Directing oxidation of cobalt nanoparticles with the capping ligand

Cobalt nanoparticles capped with long chain carboxylic acids become hollow when oxidized, while particles capped with tridodecylamine remain solid. [Display omitted] ► Capping ligand type influences oxidation of cobalt nanoparticles. ► Particle size does not influence the oxide layer for cobalt nanoparticles larger than 8 nm. ► Tridodecylamine offers better long term protection against oxidation then carboxylic acids for cobalt nanoparticles. ► Carboxylic acids promotes Kirkendal effect in oxidation of cobalt particles. The oxidation of Co nanoparticles stabilized with various ligands has been studied in an autoclave. Tridodecylamine stabilized Co nanoparticles with different sizes (8 nm, 22 nm and 36 nm) were prepared by thermal decomposition of Co 2(CO) 8 in dodecane. The oxidation of the particles was studied by introducing oxygen into the autoclave and following the oxygen consumption with a pressure meter. Tridodecylamine capped particles were initially oxidized at a high rate, however, the oxidation layer quickly inhibited further oxidation. The thickness of the oxide layer estimated from the oxygen consumption was 0.8 nm for all three particle sizes showing that the oxidation is size independent in the studied particle size range. The tridodecylamine ligand was exchanged for various long chain carboxylic acids and the oxidation was studied. While the carboxylic acids give a slower initial oxidation rate, the formed oxide layer does not inhibit further oxidation as effectively as in the case of tridodecylamine. TEM studies show that tridodecylamine capping leads to particles with a metal core surrounded by an oxide layer, while particles capped with long chain carboxylic acids form hollow cobalt oxide shells.