Highly Active Mn3–xFexO4 Spinel with Defects for Toluene Mineralization: Insights into Regulation of the Oxygen Vacancy and Active Metals

A series of highly defected Mn3–xFexO4 spinels with different amounts of oxygen vacancies and active metals were successfully synthesized by regulating the insertion of Fe ions into the crystal structure of Mn3O4 via self-polymerizable monomer adjustment of the molten Mn–Fe salt dispersion. The characterization of X-ray diffraction, Raman, scanning electron microscopy, X-ray photoelectron spectroscopy, and N2 adsorption–desorption showed that the doping of Fe increased the lattice defects, oxygen vacancy concentration, specific surface area, mesoporosity, and catalytic properties compared to Cu ions doping. Temperature-programmed reduction with hydrogen and oxygen pulse chemisorption tests determined that the doping level of Fe ions had an important influence on the oxygen vacancy content and the dispersion of active metals on the catalysts’ surfaces. For the best Mn-dispersed and most active Mn2.4Fe0.6O4 catalyst, a long-term toluene oxidation measurement running for 120 h of uninterrupted reaction, at the low temperature of 240 °C, high humidity (relative humidity = 100%), and high weight hourly space velocity of 60000 mL·g–1·h–1, was also carried out, which indicated that the catalyst possessed high stability and endurability. Moreover, the continuous oxidation route and internal principle for toluene oxidation were also revealed by the in situ diffuse-reflectance infrared Fourier transform spectroscopy and gas chromatography–mass spectrometry techniques and deep dynamics study.