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Achieving high catalytic performance with lower possible cost and higher energetic efficiency is critical for catalytic oxidation of volatile organic compounds (VOCs). However, traditional thermocatalysts generally undergo low catalytic activity and fewer active sites. Herein, this paper synthesizes nearly all-surface-atomic, ultrathin two-dimensional (2D) Co3O4 nanosheets to address these problems through offering a numerous active sites and high electron mobility. The 2D Co3O4 nanosheets (1.70 nm) exhibit catalyzation to the total oxidation of n-hexanal at the lower temperature of T90% = 202 °C, and at the space velocity of 5.0 × 104 h−1. It is over 1.2 and 6 times higher catalytic activity than that of 2D CoO nanosheets (1.71 nm) and bulk Co3O4 counterpart, respectively. Transient absorption spectroscopy analysis shows that the oxygen vacancy defect traps electrons, thereby preventing the recombination with holes, increasing the lifetime of τ1 electrons, and making electron–holes reach a non-dynamic equilibrium. The longer the electron lifetime is, the easier the oxygen vacancy defects capture electrons. Furthermore, the defects combine with oxygen to form active oxygen components. Compared with the lattice oxygen involved in the reaction of bulk Co3O4, the nanosheets change the catalytic reaction path, which effectively reduces the activation energy barrier from 34.07 to 27.15 kJ/mol. The changed surface disorder, the numerous coordinatively-unsaturated Co atoms and the high ratio of Oads/Olat on the surface of 2D Co3O4 nanosheets are responsible for the catalytic performance.
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