Modulating the steric effect over high-index facet of MnOx catalysts to enhance toluene oxidation

Engineering surface structures of metal-oxide catalysts are of utmost significance for boosting their catalytic performances. In this work, we reported the high-index (3 1 0) facets catalysts (MnOx-AAUS) with oxygen vacancies for VOCs degradation, which was synthesized via an ultrasonic-assisted redox precipitation process. Interestingly, the excellent catalytic performance of MnOx-AAUS catalysts was due to the steric effect between high-index facet with reactants and the simultaneous adsorption-activation of toluene and gaseous oxygen on the high-index (3 1 0) facets with oxygen vacancies. The T90% value of the (3 1 0) facets catalysts (600 ppm toluene, GHSV = 60,000 mL/g·h, 21 % O2/N2) was significantly lower than that of the previous (0 0 1) facets catalysts. Density functional theory (DFT) calculations, along with in-situ FT-IR spectra, revealed that the tilted adsorption configuration of toluene was conducive to simultaneous reaction with the surrounding activated oxygen species. Such the adsorption configuration of toluene/oxygen contributed to the substantially enhanced catalytic activity of the MnOx-AAUS catalyst for VOCs oxidation. This work provides new insights into the roles of high-index facets with oxygen vacancies of MnOx catalysts in the toluene oxidation and paves new avenues for the rational design of highly efficient catalysts for oxidation reactions. © 2024 Elsevier B.V.