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Heteroatom dopants can greatly modify the electronic and physical properties and catalytic performance of gold nanoclusters. In this study, we investigate the catalytic activity of [Au25-x(PET)18-xM]NH3 (PET = 2-phenylethanethiolate, and M = Cu, Co, Ni, and Zn) nanoclusters in aerobic alcohol oxidation. The [Au25-x(PET)18-xM]NH3 nanoclusters are thoroughly characterized by matrix assisted laser desorption ionization (MALDI) mass spectrometry, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), and inductively coupled plasma–mass spectrometry (ICP-MS). The XPS analyses suggest that the transition metals strongly interact with the gold atoms of the nanoclusters. The CeO2-supported nanoclusters show catalytic activity, based on the conversion of benzyl alcohol, in the order, [Au25-x(PET)18-xNi] > [Au25-x(PET)18-xCu] > [Au25-x(PET)18-xZn] > [Au25-x(PET)18-xCo]. Regarding product selectivity, the [Au25-x(PET)18-xZn] and [Au25-x(PET)18-xCo] catalysts preferably yield benzaldehyde, [Au25-x(PET)18-xCu] yields benzaldehyde and benzyl acid, and [Au25-x(PET)18-xNi] yields benzyl acid. The exposed metal atoms are considered as the catalytic active sites. Also, the catalytic performance (including activity and selectivity) of the [Au25-x(PET)18-xM] catalysts is greatly turned and mediated by the transition metal type.
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