Atomic overlayer of permeable microporous cuprous oxide on palladium promotes hydrogenation catalysis.

The interfacial sites of metal-support interface have been considered to be limited to the atomic region of metal/support perimeter, despite their high importance in catalysis. By using single-crystal surface and nanocrystal as model catalysts, we now demonstrate that the overgrowth of atomic-thick Cu 2 O on metal readily creates a two-dimensional (2D) microporous interface with Pd to enhance the hydrogenation catalysis. With the hydrogenation confined within the 2D Cu 2 O/Pd interface, the catalyst exhibits outstanding activity and selectivity in the semi-hydrogenation of alkynes. Alloying Cu(0) with Pd under the overlayer is the major contributor to the enhanced activity due to the electronic modulation to weaken the H adsorption. Moreover, the boundary or defective sites on the Cu 2 O overlayer can be passivated by terminal alkynes, reinforcing the chemical stability of Cu 2 O and thus the catalytic stability toward hydrogenation. The deep understanding allows us to extend the interfacial sites far beyond the metal/support perimeter and provide new vectors for catalyst optimization through 2D interface interaction.