The Effect of Stabilizers on the Catalytic Activity and Stability of Pd Colloidal Nanoparticles in the Suzuki Reactions in Aqueous Solution†

Abstract

Transition metal nanoparticles used in catalysis in solution are stabilized by capping the surfaces that are supposed to be used for catalysis. Determining how these two properties, that is, the catalytic activity and stability of nanoparticles, change as different capping materials are used is the aim of this work. Pd nanoparticles prepared by the reduction of metal salts in the presence of three different stabilizers hydroxyl-terminated poly(amido-amine) (PAMAM) dendrimers (G n -OH, where G n represents the n th generation), block copolymer polystyrene- b -poly(sodium acrylate) and poly( N -vinyl-2-pyrrolidone) (PVP) are used as catalysts in the Suzuki reactions in an aqueous medium to investigate the effects of these stabilizers on the metallic nanoparticle catalytic activity and stability. The stability of the Pd nanoparticles is measured by the tendency of the nanoparticles to give Pd black powder after the catalytic reaction. The Suzuki reaction is a good “acid test” for examining the stability of these nanoparticles, as it takes place when refluxed at about 100 °C for 24 h. The stability is found to depend on the type of the stabilizer, the reactant, and the base used in the reaction system. Pd nanoparticles stabilized by block copolymer, G3 dendrimer, and PVP are found to be efficient catalysts for the Suzuki reactions between phenylboronic acid (or 2-thiopheneboronic acid) and iodobenzene. G4 dendrimer is found to be an effective stabilizer; however, strong encapsulation of Pd particles in the dendrimer results in a loss of catalytic activity. The Suzuki reactions between arylboronic acids and bromoarenes catalyzed by Pd nanoparticles result in byproducts due to the homo-coupling of bromoarenes. A summary of the catalytic activity and stability of the Pd nanoparticles in these different systems is tabulated. As one would expect, these two properties are anticorrelated, that is, the most stable is the least catalytically active.