Localized surface plasmon resonance of Au/TiO2(110): substrate and size influence from in situ optical and structural investigation.

Localized Surface Plasmon Resonance (LSPR) of noble metal nanoparticles has attracted a lot of attention in recent years as enhancer of the photocatalytic activity in the visible light domain. Rare are the experimental in situ studies, coupling structural and optical responses, but they are mandatory for a deep understanding of the mechanisms underlying LSPR. Herein we present an in situ investigation during the growth of gold nanoparticles (NPs) on TiO2(110) in the 2-6 nm size range. We probed the structural and morphological properties of the supported nanoparticles by performing GIXRD and GISAXS simultaneously with their optical response in p and s polarizations recorded by SDRS. The rutile surface state turns out to have a major effect on the Au NPs growth and on their plasmonic response, both in frequency and vibration modes. The roughening of the TiO2(110) surface weakens the interaction strength between the NPs and the substrate, favoring the growth of textured in-plane randomly orientated NPs. Compared to the epitaxial clusters growing on the flat TiO2 surface, these textured NPs are characterized by a LSPR blue shift and by the presence of LSPR vibration modes perpendicular to the surface for sizes smaller than about 4 nm.

Catalytic properties of supported gold nanoparticles: new insights into the size-activity relationship gained from in operando measurements.

The relationship between the catalytic activity and the size was studied in operando in the case of gold nanoparticles on TiO2(110) model catalyst during carbon monoxide oxidation. The geometrical parameters, the shape and the dispersion of the particles on the oxide support were examined in detail. The catalytic activity was found optimum for a nanoparticle diameter of about 2 nm and a height of six atomic monolayers. Above the maximum, it fits a power law of the diameter D(-24 +/- 0.3). This indicates that the low-coordinated sites play a major role in the catalytic activity, however such a model still fails to explain the activity maximum. The nanoparticle sintering was also investigated since it is suspected of being responsible for the decrease of the catalyst activity in the course of time. It was clearly observed for particles with a size around the maximum of activity and smaller. At the very beginning of the CO conversion into CO2, the sintering is strongly activated. The nanoparticles mobility is dependent upon the TiO2(110) surface direction under consideration: it is higher along the [001]TiO2 than along the [1-10]TiO2. Then, the sintering greatly slows down. This could be explained by a nanoparticles' pinning at the step edges. The thermal energy released by the exothermic CO oxidation reaction was evaluated and it suggests that the sintering results from a more complex process than from a reaction-induced local heating.

New reactor dedicated to in operando studies of model catalysts by means of surface x-ray diffraction and grazing incidence small angle x-ray scattering.

A new experimental setup has been developed to enable in situ studies of catalyst surfaces during chemical reactions by means of surface x-ray diffraction (SXRD) and grazing incidence small angle x-ray scattering. The x-ray reactor chamber was designed for both ultrahigh-vacuum (UHV) and reactive gas environments. A laser beam heating of the sample was implemented; the sample temperature reaches 1100 K in UHV and 600 K in the presence of reactive gases. The reactor equipment allows dynamical observations of the surface with various, perfectly mixed gases at controlled partial pressures. It can run in two modes: as a bath reactor in the pressure range of 1-1000 mbars and as a continuous flow cell for pressure lower than 10(-3) mbar. The reactor is connected to an UHV preparation chamber also equipped with low energy electron diffraction and Auger spectroscopy. This setup is thus perfectly well suited to extend in situ studies to more complex surfaces, such as epitaxial films or supported nanoparticles. It offers the possibility to follow the chemically induced changes of the morphology, the structure, the composition, and growth processes of the model catalyst surface during exposure to reactive gases. As an example the Pd(8)Ni(92)(110) surface structure was followed by SXRD under a few millibars of hydrogen and during butadiene hydrogenation while the reaction was monitored by quadrupole mass spectrometry. This experiment evidenced the great sensitivity of the diffracted intensity to the subtle interaction between the surface atoms and the gas molecules.

Highly strained structure of a four-layer deposit of Pd on Ni(110): a coupled theoretical and experimental study.

The structure of a four monolayer deposit of Pd on Ni(110) has been determined by a combination of x-ray diffraction experiments and density-functional theory calculations. This Pd film presents, after annealing at 500 K, a (Nx2) reconstruction associated with a large enhancement of its catalytic activity. The N superstructure, along the dense [11;0] direction, comes from periodic edge dislocations initiated by a vacancy in the first Pd layer. In the perpendicular direction, the doubling of the period originates in a pairing-buckling displacement of the rows. This study evidences a new Pd atoms arrangement with quasi-four-fold hollow sites on the surface, which could play an important role in the exceptional catalytic activity.