Amination of isobutene with NH was investigated over Brønsted acidic zeolites at 1 atm and 453-483 K. To compare catalytic activities over different zeolites, the measured reaction rates are normalized by the number of active sites determined by tert-butylamine temperature-programmed desorption (TPD). Small- A nd medium-pore zeolites with one-dimensional channels exhibit low activity because of pore blockage by adsorbed tert-butylammonium ions. However, turnover frequencies and activation energies are not sensitive to framework identity, as long as the active site is accessible to isobutene and tert-butylamine. Kinetic measurements and FTIR spectroscopy reveal that the Brønsted acid sites in MFI are covered predominantly with tert-butylammonium ions under reaction conditions. The desorption of tert-butylamine is assisted by the concurrent adsorption of isobutene. DFT simulations show that at very low tert-butylamine partial pressures, for example, at the inlet to the reactor, tert-butylamine desorption is rate-limiting. However, at sufficiently high tert-butylamine partial pressures (>0.03 kPa), protonation of isobutene to the corresponding carbenium ion limits the rate of amination.
