On factors controlling activity of submonolayer bimetallic catalysts: nitrogen desorption

We model N2 desorption on submonolayer bimetallic surfaces consisting of Co clusters on Pt(111) via first-principles density functional theory-based kinetic Monte Carlo simulations. We find that submonolayer structures are essential to rationalize the high activity of these bimetallics in ammonia decomposition. We show that the N2 desorption temperature on Co∕Pt(111) is about 100 K higher than that on Ni∕Pt(111), despite Co∕Pt(111) binding N weaker at low N coverages. Co∕Pt(111) has substantially different lateral interactions than single metals and Ni∕Pt. The lateral interactions are rationalized with the d-band center theory. The activity of bimetallic catalysts is the result of heterogeneity of binding energies and reaction barriers among sites, and the most active site can differ on various bimetallics. Our results are in excellent agreement with experimental data and demonstrate for the first time that the zero-coverage descriptor, used until now, for catalyst activity is inadequate due not only to lacking lateral interactions but importantly to presence of multiple sites and a complex interplay of thermodynamics (binding energies, occupation) and kinetics (association barriers) on those sites.