory techniques became possible, but moreover the first structure-rich UV/vis and a resolved 1H-NMR spectra for an aromatic system two times larger than hexa-peri-hexabenzocoronene were recorded. The bulk properties in an extruded fiber as well as on the surface showed a columnar self-assembly including a phase in which a homeotropic alignment on a substrate was observed, which turns the material into an interesting candidate for future applications in electronic devices.

Advanced SPM studies on the growth of ultrathin films of organic semiconductors at metal and dielectric interfaces

Many studies on the morphology, molecular orientation, device performance, substrate nature and growth parameter dependence have been carried out since the proposal of Sexithiophene (6T) for organic electronics [ ] However, these studies were mostly performed on films thicker than 20nm and without specifically addressing the relationship between morphology and molecular orientation within the nano and micro structures of ultrathin films of 0-3 monolayers. In 2004, the observation that in OFETs only the first few monolayers at the interface in contact with the gate insulator contribute to the charge transport [ ], underlined the importance to study submonolayer films and their evolution up to a few monolayers of thickness with appropriate experimental techniques. We present here a detailed Non-contact Atomic Force Microscopy and Scanning Tunneling Microscopy study on various substrates aiming at the investigation of growth mechanisms. Most reported similar studies are performed on ideal metals in UHV. However it is important to investigate the details of organic film growth on less ideal and even technological surfaces and device testpatterns. The present work addresses the growth of ultra thin organic films in-situ and quasi real-time by NC-AFM. An organic effusion cell is installed to evaporate the organic material directly onto the SPM sample scanning stage.

Synthesis and Supramolecular Architectures of Lipophilic Derivatives of Guanine

Self-assembly relies on the association of pre-programmed building blocks through non-covalent interactions to give complex supramolecular architectures. Previous studies provided evidence for the unique self-assembly properties of semi-synthetic lipophilic guanosine derivatives which can sequestrate ions from an aqueous phase, carry them into an organic phase where they promote the generation of well-defined supramolecular assemblies. In the presence of cations lipophilic guanosines form columnar aggregates while in their absence they generate supramolecular ribbons. The aim of this thesis has been the synthesis of guanine derivatives, in particular N9-alkylated guanines and a guanosine functionalized as a perchlorotriphenylmetil moiety (Gace-a-HPTM) in order to observe their supramolecular behaviour in the absence of sugar (ribose or deoxyribose) and in the presence of a bulky and chiral substituent respectively. By using guanine instead of guanosine, while maintaining all the hydrogen bond acceptor and donor groups required for supramolecular aggregation, the steric hindrance to supramolecular aggregation is notably reduced because (i.e. guanines with groups in N9 different from sugar are expected to have a greatest conformational freedom even in presence of bulky groups in C8). Supramolecular self-assembly of these derivatives has been accomplished in solutions by NMR and CD spectroscopy and on surface by STM technique. In analogy with other guanosine derivatives, also N9-substituted guanines and GAceHPTM form either ribbon-like aggregates or cation-templated G-quartet based columnar structures.