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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.

Developing visible-light-driven photocatalysts for the catalytic dehydrogenation of organics is of great significance for sustainable solar energy utilization. Here, we first report that aromatic alcohols could be efficiently split into H 2 and aldehydes over TiO 2 under visible-light irradiation through a ligand-to-metal charge transfer (LMCT) mechanism. A series of TiO 2 catalysts with different surface contents of the hydroxyl group (−OH) have been synthesized by controlling the hydrothermal and calcination synthesis methods. An optimal H 2 production rate of 18.6 μmol h −1 is obtained on TiO 2 synthesized from the hydrothermal method with a high content of surface −OH. Experimental characterizations and comparison studies reveal that the surface −OH markedly influences the formation of LMCT complexes and thus changes the visible-light-driven photocatalytic performance. This work is anticipated to inspire further research endeavors in the design and fabrication of visible-light-driven photocatalyst systems based on the LMCT mechanism to realize the simultaneous synthesis of clean fuel and fine chemicals.