Quantitative Evidence to Challenge the Traditional Model in Heterogeneous Catalysis: Kinetic Modeling for Ethane...

The production of ethylene from ethane dehydrogenation (EDH) is of great importance in the chemical industry, where zeolites are reported to be promising catalysts and kinetic simulations using the energetics from quantum mechanical calculations might provide an effective approach to speed up the development. However, the kinetic simulations with rigorous considerations of the zeolite environment are not yet advanced. In this work, EDH over Fe/SAPO-34 is investigated using quantum mechanical calculations with kinetic simulations. We show that an excellent agreement between the reaction rates from the self-consistent kinetic simulations using the coverage-dependent kinetic model developed in this work and the experimental ones can be achieved. We demonstrate that the adsorbate-adsorbate interactions are of paramount importance to the accuracy of kinetic calculations for zeolite catalysts. Our self-consistent kinetic calculations illustrate that the CH₃CH₂• radical rather than CH₃CH₂* is a favored intermediate. Perhaps more importantly, we reveal that the traditional model to describe catalytic reactions in heterogeneous catalysis cannot be used for the kinetics of the system and it may not be appropriate for many real catalytic systems. This work not only builds a framework for accurate kinetic simulations in zeolites, but also emphasizes an important concept beyond the traditional model.