Metal-Support Synergy of Supported Gold Nanoclusters in Selective Oxidation of Alcohols

Abstract

Gold catalysts have been reported to exhibit good performance in aerobic oxidation of alcohols, but the intrinsic origin of the catalytic reactivity is still illusive. The catalyst preparation method, the morphology of the gold particles, and even the support might be key factors that determine the activity. Here, we prepared a series of gold catalysts with different supports, i.e., the hydrotalcite (HT), ZnO, MgO, Al2O3, and SiO2, by using the atomically controlled Au25 nanoclusters (NCs) as the gold precursor. The characterization results of the X-ray diffraction (XRD), UV-vis and transmission electron microscopy (TEM) show that the gold particles were mostly uniformly distributed on the supports, with a mean particle size within 3 nm. In aerobic oxidation of benzyl alcohol, the MgAl-HT- and Al2O3-supported Au25 NCs display good performances, with turnover frequency (TOF) values of ~2927 and 2892 h−1, respectively, whereas the SiO2-, MgO-, and ZnO-supported analogues show much inferior activity. The high resolution TEM and X-ray photoelectron spectra (XPS) results suggest that the interactions between gold and the supports in different samples are differing, which influences the morphology and the nature of gold. Our results further point to the importance of acid-base property of the support and the metal-support synergy rather than the gold particle size alone in achieving high-performance in selective alcohol oxidation. Moreover, this work provided a good way to design gold catalysts with controllable sizes that is crucial for understanding the reaction process in aerobic oxidation of alcohol.