A theoretical study of confinement effect of zeolite on the ethylene dimerization reaction

Abstract

The influences of pore confinement and topology effect on ethylene dimerization over a series of zeolite, like HMOR, HZSM-5, HBEA and HMCM-22, have been systematically studied by density functional theory including dispersion interaction (DFT-D). Both of the stepwise and the concerted mechanisms are considered. Compared to the corresponding 8T models, the calculated activation energies are considerably reduced in the large models of zeolite due to the pore confinement effect. Moreover, the manners of ethylene dimerization are found to be related to the pore structure of zeolite catalyst. In stepwise mechanism, HMCM-22 shows better activity as suggested by the calculated activation energies. In concerted mechanism, the energy barriers in HBEA and HMCM-22 are much lower than that in HMOR and HZMS-5, indicting a better catalytic performance. By comparing the two mechanisms happened in one zeolite, we suggest that the concerted mechanism is preferable in HBEA, HMCM-22 and HMOR zeolite with large pores, while two mechanisms compete to each other in HZSM-5 with medium-size pores.