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 presence of gold on the sidewall of a tapered, single silicon nanowire is directly quantified from core-level nanospectra using energy-filtered photoelectron emission microscopy. The uniform island-type partial coverage of gold determined as 0.42+/-0.06 (approximately 1.8 ML) is in quantitative agreement with the diameter reduction of the gold catalyst observed by scanning electron microscopy and is confirmed by a splitting of the photothresholds collected from the sidewall, from which characteristic local work functions are extracted using a model of the full secondary electron distributions.