Selective hydrogenation by Pd nanoparticles embedded in polyelectrolyte multilayers

Alternating adsorption of poly(acrylic acid) and a polyethylenimine?Pd(II) complex on alumina and subsequent reduction of Pd(II) by NaBH4 yield catalytic Pd nanoparticles embedded in multilayer polyelectrolyte films. The polyelectrolytes limit aggregation of the particles and impart catalytic selectivity in the hydrogenation of α-substituted unsaturated alcohols by restricting access to catalytic sites. Hydrogenation of allyl alcohol by encapsulated Pd(0) nanoparticles can occur as much as 24-fold faster than hydrogenation of 3-methyl-1-penten-3-ol. Additionally, the nanoparticle/polyelectrolyte system suppresses unwanted substrate isomerization, when compared to a commercial palladium catalyst. Selective diffusion through poly(acrylic acid)/polyethlyenimine membranes suggests that hydrogenation selectivities are due to different rates of diffusion to nanoparticle catalysts. First-order kinetics are also consistent with a diffusion-limited mechanism. Further exploitation of the versatility of polyelectrolyte films should increase selectivity in hydrogenation as well as other reactions. Copyright © 2004 American Chemical Society.