The effect of size, charge state and composition on the binding of propene to yttrium-doped gold clusters

The catalytic activity of metal clusters can be easily tuned by their size, charge state, or the introduction of dopant atoms. Here, the dopant-, charge- and size-dependent propene adsorption on gold (Au(n)(+)) and yttrium doped gold (Au(n−1)Y(+)) clusters (n = 4–20) was investigated using combined gas-phase reaction studies and density functional theory computations. The increased charge transfer between the cluster and propene in the cationic clusters considerably enhances the propene binding on both pure and yttrium-doped species, compared to their neutral cluster counterparts, while yttrium-doping lowers the propene binding strength in a size-dependent way compared to the pure gold clusters. Chemical bonding and energy decomposition analysis indicate that there is no covalent bond between the cluster and propene. The preferred propene binding site on a cluster is indicated by the large lobes of its LUMO, together with the low coordination number of the adsorption site. In small yttrium-doped gold clusters propene can not only bind to the electron-deficient yttrium atom, but also to the partially positively-charged gold atoms. Therefore, by controlling the charge of the clusters, as well as by introducing yttrium dopants, the propene binding strength can be tuned, opening the route for new catalytic applications.