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 Cu2O on metal readily creates a two-dimensional (2D) microporous interface with Pd to enhance the hydrogenation catalysis. With the hydrogenation confined within the 2D Cu2O/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 Cu2O overlayer can be passivated by terminal alkynes, reinforcing the chemical stability of Cu2O 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.