Plasma-Catalytic Ammonia Synthesis Beyond the Equilibrium Limit

We explore the consequences of non-thermal plasma activation on product yields in catalytic ammonia synthesis, a reaction that is equilibrium-limited at elevated temperatures. We employ a minimal microkinetic model that incorporates the influence of plasma activation on N₂ dissociation rates to predict NH₃ yields into and across the equilibrium-limited regime. NH₃ yields are predicted to exceed bulk thermodynamic equilibrium limits on materials that are thermal-rate-limited by N₂ dissociation. In all cases, yields revert to bulk equilibrium at temperatures at which thermal reaction rates exceed plasma-activated ones. Beyond-equilibrium NH₃ yields are observed in a packed bed dielectric-barrier-discharge reactor and exhibit sensitivity to catalytic material choice in a way consistent with model predictions. The approach and results highlight the opportunity to exploit synergies between non-thermal plasmas and catalysts to affect transformations at conditions inaccessible through thermal routes.