Igor Píš

Platinum-Doped CeO2 Thin Film Catalysts Prepared by Magnetron Sputtering

The interaction of Pt with CeO(2) layers was investigated by using photoelectron spectroscopy. The 30 nm thick Pt doped CeO(2) layers were deposited simultaneously by rf-magnetron sputtering on a Si(001) substrate, multiwall carbon nanotubes (CNTs) supported by a carbon diffusion layer of a polymer membrane fuel cell and on CNTs grown on the silicon wafer by the CVD technique. The synchrotron radiation X-ray photoelectron spectra showed the formation of cerium oxide with completely ionized Pt(2+,4+) species, and with the Pt(2+)/Pt(4+) ratio strongly dependent on the substrate. The TEM and XRD study showed the Pt(2+)/Pt(4+) ratio is dependent on the film structure.

Near-unity quantum yields from chloride treated CdTe colloidal quantum dots.

Colloidal quantum dots (CQDs) are promising materials for novel light sources and solar energy conversion. However, trap states associated with the CQD surface can produce non-radiative charge recombination that significantly reduces device performance. Here a facile post-synthetic treatment of CdTe CQDs is demonstrated that uses chloride ions to achieve near-complete suppression of surface trapping, resulting in an increase of photoluminescence (PL) quantum yield (QY) from ca. 5% to up to 97.2 ± 2.5%. The effect of the treatment is characterised by absorption and PL spectroscopy, PL decay, scanning transmission electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. This process also dramatically improves the air-stability of the CQDs: before treatment the PL is largely quenched after 1 hour of air-exposure, whilst the treated samples showed a PL QY of nearly 50% after more than 12 hours.

Fast One-Pot Synthesis of MoS2/Crumpled Graphene p–n Nanonjunctions for Enhanced Photoelectrochemical Hydrogen Production

Aerosol processing enables the preparation of hierarchical graphene nanocomposites with special crumpled morphology in high yield and in a short time. Using modular insertion of suitable precursors in the starting solution, it is possible to synthesize different types of graphene-based materials ranging from heteroatom-doped graphene nanoballs to hierarchical nanohybrids made up by nitrogen-doped crumpled graphene nanosacks that wrap finely dispersed MoS2 nanoparticles. These materials are carefully investigated by microscopic (SEM, standard and HR TEM), diffraction (grazing incidence X-ray diffraction (GIXRD)) and spectroscopic (high resolution photoemission, Raman and UV-visible spectroscopy) techniques, evidencing that nitrogen dopants provide anchoring sites for MoS2 nanoparticles, whereas crumpling of graphene sheets drastically limits aggregation. The activity of these materials is tested toward the photoelectrochemical production of hydrogen, obtaining that N-doped graphene/MoS2 nanohybrids are seven times more efficient with respect to single MoS2 because of the formation of local p-n MoS2/N-doped graphene nanojunctions, which allow an efficient charge carrier separation.

Influence of TiO2 electronic structure and strong metal–support interaction on plasmonic Au photocatalytic oxidations

Aiming at understanding how plasmonic reactions depend on important parameters such as metal loading and strong metal–support interaction (SMSI), we report the plasmonic photodegradation of formic acid (FA) under green LED irradiation employing three TiO2 supports (stoichiometric TiO2, N-doped TiO2, black TiO2) modified with Au nanoparticles (NPs) 3–6 nm in size. The rate of FA photooxidation follows different trends depending on Au loading for stoichiometric and doped Au/TiO2 materials. In the first case, the only contribution of hot electron transfer produces a volcano-shaped curve of photoreaction rates with increasing Au loading. When TiO2 contains intra-bandgap states the photoactivity increases linearly with the amount of Au NPs due to the concomitant enhancement produced by hot electron transfer and plasmon resonant energy transfer (PRET). The role of PRET is supported by finite element method simulations, which show that the increase in both Au NP inter-distance and SMSI enhances the probability of charge carrier generation at the Au/TiO2 interface.

Observation and simulation of hard x ray photoelectron diffraction to determine polarity of polycrystalline zinc oxide films with rotation domains

X ray photoelectron diffraction (XPD) patterns of polar zinc oxide (ZnO) surfaces were investigated experimentally using hard x rays and monochromatized Cr Kα radiation and theoretically using a cluster model approach and a dynamical Bloch wave approach. We focused on photoelectrons emitted from the Zn 2p3/2 and O 1s orbitals in the analysis. The obtained XPD patterns for the (0001) and (0001¯) surfaces of a ZnO single crystal were distinct for a given emitter and polarity. Polarity determination of c-axis-textured polycrystalline ZnO thin films was also achieved with the concept of XPD, even though the in-plane orientation of the columnar ZnO grains was random.

