Exploring the rate-control step of toluene oxidation over the novel octahedral Pt/Mn3O4 catalyst with stable low-temperature catalytic performance via in situ DRIFTS

The high efficiency and stability of catalysts are crucial for their practical application in toluene oxidation. Herein, a novel octahedral Pt/Mn3O4-110 catalyst with excellent structural stability was synthesized and 100% toluene conversion can be achieved at low-temperature 160 ºC. XRD and Raman results indicated that the structure of Pt/Mn3O4-110 can be well maintained after 120 h on-stream reaction, the resistance to H2O (3 or 5 vol.%) and high concentration toluene (3000 ppm)/CO2 (5 vol.%) tests. In situ DRIFTS comparative studies between Pt/Mn3O4-110 and Pt/Mn3O4-100 (30% toluene conversion at 160 ºC) samples demonstrated that the rate-control steps of toluene oxidation on Pt/Mn3O4-110 and Pt/Mn3O4-100 were both the further oxidation of benzoate species in the presence of gas-phase oxygen, while the transformation of benzaldehyde to benzoate species was the rate-control step on Pt/Mn3O4-100 in the absence of gas-phase oxygen. The weaker Mn-O bonds, richer oxygen vacancies and higher mobility of oxygen species on Pt/Mn3O4-110 sample than that of Pt/Mn3O4-100 are beneficial for the easier release of lattice oxygen from the surface of catalyst and then participated in toluene oxidation via Mars-van Krevelen mechanism, contributing to easier oxidation of benzaldehyde to benzoate species and formation of formic acid and bicarbonate species.