Understanding the effect of the divalent cations (Ni, Cu, and Zn) exchanged FAU zeolite on the kinetic of CO cycloaddition with ethylene oxide: A DFT study.

Epoxide ring opening and cycloaddition with CO is one of the promising routes to convert CO to more valuable industrial chemicals. In this work, density functional theory calculations with the M06-L/6-31G(d,p) level of theory have been employed to study the cycloaddition of ethylene oxide (EO) with CO over M(II)-faujasite zeolite (M = Ni, Cu, and Zn) in the absence of a co-catalyst. The influence of the exchanged metals strongly dominates the adsorption of EO. The binding energies of EO on the active site are -39.9 (Ni-FAU), -24.2 (Cu-FAU), and -35.0 (Zn-FAU) kcal/mol, respectively. The reaction mechanism is proposed to occur via the concerted mechanism, in which the metals initiate the EO ring opening and the formation of two new C-O bonds between the adsorbed EO and CO proceed in a single step. The activation energy of the reaction catalyzed by Cu-FAU is 24.2 kcal/mol whereas that of Ni and Zn-FAU is found to be 31.1 and 31.4 kcal/mol, respectively. Moderate adsorption of EO and a larger electron transfer at the transition state are the important keys that reduce the activation energy for the Cu-FAU lower than in the other systems.