DFT and SISSO studies on the CO2 cycloaddition reaction to ethylene oxide catalyzed by intraframework M(ii)-BEA zeolites†
Abstract
CO2 cycloaddition with EO over M(II)-intraframework BEA zeolites, with and without TMAI as a co-catalyst, is investigated using the M06-L functional. Without a co-catalyst, the catalytic process occurs through a concerted mechanism. The activation energy is calculated to be 39.9, 38.9, 38.6, and 39.6 kcal mol−1 for M-DeAlBEA zeolites (M = Ni, Cu, Zn, and Mg), respectively. In the presence of the co-catalyst, the catalytic process proceeds through three consecutive steps: ring opening, CO2 activation, and ring closure, with the latter being the rate-determining step (RDS) of the reaction. The incorporation of TMAI plays a crucial role in activating EO and CO2, leading to a more kinetically favorable formation of ethylene carbonate compared to the concerted pathway. From the energy span model, the activation energies of the RDS for the stepwise CO2 cycloaddition are 16.8, 24.7, 14.7, and 14.1 kcal mol−1, respectively. The SISSO algorithm has been employed to develop a mathematical expression for predicting the highest activation energy required for EC production via two pathways. The highest activation energy for CO2 cycloaddition can be approximated using the molecular orbital (MO) energies of the zeolite and co-catalyst, along with the EO and CO2 adsorption free energies. The SISSO-derived activation energies closely match the DFT-calculated values, achieving an R2 value of 0.998 and an RMSE of 1.52 kcal mol−1.