Influence of Capping Ligands on the Catalytic Performances of Cobalt Nanoparticles Prepared with the Organometallic Route

Cobalt nanorods and cobalt nanoplatelets, prepared by the same organometallic route with two different metal precursors, were tested for the first time in the acceptor-less dehydrogenation of 2-octanol. The nature of the metal precursor determines not only nanoparticle morphology but also their surface chemistry. While cobalt nanorods showed high conversions (up to 85% after 24 h) and complete selectivity toward 2-octanone with concomitant molecular hydrogen production, cobalt nanoplatelets were practically inactive. Here, we show that this striking difference in the catalytic properties is not associated with facet-dependent differences in reactivity, but rather with different surface chemistry. The activity critically depends on the coordinating ability of the adsorbed species under catalytic reaction conditions and to a smaller degree on their concentration, as evidenced by ligand exchange experiments at room temperature as well as by direct addition of ligands in the reaction during catalysis by cobalt nanorods. This study shows that to optimize performances with unsupported metal nanocatalysts, the capping ligands should be selected by considering their ability to reversibly dissociate from the metal surface during catalysis.