Crystal Plane Effect of Co3O4 on Styrene Catalytic Oxidation: Insights into the Role of Co3+ and Oxygen Mobility at Diverse Temperatures

In the oxidation reaction of volatile organic compounds catalyzed by metal oxides, distinguishing the role of active metal sites and oxygen mobility at specific preferentially exposed crystal planes and diverse temperatures is challenging. Herein, Co₃O₄ catalysts with four different preferentially exposed crystal planes [(220), (222), (311), and (422)] and oxygen vacancy formation energies were synthesized and evaluated in styrene complete oxidation. It is demonstrated that the Co₃O₄ sheet (Co₃O₄-I) presents the highest C₈H₈ catalytic oxidation activity (R_{250 °C} = 8.26 μmol g^-1 s^-1 and WHSV = 120,000 mL h^-1 g^-1). Density functional theory studies reveal that it is difficult for the (311) and (222) crystal planes to form oxygen vacancies, but the (222) crystal plane is the most favorable for C₈H₈ adsorption regardless of the presence of oxygen vacancies. The combined analysis of temperature-programmed desorption and temperature-programmed surface reaction of C₈H₈ proves that Co₃O₄-I possesses the best C₈H₈ oxidation ability. It is proposed that specific surface area is vital at low temperature (below 250 °C) because it is related to the amount of surface-adsorbed oxygen species and low-temperature reducibility, while the ratio of surface Co³⁺/Co²⁺ plays a decisive role at higher temperature because of facile lattice oxygen mobility. In situ diffuse reflectance infrared Fourier spectroscopy and the ¹⁸O₂ isotope experiment demonstrate that C₈H₈ oxidation over Co₃O₄-I, Co₃O₄-S, Co₃O₄-C, and Co₃O₄-F is mainly dominated by the Mars-van Krevelen mechanism. Furthermore, Co₃O₄-I shows superior thermal stability (57 h) and water resistance (1, 3, and 5 vol % H₂O), which has the potential to be conducted in the actual industrial application.