The superior photocatalytic activity of TiO nanocrystals with exposed high-energy (001) facets, achieved through the use of hydrofluoric acid as a shape-directing reagent, is widely reported. However, in this study, we report for the first time the detrimental effect of surface fluorination on the photoreactivity of high-energy faceted TiO nanocrystals towards NO oxidation (resulting in a NO removal rate of only 5.9%). This study aims to overcome this limitation by exploring surface defluorination as an effective strategy to enhance the photocatalytic oxidation of NO on TiO nanocrystals enclosed with (001) facets. We found that surface defluorination, achieved through either NaOH washing (resulting in an improved NO removal rate of 23.2%) or calcination (yielding an enhanced NO removal rate of 52%), leads to a large increase in the photocatalytic oxidation of NO on TiO nanocrystals with enclosed (001) facets. Defluorination processes stimulate charge separation, effectively retarding recombination and significantly promoting the production of reactive oxygen species, including superoxide radicals (·O), singlet oxygen (O), and hydroxyl radicals (·OH). Both diffuse reflectance infrared Fourier-transform spectroscopy and density functional theory calculations confirm the higher adsorption of NO after defluorination, thus facilitating the oxidation of NO on TiO nanocrystals.
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