Amorphous alumina overcoats generated by atomic layer deposition (ALD) have been shown to improve the selectivity and durability of supported metal catalysts in many reactions. Several mechanisms have been proposed to explain the enhanced catalytic performance, but the accessibilities of reactants through the amorphous overcoats remain elusive, which is crucial for understanding reaction mechanisms. Here, we show that an AlOx ALD overcoat is able to improve the alkene product selectivity of a supported Pd catalyst in acetylene (C2H2) hydrogenation. We further demonstrate that the AlOx ALD overcoat blocks the access of C2H2 (kinetic diameter of 0.33 nm), O2 (0.35 nm), and CO (0.38 nm) but allows H2 (0.29 nm) to access Pd surfaces. A H-D exchange experiment suggests that H2 might dissociate heterolytically at the Pd-AlOx interface. These findings are in favor of a hydrogen spillover mechanism.
Keywords: amorphous overcoat; atomic layer deposition; heterolytic hydrogen dissociation; hydrogen spillover; selective hydrogenation.