The oxidation of NO over Bronsted acid sites in chabazite (CHA) zeolites shows an atypical temperature dependence; at low temperature the apparent activation energy is negative, but it becomes positive as the temperature exceeds a transition temperature. To explain this behavior we used density functional theory and statistical mechanics to investigate high and low temperature mechanisms for this reaction and propose a dynamic active site change in response to temperature variation. Our simulations show that the apparent activation barrier in the low temperature regime is more negative over Bronsted acidic CHA as compared to the siliceous zeolite framework. This effect is attributed to further enthalpic stabilization of the transition states by physical interaction with the H-CHA Bronsted acid sites. At elevated temperature, our calculations support both the existence and the significant catalytic role of NO+ in providing a modified active site. The temperature dependent transformation of the active site from H-CHA to NO-CHA sites may occur via two plausible ion-exchange mechanisms that define a transition temperature for the reaction. This transition temperature can be tuned by incorporating different trivalent metal atoms (B, Al, Ga or In) within the CHA framework. We found the lowest transition temperature for H-[In] CHA and H-[Ga]CHA. The ability to control the dynamic response of the active site and the associated switch between low and high temperature mechanism with negative and positive apparent activation energy, respectively, is of fundamental interest for the design of zeolite catalysts operating in the presence of NO. (c) 2020 Elsevier Inc. All rights reserved.