Tuning surface reactivity by finite size effects: role of orbital symmetry in the $d-$band model

Catalytic activity depends sensitively on the strength of the interactions between reactant molecules and catalyst surface: too weak and the catalyst cannot capture enough molecules to react; too strong and the reaction products do not desorb, blocking further reactions. The ability to control the binding strength of molecules to metal surfaces is thus fundamental to the design of efficient and selective catalysts. Catalyst design often relies on increasing the interaction strength on relatively non-reactive materials by introducing active sites. Here, we present a complementary approach: we exploit finite size effects in the electronic structure of ultrathin Pd(111) films grown on Ru(0001) to tune their reactivity by changing the film thickness one atom layer at a time. While bulk Pd(111) is reactive toward oxygen, we find that Pd films thinner than 6 atom layers are surprisingly inert to oxidation. This observation can be explained with the $d$-band model only when it is applied to the orbitals directly involved in the bonding. The insight into orbital specific contributions to surface reactivity could be useful in the design of catalysts.