A Density Functional Theory Study of Direct Oxidation of Benzene to Phenol by N₂O on a [FeO]¹⁺-ZSM-5 Cluster

Abstract

Density functional theory calculations were carried out in a study of the oxidation of benzene to phenol by N 2 O on a model (FeO) 1+ -ZSM-5 cluster: the [(SiH 3 ) 4 AlO 4( FeO)] cluster. This cluster models the reactivity of Fe 3+ oxidic clusters. Results are to be compared with an earlier study (J. Phys. Chem. C 2009, 113, 15307) on a model Fe 2+ -ZSM-5 cluster. The true activation energies for the elementary reaction step in which phenol is produced appear to be comparable. The major difference between the two systems appears to be the relative stabilities of the intermediate phenolates. On the Fe 3+ -containing cationic cluster, this appears to be uniquely stable. This result suggests that the experimentally observed preference of Fe 2+ sites over (FeO) 1+ on ZSM-5 for benzene oxidation to phenol by N 2 O is due to the reduced formation of adsorbed phenolate, which is possibly an intermediate for deactivation.

Epoxidation of Ethylene by Silver Oxide (Ag2O) Cluster: A Density Functional Theory Study

“…These geometries were obtained along a reaction coordinate. According to our very recent theoretical experience [36][37][38] transition states geometries were very close to the peak points of the profile.…”

Epoxidation of Propylene on a [Ag14O9] Cluster Representing Ag2O (001) Surface: A Density Functional Theory Study

“…These approximate transition state (ATS) geometries were obtained along a reaction coordinate. According to our very recent theoretical experience [32][33][34][35][36][37], transition states geometries were very close to the peak points of the profiles. Moreover, the activation barriers based on ATS calculated for ethylene epoxidation by using the Ag 14 O 9 (001) cluster [17] were in good agreement with the values computed on periodic silver oxide (001) slab surface [18].…”

Catalytic properties of extraframework iron-containing species in ZSM-5 for N2O decomposition

“…It is known that high-spin states are preferred for Fe [22,26,53,68]. Previous theoretical investigations on antiferromagnetic binuclear iron complexes in Fe/ZSM-5 have proposed that including the spin-state transition has only a minor effect on the reaction mechanism of the N 2 O decomposition [22,26,54].…”