Stability of the Reaction Intermediates of Ethylbenzene Disproportionation over Medium-Pore Zeolites with Different Framework Topologies: A Theoretical Investigation

The strain energies of the main reaction intermediates (i.e., monoethylated diphenylethane (mEDPE) and diethylated diphenylethane (dEDPE) derivatives), which can be formed during ethylbenzene (EB) disproportionation over six 10-ring zeolites with different framework topologies, as well as over the large-pore zeolite Y, were determined by the density functional theory calculations in order to more precisely investigate the effects of the pore structure of medium-pore zeolites on their formations. It was found that while the strain energies of mEDPE and dEDPE intermediates in zeolite Y, MCM-22 and TNU-9, were always lower than 19.6 kJ mol–1, some of them were characterized by considerably higher energies (>32.8 kJ mol–1) when positioned in the intersection channels of ZSM-5 and ZSM-57. As expected, in addition, all the mEDPE and dEDPE derivatives embedded in TNU-10 and ZSM-22 with narrower 10-ring channels were strongly distorted, giving them much higher strain energies (>37.7 kJ mol–1), which were in excellent agreements with our recently reported experimental results (J. Phys. Chem. C 2010, 115, 16124). This led us to conclude that the size and shape of void spaces in the medium-pore zeolites play a crucial role in governing the type of mEDPE and dEDPE formations during the EB disproportionation. Our work also shows that the strain energies of various reaction intermediates confined within zeolites with different pore topologies could be regarded as a useful quantitative means in better understanding the shape-selective nature of this important class of microporous crystalline catalysts.