A Reaction Mechanism of Methane Coupling on a Silica-Supported Single-Site Tantalum Catalyst

Density functional theory calculations were utilized to study the reaction mechanisms of nonoxidative coupling of methane (NOCM) occurring on a silica-supported single-site tantalum (Ta) catalyst. Two catalytic cycles, namely, catalytic cycles A (CCA) and B (CCB), as well as other competing pathways, were investigated by exploring the potential energy surfaces for the reactions of interest. The supported methyltantalum [(≡SiO3)2Ta–CH3] and tantalum hydride [(≡SiO3)2Ta–H] catalyzed the reaction of NOCM through CCA and CCB, respectively. CCA and CCB comprise five and six elementary steps, respectively. The two rate-determining states for both catalytic cycles were elucidated. The turnover number of methane conversion catalyzed by the supported methyltantalum was about 105 larger than that catalyzed by the supported tantalum hydride. This large difference indicates that the former species is predominantly responsible for the conversion of methane to ethane