Catalysis Today, Vol.207, 170-179, 2013
Aerobic oxidation of alpha,beta-unsaturated alcohols using sequentially-grown AuPd nanoparticles in water and tetraalkylphosphonium ionic liquids
Metallic and bimetallic nanoparticles (NPs) (Au, Pd, and AuPd) were synthesized in water with poly(vinylpyrroldine) (PVP) as a polymer stabilizer, as well as in tetraalkylphosphonium chloride ionic liquids (ILs). A borohydride reduction technique was used for the preparation of the monometallic NPs, while a sequential reduction strategy was seen to generate the putative core-shell varieties. Pd and sequentially grown Au-Pd NPs were seen to serve as efficient catalysts for the oxidation of alpha,beta-unsaturated alcohols, while the Au NPs themselves showed minimal activity. However, a system with both Au NPs and a Pd(II) salt (K2PdCl4) also efficiently catalyzed the oxidation reaction in water. A number of aliphatic and aromatic unsaturated alcohols were oxidized using oxygen as an oxidant with these as-prepared catalysts at 60 degrees C in the absence of base. TEM and EXAFS studies of the nanoparticle catalysts before and after the oxidation reaction revealed that the Pd(II) salt was reduced in situ during catalytic conditions, and that there was large changes in particle size and morphology after catalysis, which suggests Ostwald ripening and the presence of a redox mechanism. In the IL system, the ease of Pd reduction led to high activities for many alpha,beta-unsaturated alcohols in the absence of the Au promoter. (C) 2012 Elsevier B. V. All rights reserved.