Oxygen vacancy clusters essential for the catalytic activity of CeO2 nanocubes for o-xylene oxidation.

Catalytic oxidation of o-xylene was investigated on CeO2 nanocubes calcined at 350, 450, 550, and 650 °C, among which the samples calcined at 550 °C exhibited the highest activity and long durability. Positron annihilation spectroscopy measurements revealed that the size and distribution of oxygen vacancies for CeO2 nanocubes could be tuned by carefully controlling the calcination temperature. An excellent linear correlation between a factor related to size and density of oxygen vacancy clusters and reaction rate of o-xylene oxidation was revealed on ceria nanocubes. This means that oxygen vacancy clusters with suitable size and distribution are responsible for catalytic reaction via simultaneous adsorption and activation of oxygen and o-xylene. Electron spin resonance spectra revealed that over the CeO2 cubes, water vapor significantly promoted the formation of ∙OH radicals with a sharp decrease in the signals relating to oxygen vacancies, accelerating the transformation of o-xylene to the intermediate benzoate species, resulting in an enhancement of catalytic activity. Water thus serves as a "smart" molecule; its introduction into the feed mixture further confirmed the key role of oxygen vacancies in the catalytic performance of CeO2 nanocubes. A possible mechanism of oxygen vacancy formation during the calcination process was also proposed.