Factors Controlling the Reactivity of Catalytically Active Monolayers on Metal Substrates

The focus of this work is on the Pt/MS structures (MS = Au, Ir, Ru, or Pt substrate), as promising electrocatalysts and a prototype for more general systems: (active element monolayer)/(metal substrate) (AE/MS). We evaluate from first principles the effects of AE monolayer strain and the interlayer AE MS electronic state hybridization on surface reactivity and reveal rationale for the interlayer hybridization to dominate over the strain effect in determining the AE/MS surface reactivity. We find, however, that, if AE is weakly bound to MS, the surface electronic structure does not suffice to characterize the surface reactivity, because of involvement of other factors related to lattice response to adsorption of a reaction intermediate. Guided by our findings, we trace surface reactivity to a newly introduced hybridization parameter that reflects important features of the electronic structure of the AE/MS surface, which are not taken into account in the original d-band center model.