Cationic Polymer Coating Increases the Catalytic Activity of Gold Nanoparticles toward Anionic Substrates.

Organic coatings on catalytic metal nanoparticles (NPs) typically hinder their activity due to the blocking of active sites. Therefore, considerable effort is made to remove organic ligands when preparing supported NP catalytic materials. Here, cationic polyelectrolyte coatings are shown to increase the catalytic activity of partially embedded gold nanoislands (Au NIs) toward transfer hydrogenation and oxidation reactions with anionic substrates compared to the activity of identical but uncoated Au NIs. Any potential steric hindrance caused by the coating is countered by a decrease in the activation energy of the reaction by half, resulting in overall enhancement. The direct comparison to identical but uncoated NPs isolates the role of the coating and provides conclusive evidence of enhancement. Our findings show that engineering the microenvironment of heterogeneous catalysts, creating hybrid materials that cooperatively interact with the reactants involved, is a viable and exciting path to improving their performance.