Hard-X-ray Photoelectron Diffraction from Si(001) Covered by a 0–7-nm-Thick SiO2 Layer

X-ray photoelectron diffraction has become a common method to determine element-specific local atomic surface structure. The use of hard X-rays makes this method bulk-sensitive and capable of studying the atomic structure of new materials such as multilayers and buried layers. We present the first Cr Kα-excited angle-resolved photoelectron diffraction from Si(001) covered by a 0–7-nm-thick SiO2 layer and demonstrate the information depth of this technique. The measured results are compared with a cluster model simulation.

Control of the Intermolecular Coupling of Dibromotetracene on Cu(110) by the Sequential Activation of CBr and CH Bonds

Dibromotetracene molecules are deposited on the Cu(110) surface at room temperature. The complex evolution of this system has been monitored at different temperatures (i.e., 298, 523, 673, and 723 K) by means of a variety of complementary techniques that range from STM and temperature-programmed desorption (TPD) to high-resolution X-ray spectroscopy (XPS) and near-edge X-ray absorption fine structure spectroscopy (NEXAFS). State-of-the-art density-functional calculations were used to determine the chemical processes that take place on the surface. After deposition at room temperature, the organic molecules are transformed into organometallic monomers through debromination and carbon-radical binding to copper adatoms. Organometallic dimers, trimers, or small oligomers, which present copper-bridged molecules, are formed by increasing the temperature. Surprisingly, further heating to 673 K causes the formation of elongated chains along the Cu(110) close-packed rows as a consequence of radical-site migration to the thermodynamically more stable molecule heads. Finally, massive dehydrogenation occurs at the highest temperature followed by ring condensation to nanographenic patches. This study is a paradigmatic example of how intermolecular coupling can be modulated by the stepwise control of a simple parameter, such as temperature, through a sequence of domino reactions.

Silver nanoparticles linked by a Pt-containing organometallic dithiol bridge: study of local structure and interface by XAFS and SR-XPS

Silver nanoparticles (AgNPs) functionalized with an organometallic bifunctional thiol containing Pt(ii) centers, generated in situ from trans-trans-[thioacetyl-bistributylphosphine-diethynylbiphenyl-diplatinum(ii)], were synthesized with different sulphur/metal molar ratios (i.e. AgNPs-1 and AgNPs-2) with the aim to obtain nanosystems of different mean size and self-organization behaviour. AgNPs spontaneously self-assemble, giving rise to 2D networks, as previously assessed. In this work a deeper insight into the chemico-physical properties of these AgNPs is proposed by means of synchrotron radiation induced X-ray photoelectron spectroscopy (SR-XPS) and X-ray absorption fine structure spectroscopy (XAFS) techniques. The results are discussed in order to probe the interaction at the interface between a noble metal and a thiol ligand at the atomic level and the aim of this study is to shed light on the chemical structure and self-organization details of nanosystems. The nature of the chemical interaction between the dithiol ligand and the Ag atoms on the nanoparticle surface was investigated by combining SR-XPS (S2p, Ag3d core levels) and XAS (S and Ag K-edges) analysis. UV-visible absorption and emission measurements were also carried out on all samples and compared with TD-DFT calculations so as to get a better understanding of their optical behavior and establish the nature of the excitation and emission processes.

Synthesis of graphene nanoribbons with a defined mixed edge-site sequence by surface assisted polymerization of (1,6)-dibromopyrene on Ag(110)

By a combination of scanning tunneling microscopy, X-ray spectroscopic techniques and density functional theory calculations, we prove the formation of extended patterns of parallel, graphene nanoribbons with alternate zig-zag and armchair edges and selected width by surface-assisted Ullmann coupling polymerization and dehydrogenation of 1,6-dibromopyrene (C16H8Br2). Besides the relevance of these nanostructures for their possible application in nanodevices, we demonstrate the peculiarity of halogenated pyrene derivatives for the formation of nanoribbons, in particular on Ag(110). These results open the possibility of tuning the shape and dimension of nanoribbons (and hence the correlated electronic properties) by choosing suitably tailored or on-purpose designed molecular precursors.

Gold nanoparticles functionalized by rhodamine B isothiocyanate: a new tool to control plasmonic effects

Gold nanoparticles with an average diameter of 10 nm, functionalized by the dye molecule rhodamine B isothiocyanate, have been synthesized. The resulting material has been extensively characterized both chemically, to investigate the bonding between the dye molecules and the nanoparticles, and physically, to understand the details of the aggregation induced by interaction between dye molecules on different nanoparticles. The plasmonic response of the system has been further characterized by measurement and theoretical simulation of the static UV-Vis extinction spectra of the aggregates produced following different synthesis procedures. The model parameters used in the simulation gave further useful information on the aggregation and its relationship to the plasmonic response. Finally, we investigated the time dependence of the plasmonic effects of the nanoparticles and fluorescence of the dye molecule using an ultrafast pump-probe optical method. By modulating the quantity of dye molecules on the surface of the nanoparticles it was possible to exert fine control over the plasmonic response of nanoparticles.