Fe₂ O⁺ Cation Mediated Propane Oxidation by Dioxygen in the Gas Phase

The mass-selected Fe₂ O⁺ cation mediated propane oxidation by O₂ was investigated by mass spectrometry and density functional theory calculations. In the reaction of Fe₂ O⁺ with C₃ H₈ , H₂ was liberated by C-H bond activation to give Fe₂ OC₃ H₆⁺ . Interestingly, when a mixture of C₃ H₈ /O₂ was introduced into the reactor, an intense signal that corresponded to the Fe₂ O₂⁺ cation was present; the experiments indicated that O₂ was activated in its reaction with Fe₂ O(C₃ H₆ )⁺ to give Fe₂ O₂⁺ and C₃ H₆ O (acetone or propanal). A Langmuir-Hinshelwood-like mechanism was adopted in the propane oxidation reaction by O₂ on gas-phase Fe₂ O⁺ cations. In comparison with the absence of Fe₂ O₂⁺ in the reaction of Fe₂ O⁺ with O₂ , the ligand effect of C₃ H₆ on Fe₂ OC₃ H₆⁺ is important in the oxygen activation reaction. The theoretical results are consistent with the experimental observations. The propane oxidation by O₂ in the presence of Fe₂ O⁺ might be applied as a model for alkane and O₂ activations over iron oxide catalysts, and the mechanisms and kinetic data are useful for understanding corresponding heterogeneous reactions.