4.2 Article

Investigation of the ozone-induced oxidation of soot over LaMnO3 catalyst using O3/O2 temperature-programmed desorption experiments

Journal

REACTION KINETICS MECHANISMS AND CATALYSIS
Volume 133, Issue 1, Pages 259-276

Publisher

SPRINGER
DOI: 10.1007/s11144-021-01977-y

Keywords

Ozone; Soot oxidation; LaMnO3; Citric acid sol-gel method; Temperature-programmed desorption

Funding

  1. Basic Science Research Program through the National Research Foundation of Korea (NRF) - Ministry of Science ICT (MSIT) [NRF-2016R1A5A1009592]

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This study investigated the catalytic redox cycle occurring on the surface of a lanthanum manganese oxide catalyst, with superoxide ions combined with Mn4+ ions playing a key role in promoting ozone-induced soot oxidation. The redox cycle involved the migration of superoxide ions over surface Mn4+ sites and the Mn4+-to-Mn3+ transition to complete the cycle of oxidation. Evidence suggested that the redox cycle exclusively occurred on the catalyst's surface.
In this study, we investigated how the catalytic redox cycle occurs over a lanthanum manganese oxide (LaMnO3) catalyst when applied to the ozone-induced oxidation of soot. This was accomplished by tracking the catalysis using O-3/O-2 temperature-programmed desorption coupled with X-ray photoelectron spectroscopy (XPS). We prepared the catalyst by the citric acid sol-gel method to obtain a catalyst with a uniform perovskite phase and improved specific surface area. The catalyst was remarkably active in promoting ozone-induced soot oxidation within the temperature range of 25-125 degrees C. The active oxygen species were superoxide ions combined with Mn4+ ions on the catalyst surface. It was presumed the superoxide ion migrates over the surface Mn4+ sites and either desorbs as molecular oxygen or oxidizes the soot particles if it reaches the interface between soot and catalyst particles. The redox cycle was completed by the Mn4+-to-Mn3+ transition, which accompanied the detachment of superoxide ions. No evidence was found to support the involvement of the bulk phase of the catalyst with the redox cycle. The ozone-induced redox cycle was presumed to exclusively occur on the surface of the catalyst.

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