Active Sites of Pd-Doped Flat and Stepped Cu(111) Surfaces for H2 Dissociation in Heterogeneous Catalytic Hydrogenation

It has been shown in recent experiments that the Cu(111) surface doped by a small amount of Pd atoms can exhibit excellent catalytic performance toward the dissociation of H2 molecules. Here we performed systematic first-principles calculations to investigate the corresponding mechanism. Our results clearly demonstrate that a very small number of Pd atoms in the subsurface layer can effectively reduce the energy barrier of H2 dissociation, making the ensembles composed of the surface and contiguous subsurface Pd atoms as the active sites. The catalytic activity can be further improved if the Pd atoms are doped in the stepped Cu surfaces. The impact of the subsurface Pd atoms comes from an enhanced surface–adsorbate interaction caused by adjusting the electronic structure of the substrate. The important role played by the subsurface atoms offers an efficient approach to finely tune the surface activity by a very limited number of atoms. Our findings should be very useful for understanding and improving the...