The origin of the catalytic activity of gold nanoparticles remains debated despite extensive studies. This in operando work investigates the relationship between catalytic activity and size/shape of gold nanoparticles supported on TiO2(110) during CO oxidation. The nanoparticles were synthesized by vapor deposition in ultrahigh vacuum. Their geometry was monitored in the presence of O2, Ar, or a mixture of O2 + CO and of Ar + CO by grazing incidence small-angle X-ray scattering simultaneously with the catalytic activity. The occurrence of CO oxidation induces a sintering directly correlated to the reaction rate. The catalytic activity is optimum for a nanoparticle’s diameter of 2.1 ± 0.3 nm and a height of about six atomic layers. Below this size, the activity drop corresponds to a height decrease. Rescaling of activities obtained in different experimental conditions shows consistency of these results with published data using both “model” and “real” catalysts.
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.
It is well known that gold nanoparticles supported on TiO2 act as a catalyst for CO oxidation, even below room temperature. Despite extensive studies, the origin of this catalytic activity remains under debate. Indeed, when the particle size decreases, many changes may occur; thus modifying the nanoparticles' electronic properties and consequently their catalytic performances. Thanks to a state-of-the-art home-developed setup, model catalysts can be prepared in ultra-high vacuum and their morphology then studied in operando conditions by Grazing Incidence Small Angle X-ray Scattering, as well as their atomic structure by Grazing Incidence X-ray Diffraction as a function of their catalytic activity. We previously reported on the existence of a catalytic activity maximum observed for three-dimensional gold nanoparticles with a diameter of 2-3 nm and a height of 6-7 atomic planes. In the present work we correlate this size dependence of the catalytic activity to the nanoparticles' atomic structure. We show that even when their size decreases below the optimum diameter, the gold nanoparticles keep the face-centered cubic structure characteristic of bulk gold. Nevertheless, for these smallest nanoparticles, the lattice parameter presents anisotropic strains with a larger contraction in the direction perpendicular to the surface. Moreover a careful analysis of the atomic-scale morphology around the catalytic activity maximum tends to evidence the role of sites with a specific geometry at the interface between the nanoparticles and the substrate. This argues for models where atoms at the interface periphery act as catalytically active sites for carbon monoxide oxidation.
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