Low-temperature selective oxidation of methane over distant binuclear cationic centers in zeolites

Abstract Highly active oxygen capable to selectively oxidize methane to methanol at low temperature can be prepared in transition-metal cation exchanged zeolites. Here we show that the α -oxygen stabilized by the negative charges of two framework aluminum atoms can be prepared by the dissociation of...

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Bibliographic Details
Published in:Communications chemistry 2019-06, Vol.2 (1), Article 71
Main Authors: Tabor, Edyta, Lemishka, Mariia, Sobalik, Zdenek, Mlekodaj, Kinga, Andrikopoulos, Prokopis C., Dedecek, Jiri, Sklenak, Stepan
Format: Article
Language:English
Subjects:
Aluminum
Cation exchanging
Cobalt
Formic acid
Iron
Low temperature
Metal ions
Methane
Methanol
Nitrous oxide
Oxidation
Oxygen atoms
Transition metals
Vapor phases
Water vapor
Zeolites
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Summary:Abstract Highly active oxygen capable to selectively oxidize methane to methanol at low temperature can be prepared in transition-metal cation exchanged zeolites. Here we show that the α -oxygen stabilized by the negative charges of two framework aluminum atoms can be prepared by the dissociation of nitrous oxide over distant binuclear cation structures (M(II)…M(II), M = cobalt, nickel, and iron) accommodated in two adjacent 6-rings forming cationic sites in the ferrierite zeolite. This α -oxygen species is analogous to that known only for iron exchanged zeolites. In contrast to divalent iron cations, only binuclear divalent cobalt cationic structures and not isolated divalent cobalt cations are active. Created methoxy moieties are easily protonated to yield methanol, formaldehyde, and formic acid which are desorbed to the gas phase without the aid of water vapor while previous studies showed that highly stable methoxy groups were formed on isolated iron cations in iron exchanged ZSM-5 zeolites.
ISSN:2399-3669
2399-3669
DOI:10.1038/s42004-019-0173-9