NO formation by N2/O2 plasma catalysis: The impact of surface reactions, gas-phase reactions, and mass transport

Pathways and timescales relevant to facilitate plasma-assisted N2-O2 reactions are assessed by measuring the consumption of plasma-derived N and the formation of NO in the gas phase and over Ag catalytic surfaces. These measurements are enabled by a setup that enables N2 activation in an atmospheric pressure RF plasma jet, enables O2 addition in the plasma afterglow, facilitates reactions over an Ag wire catalyst, and allows species density quantification by molecular beam mass spectrometry. Gas-phase reactions consume N but do not form NO with high selectivity. The presence of the non-porous Ag wire catalyst increases the rate of N conversion to NO, though mass transfer processes, not surface reactions, dictate the rate of N consumption. When O2 concentrations and the ratio of the surface area of the catalyst to the void volume of the reactor are high (3-5 mol% O2, 10900 m-1), N conversion to NO reaches 100 % selectivity. When both N2 and O2 are fed through the plasma jet, gas-phase NO production increases 10x, although plasma and gas-phase processes do not exclusively produce NO. Above a threshold NO density, N cannot diffuse to the catalyst surface faster than it is consumed in the gas phase by reactions with NO. Thus, the use of heterogeneous catalysts to enhance plasma-driven NxOy formation and control NxOy product selectivity is limited to cases where diffusive transport of N from the gas phase to the catalyst surface is faster than consumption of N from gas-phase reactions with NO.