Electrostatic Origins of Linear Scaling Relationships at Bifunctional Metal/Oxide Interfaces: A Case Study of Au Nanoparticles on Doped MgO Substrates.

Linear scaling relationships (SRs), which relate binding energies of adsorbates across a space of catalyst surfaces, have been extensively explored for metal and oxide surfaces, but little is known about their properties at interfaces between metal nanoparticles and oxide supports, which are ubiquitous in heterogeneous catalysis. Using periodic DFT calculations, scaling principles are extended to bifunctional Au/oxide interfaces. Adopting a Au nanorod on doped MgO (100) as a model, SRs for species participating in water gas shift, methanol synthesis, and oxidation reactions are reported. SR slopes are not constrained by the bond order conservation rule postulated for metals, oxides, and zeolites, potentially permitting greater flexibility in catalyst design strategies. The deviation from bond counting, along with the physical origin of scaling behavior at interfaces, are explored using a conceptual framework involving electrostatic interactions at the Au/oxide interface.