The NO oxidation reaction kinetics over a number of zeolite structures were investigated at temperatures above 423 K using plug-flow microreactors and in situ FTIR spectroscopy. Fast catalytic NO oxidation rates (up to 1000x) are observed over H- and Na-exchanged zeolite frameworks (BEA, MFI, and CHA) at temperatures above 423 K with respect to the gas-phase reaction. NO oxidation rates increase with temperature over H- and Na-zeolites, while siliceous zeolites display little activity. Activation energies scale in the order of CHA < MFI < BEA (40.8-55.5 kJ mol(-1)), and application of transition state theory shows that the formation of the activated complex is an enthalpically controlled process that benefits from smaller zeolite pore size. In all samples, rates are proportional to NO and O-2 concentrations, in contrast to low-temperature catalytic rates Loiland et al. [33], which are second order in NO and first order in O-2. This difference indicates that a new reaction mechanism is operative above 423 K. In-situ FOR studies reveal that NO coordinated at framework sites in the zeolite pores (Si-O-(NO+)-Al) plays a direct role in the catalysis, and they also reveal that the NO+ oxidation rate is proportional to the amount of NO+ present in the sample. Furthermore, it is found that NO+ is in equilibrium with gas-phase NO and that desorption of NO (as NO) yields an oxidized acid site (Si-O. Al). No evidence of NO+ formation is observed over the siliceous zeolite samples. A working model of the reaction mechanism for the high-temperature NO oxidation reaction is proposed for acidic zeolites that is consistent with the observed form of the rate equation and the observed NO+ reaction intermediate. (C) 2015 Elsevier Inc. All rights reserved.