Mechanism of hydrogen adsorption on gold nanoparticles and charge transfer probed by anisotropic surface plasmon resonance.

The adsorption of hydrogen on Au nanoparticles (NPs) of size of the order of 10 nm has been investigated by use of localised surface plasmon resonances (LSPR) in the NPs. The samples, formed by Au NPs obtained by oblique angle deposition on glass substrates, display a strong optical dichroism due to two different plasmon resonances dependent on the polarisation of light. This ensured the use of Transmittance Anisotropy Spectroscopy, a sensitive derivative optical technique, which permitted one to measure shifts of the LSPR as small as 0.02 nm upon H adsorption, which are not accessible by conventional plasmonic methods. The measured signal is proportional to the area of the NPs, which shows that H atoms diffuse on their facets. A negative charge transfer from Au to H is clearly demonstrated.

Unusual two-stage kinetics of ethylene adsorption on Si(100) unraveled by surface optical spectroscopy and Monte Carlo simulation.

The adsorption of ethylene on a Si(100)-2×1 surface in an ultrahigh vacuum has been monitored at room temperature by use of real-time surface differential reflectance spectroscopy, which clearly demonstrated that the adsorption follows a two-stage process. About half a monolayer is obtained for 1 L, while the second stage is much slower, yielding the complete monolayer for an exposure of ∼400 L. The kinetics over the full range has been successfully reproduced by a Monte Carlo calculation. The key point of this two-stage adsorption kinetic lies in the reduced adsorption probability (by a factor of several hundreds) on the Si dimers, neighbors of dimers which have already reacted, with respect to the adsorption probability on isolated dimers. This new kind of adsorption kinetics, due to a repulsion between already adsorbed molecules and additional molecules impinging on the surface, makes it a textbook case for a "cooperative" adsorption process.

HRTEM and STEM-HAADF characterisation of Au-TiO2 and Au-Al2O3 catalysts for a better understanding of the parameters influencing their properties in CO oxidation.

Gold catalysts supported on titania (Au-TiO(2)) and alumina (Au-Al(2)O(3)) were prepared by deposition-precipitation with urea and then activated before characterisation and reaction in CO oxidation, either by calcination in air at 500 °C or reduction under H(2) at 300 °C. Gold nanoparticles with average size in the range 2-4 nm were obtained, with calcination leading to larger gold nanoparticles than reduction. For Au-TiO(2), high activity was observed in CO oxidation at room temperature, independent of the activation treatment. This high activity could not be correlated to the presence of sub-nanometer gold clusters as reported in the literature, since they could not be detected by atomic-resolution high-angle annular dark-field scanning-transmission electron microscopy (HAADF-STEM). In the case of Au-Al(2)O(3), the performance in CO oxidation was found to strongly depend on the water content in the reaction gas feed and on the activation conditions, with calcination resulting in a poorly active catalyst whereas reduction gave activity of the same order as Au-TiO(2). A comparative study of Au-TiO(2) and Au-Al(2)O(3) by electron microscopy did not reveal distinct differences in the shapes of the Au nanoparticles, which are mostly flattened through interaction with the substrate in both samples, with side profile shapes varying from rounded hemispherical to well faceted truncated cubo-octahedra. More faceting is found for the samples calcined at 500 °C than reduced at 300 °C. Various possible parameters affecting the catalytic properties of gold in CO oxidation are discussed in the context of the relevant literature.

The Ground State of Epitaxial Germanene on Ag(111).

Two-dimensional (2D) honeycomb lattices beyond graphene, such as germanene, appear very promising due to their outstanding electronic properties, such as the quantum spin Hall effects. While there have been many claims of germanene monolayers up to now, no experimental evidence of a honeycomb structure has been provided up to now for these grown monolayers. Using scanning tunneling microscopy (STM), surface X-ray diffraction (SXRD), and density functional theory, we have elucidated the Ge-induced (109×109)R±24.5° reconstruction on Ag(111). We demonstrate that a powerful algorithm combining SXRD with STM allows us to solve a giant surface reconstruction with more than a hundred atoms per unit cell. Its extensive unit cell indeed consists of 98 2-fold or 3-fold coordinated Ge atoms, forming a periodic arrangement of pentagons, hexagons, and heptagons, with the inclusion of six dispersed Ag atoms. By analogy, we show that the (77×77)R±19.1° reconstruction obtained by segregation of Ge through an epitaxial Ag/Ge(111) film possesses a similar structure, i.e., Ge pentagons/hexagons/heptagons with a few Ag atoms. Such an organization is more stable than that of pure Ge monolayers and can be assigned to the ground state of epitaxial germanene.

Gas-induced selective re-orientation of Au-Cu nanoparticles on TiO2 (110).

Au-Cu bimetallic nanoparticles (NPs) grown on TiO2(110) have been followed in situ using grazing incidence X-ray diffraction and X-ray photoemission spectroscopy from their synthesis to their exposure to a CO/O2 mixture at low pressure (P < 10-5 mbar) and at different temperatures (300 K-470 K). As-prepared samples are composed of two types of alloyed NPs: randomly oriented and epitaxial NPs. Whereas the introduction of CO has no effect on the structure of the NPs, an O2 introduction triggers a Cu surface segregation phenomenon resulting in the formation of a Cu2O shell reducible by annealing the sample over 430 K. A selective re-orientation of the nanoparticles, induced by the exposure to a CO/O2 mixture, is observed where the randomly oriented NPs take advantage of the mobility induced by the Cu segregation to re-orient their Au-rich core relatively to the TiO2(110) substrate following specifically the orientation ((111)NPs//(110)TiO2) when others epitaxial relationships were observed on the as-prepared sample.

