Effect of N- and P‑Type Doping on the Oxygen-Binding Energy and Oxygen Spillover of Supported Palladium Clusters

The oxygen-binding energy is one of the primary factors determining catalytic activity in oxidation reactions. One strategy for controlling the binding of a reactant to a surface is to dope the surface to create complementary donor–acceptor pairs. As oxygen is an acceptor, we have investigated the effect of doping on the oxygen-binding energy on Pd atoms and clusters supported on a rutile TiO₂(110) surface. We find that the P-type doping of the TiO₂ surface dramatically reduces the O-binding energy to Pd. When extended to Pd₄-supported clusters, we find that the P-type dopant decreases the energy for the oxygen to bind at spillover sites directly to the TiO₂ surface. In Pd₄O₂, the oxygen-binding energy is reduced with P-type doping, suggesting that this strategy may be used to control the oxygen-binding energy to supported catalysts.