Hydroxyapatite-supported palladium nanoclusters: a highly active heterogeneous catalyst for selective oxidation of alcohols by use of molecular oxygen

Treatment of a stoichiometric hydroxyapatite (HAP), Ca10(PO4)6(OH)2, with PdCl2(PhCN)2 gives a new type of palladium-grafted hydroxyapatite. Analysis by means of powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray (EDX), IR, and Pd K-edge X-ray absorption fine structure (XAFS) proves that a monomeric PdCl2 species is chemisorbed on the HAP surface, which is readily transformed into Pd nanoclusters with a narrow size distribution in the presence of alcohol. Nanoclustered Pd0 species can effectively promote the alcohol oxidation under an atmospheric O2 pressure, giving a remarkably high turnover number (TON) of up to 236,000 with an excellent turnover frequency (TOF) of approximately 9800 h(-1) for a 250-mmol-scale oxidation of 1-phenylethanol under solvent-free conditions. In addition to advantages such as a simple workup procedure and the ability to recycle the catalyst, the present Pd catalyst does not require additives to complete the catalytic cycle. The diameters of the generated Pd nanoclusters can be controlled upon acting on the alcohol substrates used. Oxidation of alcohols is proposed to occur primarily on low-coordination sites within a regular arrangement of the Pd nanocluster by performing calculations on the palladium crystallites.