Splitting dioxygen over distant binuclear transition metal cationic sites in zeolites. Effect of the transition metal cation. Issue 10 (4th February 2021)

• Record Type: Journal Article
• Authors: Dedecek, Jiri; Tabor, Edyta; Andrikopoulos, Prokopis C.; Sklenak, Stepan
• Is Part Of: International journal of quantum chemistry. Volume 121:Issue 10(2021)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2021-02-04
• Subjects: alpha oxygen -- density functional calculations -- splitting dioxygen -- VASP -- zeolites; Quantum chemistry -- Periodicals; 541.28
• DOI: 10.1002/qua.26611
• Languages: English
• ISSNs: 0020-7608

Abstract

Abstract: Splitting dioxygen to yield highly active oxygen species attracts enormous attention due to its potential in direct oxidation reactions, mainly in transformation of methane into valuable products. Distant binuclear cationic Fe(II) centers in Fe‐ferrierite have recently been shown to be active in splitting dioxygen at room temperature to form very active oxygen species able to oxidize methane to methanol at room temperature as well. Computational models of the distant binuclear transition metal cationic sites (Co(II), Mn(II), and Fe(II)) stabilized in the ferrierite matrix were investigated by periodic density‐functional theory calculations including molecular dynamics simulations. The results reveal that the M(II) cations capable of the M(II) → M(IV) redox cycle with the M…M distance of ca 7.4 Å stabilized in two adjacent β sites of ferrierite can split dioxygen. Our study opens the possibility of developing tunable zeolite‐based systems for the activation of dioxygen employed for direct oxidations. Abstract : Formation of oxygen atoms able to directly oxidize methane to methanol at room temperature: The activity in splitting dioxygen represents a general property of the distant binuclear cationic centers of transition metals capable of the M(II) → M(IV) redox cycle stabilized in the aluminosilicate matrix of the ferrierite zeolite.