Insight into the effect of manganese substitution on mesoporous hollow spinel cobalt oxides for catalytic oxidation of toluene.

The cobalt oxides and manganese oxides have high-activity potential for catalytic oxidation of volatile organic compounds (VOCs), while the mesoporous hollow morphology is crucial to the mass transfer of reactant and product. Therefore, it is worth investigating the effect of manganese substitution in mesoporous hollow cobalt oxides on catalytic oxidation. Herein, a partially disordered spinel structure is formed by the Mn substitution in CoO and the mesoporous hollow microsphere is improved in morphology homogeneity with the decrease of Co/Mn ratio in the range of 1.8-28.8. The 5Co1Mn (Mn-substituted CoO with Co/Mn at 5.4) exhibits outstanding catalytic activity for toluene oxidation with 50% CO generation at 237 °C, which is 21 °C lower than CoO. Moreover, the 5Co1Mn displays satisfactory stability in reusability, lifetime, and water resistance. The small defective crystallite, mesoporous hollow morphology, and high specific surface area endow Mn-substituted CoO with more surface chemical adsorbed oxygen, enhancing the catalytic oxidation of toluene. Theoretical calculation on (311) plane of CoO reveals that Mn or Mn substitution increases the formation energy of oxygen vacancy and makes it difficult to adsorb gaseous oxygen on the defective surface. The interaction between Co and Mn impedes the improvement of toluene oxidation because the mobility of lattice oxygen, the surface distribution of Co, and the ratio of surface adsorbed oxygen to surface lattice oxygen are hindered by Mn substitution. The chemical adsorbed oxygen is more active than lattice oxygen in the oxidation of adsorbed intermediates (phenolate, benzoate species, etc.). The Langmuir-Hinshelwood mechanism dominates in the catalytic oxidation at 200-250 °C, while the catalytic oxidation follows both the Langmuir-Hinshelwood mechanism and Mars-van Krevelen mechanism above 250 °C. This work provides some enlightenment for exploring the role of surface oxygen species in VOCs oxidation and uncovering the interaction in binary spinel oxides.