TitleInfluence of the cobalt particle size in the CO hydrogenation reaction studied by in situ X-ray absorption spectroscopy To whom correspondence should be addressed. E-mail: MBSalmeron@lbl.govThe influence of particle size in the carbon monoxide hydrogenation reaction has been studied using cobalt nanoparticles (NP) with narrow size distribution prepared by colloidal chemistry. The surfactant covering the NP after synthesis could be removed by heating to 200-270ºC in H 2 . Soft X ray absorption spectroscopy was performed in a gas flow cell under reaction conditions of H 2 and CO at atmospheric pressure. Flow of pure hydrogen at 350ºC removed the protecting surfactant layer and reduced the NP from oxidized to metallic. The NP remained metallic during the methanation reaction with their surface covered by CO. The methanation turnover frequency of silica supported NP was found to decrease with diameter below 10 nm, while the reaction activation energy was found to be independent of NP size. H-D exchange experiments indicated that it is the dissociation of H 2 that is responsible for the observed decrease in activity with size.2 KEYWORDS. Cobalt, nanoparticles, Fischer-Tropsch, X-ray absorption (XAS), in situ studies, soft xray spectroscopy, particle size dependence.