title: Non-lattice surface oxygen species implicated in the catalytic partial oxidation of decane to oxygenated aromatics.
abstract: The one-step transformation of C(7)-C(12) linear alkanes into more valuable oxygenates provides heterogeneous catalysis with a major challenge. In evaluating the potential of a classic mixed-metal-oxide catalyst, we demonstrate new insights into the reactivity of adsorbed oxygen species. During the aerobic gas-phase conversion of n-decane over iron molybdate, the product distribution correlates with the condition of the catalyst. Selectivity to oxygenated aromatics peaks at 350 °C while the catalyst is in a fully oxidized state, whereas decene and aromatic hydrocarbons dominate at higher temperatures. The high-temperature performance is consistent with an underlying redox mechanism in which lattice oxide ions abstract hydrogen from decane. At lower temperatures, the formation of oxygenated aromatics competes with the formation of CO(2), implying that electrophilic adsorbed oxygen is involved in both reactions. We suggest, therefore, that so-called non-selective oxygen is capable of insertion into carbon-rich surface intermediates to generate aromatic partial oxidation products.
authors.affiliation: Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Cardiff CF10 3AT, UK.
authors.forename: Sivaram
authors.initials: S
authors.lastname: Pradhan
authors.forename: Jonathan K
authors.initials: JK
authors.lastname: Bartley
authors.forename: Donald
authors.initials: D
authors.lastname: Bethell
authors.forename: Albert F
authors.initials: AF
authors.lastname: Carley
authors.forename: Marco
authors.initials: M
authors.lastname: Conte
authors.forename: Stan
authors.initials: S
authors.lastname: Golunski
authors.forename: Matthew P
authors.initials: MP
authors.lastname: House
authors.forename: Robert L
authors.initials: RL
authors.lastname: Jenkins
authors.forename: Rhys
authors.initials: R
authors.lastname: Lloyd
authors.forename: Graham J
authors.initials: GJ
authors.lastname: Hutchings
mesh_terms: D000473:Alkanes / Q000737:chemistry*; D002384:Catalysis; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D033362:Powder Diffraction
chemical_list: D000473:Alkanes; C012867:decane; D010100:Oxygen