title: Catalytic and mechanistic insights of the low-temperature selective oxidation of methane over Cu-promoted Fe-ZSM-5.
abstract: The partial oxidation of methane to methanol presents one of the most challenging targets in catalysis. Although this is the focus of much research, until recently, approaches had proceeded at low catalytic rates (<10 h(-1)), not resulted in a closed catalytic cycle, or were unable to produce methanol with a reasonable selectivity. Recent research has demonstrated, however, that a system composed of an iron- and copper-containing zeolite is able to catalytically convert methane to methanol with turnover frequencies (TOFs) of over 14,000 h(-1) by using H(2)O(2) as terminal oxidant. However, the precise roles of the catalyst and the full mechanistic cycle remain unclear. We hereby report a systematic study of the kinetic parameters and mechanistic features of the process, and present a reaction network consisting of the activation of methane, the formation of an activated hydroperoxy species, and the by-production of hydroxyl radicals. The catalytic system in question results in a low-energy methane activation route, and allows selective C(1)-oxidation to proceed under intrinsically mild reaction conditions.
authors.affiliation: Cardiff Catalysis Institute, School of Chemistry, Cardiff University, UK. ceri.hammond@chem.ethz.ch
authors.forename: Ceri
authors.initials: C
authors.lastname: Hammond
authors.forename: Robert L
authors.initials: RL
authors.lastname: Jenkins
authors.forename: Nikolaos
authors.initials: N
authors.lastname: Dimitratos
authors.forename: Jose Antonio
authors.initials: JA
authors.lastname: Lopez-Sanchez
authors.forename: Mohd Hasbi
authors.initials: MH
authors.lastname: ab Rahim
authors.forename: Michael M
authors.initials: MM
authors.lastname: Forde
authors.forename: Adam
authors.initials: A
authors.lastname: Thetford
authors.forename: Damien M
authors.initials: DM
authors.lastname: Murphy
authors.forename: Henk
authors.initials: H
authors.lastname: Hagen
authors.forename: Eric E
authors.initials: EE
authors.lastname: Stangland
authors.forename: Jacob M
authors.initials: JM
authors.lastname: Moulijn
authors.forename: Stuart H
authors.initials: SH
authors.lastname: Taylor
authors.forename: David J
authors.initials: DJ
authors.lastname: Willock
authors.forename: Graham J
authors.initials: GJ
authors.lastname: Hutchings