Propane Dehydrogenation Catalyzed by ZSM-5 Zeolites. A Mechanistic Study Based on the Selective Energy Transfer (SET) Theory

摘要

Experimentally determined activation energies of propane dehydrogenation catalyzed by ZSM-5 zeolites have been used to test the SET theory. The basis of this theory is that the catalyst system transfers vibrational energy via a resonance process to a specific vibration mode of the reacting molecule. Being excited up to a certain number of vibrational quanta the molecule is brought to reaction. By analyzing the above-mentioned activation energies we found the wave number of this “specific mode” to be 1065 cm−1. This is very close to the rocking vibration of propane (1053 cm−1). We suggest that the propane molecule reacts when excited so that the CH₃ group has been forced towards a flat structure with a carbon atom hybridization that is more sp2 than sp3. Consequently there is no way for three H-atoms to bind to the carbon and one of them must leave. This is the starting point of the reaction. The isokinetic temperature of the system was found as T_iso = 727 ± 4 K. From the SET formula for T_iso when both energy-donating (ω) and energy-accepting (ν) vibrations have the same frequency, viz., T_iso = Nhcν/2R, we obtain ν = ω = 1011 ± 6 cm−1. This agrees rather well with the CH₃ rocking mode (1053 cm−1) and also with asymmetric “TO₄” stretching vibrations of the zeolite structure (ω).