In Situ Fabrication of Highly Dispersed Co–Fe-Doped-δ-MnO2 Catalyst by a Facile Redox-Driving MOFs-Derived Method for Low-Temperature Oxidation of Toluene

Cost-efficient and durable manganese-based catalysts are in great demand for the catalytic elimination of volatile organic compounds (VOCs), which are dominated not only by the nanostructures but also by the oxygen vacancies and Mn-O bond in the catalysts. Herein, a series of nanostructured Co-Fe-doped-δ-MnO₂ catalysts (Co-Fe-δ-MnO₂) with high dispersion were in situ fabricated by employing metal-organic-frameworks (MOFs) as reducing agents, dopants, and templates all at the same time. The as-obtained Co-Fe-δ-MnO₂-20% catalyst exhibited robust durability and high catalytic activity (225 °C) for toluene combustion even in the presence of 5 vol % water vapor, which is 50 °C lower than that of pristine δ-MnO₂. Various characterizations revealed that the homogeneously dispersed codoping of Co and Fe ions into δ-MnO₂ promotes the generation of oxygen vacancies and weakens the strength of the Mn-O bond, thus increasing the amount of adsorbed oxygen (O_ads) and improving the mobility of lattice oxygen (O_latt). Meanwhile, due to successfully inheriting the framework structures of MOFs, the obtained catalyst exhibited a high surface area and three-dimensional mesoporous structure, which contributes to diffusion and increases the number of active sites. Moreover, in situ DRIFTS results confirmed that the toluene degradation mechanism on the Co-Fe-δ-MnO₂-20% follows the MVK mechanism and revealed that more O_ads and high-mobility O_latt induced by this novel method contribute to accumulating and mineralizing key intermediates (benzoate) and thus promote toluene oxidation. In conclusion, this work stimulates the opportunities to develop Co-Fe-δ-MnO₂ as a class of nonprecious-metal-based catalysts for controlling VOC emissions.