Catalyst deactivation is an important topic for industrial catalyst development. Sintering of small cobalt crystallites is one of the deactivation mechanisms of cobalt-based Fischer–Tropsch synthesis (FTS) catalysts. This study investigates the mechanism of cobalt sintering at low-conversion FTS conditions. A Co/SiO2/Si(1 0 0) model catalyst is exposed to 20 bar dry synthesis gas (H2/CO: 2/1) at 230 °C for 10 h. Cobalt nanoparticles were characterized before and after treatment using transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). TEM images of identical locations on the model catalyst showed a loss of some small crystallites and decrease in size of some crystallites. Sintering is dominated by an Ostwald r...