Transition from silicene monolayer to thin Si films on Ag(111): comparison between experimental data and Monte Carlo simulation.

Scanning tunneling microscopy (STM), Auger electron spectroscopy (AES) and low energy electron diffraction have been used to follow the growth of Si films on Ag(111) at various temperatures. Using a simple growth model, we have simulated the distribution of film thickness as a function of coverage during evaporation, for the different temperatures. In the temperature regime where multilayer silicene has been claimed to form (470-500 K), a good agreement is found with AES intensity variations and STM measurements within a Ag surfactant mediated growth, whereas a model with multilayer silicene growth fails to reproduce the AES measurements.

Resolving the Controversial Existence of Silicene and Germanene Nanosheets Grown on Graphite.

The highly oriented pyrolytic graphite (HOPG) surface, consisting of a dangling bond-free lattice, is regarded as a potential substrate for van der Waals heteroepitaxy of two-dimensional layered materials. In this work, the growth of silicon and germanium on HOPG is investigated with scanning tunneling microscopy by using typical synthesis conditions for silicene and germanene on metal surfaces. At low coverages, the deposition of Si and Ge gives rise to tiny and sparse clusters that are surrounded by a honeycomb superstructure. From the detailed analysis of the superstructure, its comparison with the one encountered on the bare and clean HOPG surface, and simulations of the electron density, we conclude that the superstructure is caused by charge density modulations in the HOPG surface. At high coverages, we find the formation of clusters, assembled in filamentary patterns, which indicates a Volmer-Weber growth mode instead of a layer-by-layer growth mode. This coverage-dependent study sets the stage for revisiting recent results alleging the synthesis of silicene and germanene on the HOPG surface.

Adsorption of phenylacetylene on Si(100)-2 x 1: kinetics and structure of the adlayer.

Direct adsorption of phenylacetylene on clean silicon surface Si(100)-2 x 1 is studied in ultrahigh vacuum (UHV). The combination of scanning tunnel microscopy (STM) and surface differential reflectance spectroscopy (SDRS) with Monte Carlo calculations are put together to draw a realistic kinetic model of the evolution of the surface coverage as a function of the molecular exposure. STM images of weakly covered surfaces provide evidence of two very distinct adsorption geometries for phenylacetylene, with slightly different initial sticking probabilities. One configuration is detected with STM as a bright spot that occupies two dangling bonds of a single dimer, whereas the other configuration occupies three dangling bonds of adjacent dimers. These data are used to implement a Monte Carlo model which further serves to design an accurate kinetic model. The resulting evolution toward saturation is compared to the optical data from surface differential reflectance spectroscopy (SDRS). SDRS is an in situ technique that monitors the exact proportion of affected adsorption sites and therefore gives access to the surface coverage which is evaluated at 0.65. We investigate the effect of surface temperature on this adsorption mechanism and show that it has no major effect either on kinetics or on structure, unless it passes the threshold of dissociation measured at ca. 200 degrees C. This offers a comprehensive image of the whole adsorption process of phenylacetylene from initial up to complete saturation.

Tailoring Anisotropic Interactions between Soft Nanospheres Using Dense Arrays of Smectic Liquid Crystal Edge Dislocations.

We investigated composite films of gold nanoparticles (NPs)/liquid crystal (LC) defects as a model system to understand the key parameters, which allow for an accurate control of NP anisotropic self-assemblies using soft templates. We combined spectrophotometry, Raman spectroscopy, and grazing incidence small-angle X-ray scattering with calculations of dipole coupling models and soft sphere interactions. We demonstrate that dense arrays of elementary edge dislocations can strongly localize small NPs along the defect cores, resulting in formation of parallel chains of NPs. Furthermore, we show that within the dislocation cores the inter-NP distances can be tuned. This phenomenon appears to be driven by the competition between "soft (nano)sphere" attraction and LC-induced repulsion. We evidence two extreme regimes controlled by the solvent evaporation: (i) when the solvent evaporates abruptly, the spacing between neighboring NPs in the chains is dominated by van der Waals interactions between interdigitated capping ligands, leading to chains of close-packed NPs; (ii) when the solvent evaporates slowly, strong interdigitation between the is avoided, leading to a dominating LC-induced repulsion between NPs associated with the replacement of disordered cores by NPs. The templating of NPs by topological defects, beyond the technological inquiries, may enable creation, investigation, and manipulation of unique collective features for a wide range of nanomaterials.

Real-time monitoring of growing nanoparticles.

One challenge in the production of nanometer-sized objects with given properties is to control their growth at a macroscopic scale in situ and in real time. A dedicated ultrahigh-vacuum grazing-incidence small-angle x-ray scattering setup has been developed, yielding high sensitivity and dynamics. Its capabilities to derive the average particle shape and size and the film growth mode and ordering and to probe both surfaces and buried interfaces are illustrated for two prototypical cases: the model catalyst Pd/MgO(100) and the self-organized Co/Au(111) system. A wide range of technologically important systems can potentially be investigated in various gaseous environments.