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Size hierarchy is a distinct feature of nanogold-catalysts as it can strongly affect their performance in various reactions. We developed a simple method to generate AunSm nanoclusters of different sizes by thermal treatment of an Au144(PET)60 (PET: phenylethanethiol) parent cluster. These clusters, deposited on activated carbon, exhibit excellent catalytic performance in the hydrochlorination of acetylene. In-situ ultraviolet laser dissociation high-resolution mass spectrometry of the parent cluster in the presence of acetylene revealed a remarkable cluster size-dependence of acetylene adsorption, which is a crucial step in the hydrochlorination. Systematic density functional theory calculations of the reaction pathways on the differently-sized clusters provide deeper insight into the cluster size dependence of the adsorption energies of the reactants and afforded a scaling relationship between the adsorption energy of acetylene and the co-adsorption energies of the reactants (C2H2 and HCl), which could enable a qualitative prediction of the optimal AunSm cluster for the hydrochlorination of acetylene.
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