title: The origin of shape sensitivity in palladium-catalyzed Suzuki-Miyaura cross coupling reactions.
abstract: The shape sensitivity of Pd catalysts in Suzuki-Miyaura coupling reactions is studied using nanocrystals enclosed by well-defined surface facets. The catalytic performance of Pd nanocrystals with cubic, cuboctahedral and octahedral morphologies are compared. Superior catalytic reactivity is observed for Pd NCs with {100} surface facets compared to {111} facets. The origin of the enhanced reactivity associated with a cubic morphology is related to the leaching susceptibility of the nanocrystals. Molecular oxygen plays a key role in facilitating the leaching of Pd atoms from the surface of the nanocrystals. The interaction of O2 with Pd is itself facet-dependent, which in turn gives rise to more efficient leaching from {100} facets, compared to {111} facets under the reaction conditions.
authors.affiliation: Department of Chemistry, Analytical and Biological Chemistry Research Facility and Tyndall National Institute, University College Cork, Cork (Ireland); Centre for Research on Adaptive Nanostructures and Nanodevices (CRANN), Trinity College, Dublin (Ireland).
authors.forename: Gillian
authors.initials: G
authors.lastname: Collins
authors.forename: Michael
authors.initials: M
authors.lastname: Schmidt
authors.forename: Colm
authors.initials: C
authors.lastname: O'Dwyer
authors.forename: Justin D
authors.initials: JD
authors.lastname: Holmes
authors.forename: Gerard P
authors.initials: GP
authors.lastname: McGlacken
mesh_terms: D002384:Catalysis; D008958:Models, Molecular; D015394:Molecular Structure; D010165:Palladium / Q000737:chemistry*
chemical_list: D010165:Palladium
keywords: Suzuki-Miyaura coupling; heterogeneous catalysis; palladium; surface facet