To estimate the adsorption rate of vibrationally excited molecules, the dissociative adsorption rates were modified to be an explicit function of N 2 and O 2 vibrational states. The non-Boltzmann population densities of vibrationally excited N 2 and O 2 states in the plasma were estimated using the Treanor formula at different vibrational temperatures. The rate constant of each vibrational state are estimated individually and the overall rate constant is calculated with the summation of all vibrational states. The first ten vibrational excited states were included because of the depopulation of highly excited levels. See details in Supplementary Methods. The adsorption of N and O (Reaction 2a and 2b) were included in the plasma catalysis model. P O P O2 is set as 10 P N P N2 since O 2 dissociation fraction is observed to be about one order of magnitude higher than N 2 in N 2 -O 2 plasmas. Plasma reactions Experimentally measured forward rate constants for reactions in the Zeldovich mechanism were used (Supplementary Table ). The backward rate constants were calculated with standard free energies to enforce thermal consistency. The calculated backward rate constants are in agreement with experimental measurements. Vibrational excitation of N 2 and O 2 are included using the same methods in plasma catalysis. Integral reactor models to predict the NO yield of plasma reactions and coupled plasma and catalysts are detailed in Supplementary Methods. In these models, we assume the flow is well-mixed in the reactor. The ordinary equation of gas compositions and surface coverages were solved