O-atom transport catalysis by neutral manganese oxide clusters in the gas phase: reactions with CO, C2H4, NO2, and O2.

Reactions of CO, C2H4, NO2, and O2 with neutral MnmOn clusters in a fast flow reactor are investigated both experimentally and theoretically. Single photon ionization at 118 nm is used to detect neutral cluster distributions through time of flight mass spectrometry. MnmOn clusters are generated through laser ablation of a manganese target in the presence of 5% O2/He carrier gas. A strong size dependent reactivity of MnmOn clusters is characterized. Reactions Mn2O5/Mn3O7 + CO → Mn2O4/Mn3O6 + CO2 are found for CO oxidation by MnmOn clusters, while only association products Mn2O3-5C2H4 and Mn3O5-7C2H4 are observed for reactions of C2H4 with small MnmOn clusters. Reactions of MnmOn clusters with NO2 and O2 are also investigated, and the small Mn2On clusters are easily oxidized by NO2. This activation suggests that a catalytic cycle can be generated for the Mn2O5 cluster: Mn2O5 + CO + NO2 → Mn2O4 + CO2 + NO2 → Mn2O5 + CO2 + NO. Density functional theory (DFT) calculations are performed to explore the potential...