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The Origin of Shape Sensitivity in Palladium‐Catalyzed Suzuki–Miyaura Cross Coupling Reactions
Author(s) -
Collins Gillian,
Schmidt Michael,
O'Dwyer Colm,
Holmes Justin D.,
McGlacken Gerard P.
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201400483
Subject(s) - catalysis , nanocrystal , palladium , reactivity (psychology) , octahedron , leaching (pedology) , coupling reaction , chemistry , facet (psychology) , materials science , crystallography , chemical engineering , photochemistry , nanotechnology , crystal structure , organic chemistry , medicine , psychology , social psychology , alternative medicine , environmental science , personality , pathology , big five personality traits , soil science , engineering , soil water
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 O 2 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.