Ga⁺-Chabazite Zeolite: A Highly Selective Catalyst for Nonoxidative Propane Dehydrogenation

Abstract

Ga-chabazite zeolites (Ga-CHA) have been found to efficiently catalyze propane dehydrogenation with high propylene selectivity (96%). In situ Fourier transform infrared spectroscopy and pulse titrations are employed to determine that upon reduction, surface Ga₂O₃ is reduced and diffuses into the zeolite pores, displacing the Brønsted acid sites and forming extra-framework Ga⁺ sites. This isolated Ga⁺ site reacts reversibly with H₂ to form GaH_<i>x</i> (2034 cm^-1) with an enthalpy of formation of ∼-51.2 kJ·mol^-1, a result supported by density functional theory calculations. The initial C₃H₈ dehydrogenation rates decrease rapidly (40%) during the first 100 min and then decline slowly afterward, while the C₃H₆ selectivity is stable at ∼96%. The reduction in the reaction rate is correlated with the formation of polycyclic aromatics inside the zeolite (using UV-vis spectroscopy) indicating that the accumulation of polycyclic aromatics is the main cause of the deactivation. The carbon species formed can be easily oxidized at 600 °C with complete recovery of the PDH catalytic properties. The correlations between GaH_<i>x</i> vs Ga/Al ratio and PDH rates vs Ga/Al ratio show that extra-framework Ga⁺ is the active center catalyzing propane dehydrogenation. The higher reaction rate on Ga⁺ than In⁺ in CHA zeolites, by a factor of 43, is the result of differences in the stabilization of the transition state due to the higher stability of Ga³⁺ vs In³⁺. The uniformity of the Ga⁺ sites in this material makes it an excellent model for the molecular understanding of metal cation-exchanged hydrocarbon interactions in zeolites.