Leveraging Expertise in Thermal Catalysis to Understand Plasma Catalysis

Best practices in testing heterogeneous catalysts are translated to plasma-catalytic experiments. Independent determination of plasma-catalytic and plasma-chemical contributions is essential. Non-porous catalyst particles are preferred because active sites inside sub-micron pores cannot contribute. Temperature variation is needed to determine kinetics, despite the complexity of thermal effects in plasma. Rigorous checks on catalyst deactivation and mass balance are needed. Plasma enhanced reversed reactions should be minimized by keeping conversion low and far from thermodynamic equilibrium, preventing underestimation of the rate of forward reaction. In contrast, plasma-catalytic studies often aim at conversions surpassing thermodynamic equilibrium, not obtaining any information on kinetics. Calculation of catalyst activity per active sites (turn-over-frequency) requires also appropriate characterization to determine the number of active sites. The relationship between kinetics and thermodynamics for plasma-catalysis is discussed using endothermic decomposition of CO₂ and exothermic synthesis of ammonia from N₂ and H₂ as examples. Assuming Langmuir-Hinshelwood and Eley-Rideal mechanisms, the effect of excitation of reactant molecules on activation barriers and surface coverages are discussed, influencing reaction rates. The consequences of reversed reactions are considered. Plasma-catalysis with catalysts applied for thermal catalysis at much higher temperature should be avoided, as adsorbed species are bonded too strongly resulting in low rates.