Dominant anatase TiO2 (0 0 1) with rich surface hydroxyls as catalytic active sites for selective catalytic oxidation of cyclohexylamine to cyclohexanone oxime

•Anatase TiO2 (001) catalyst exhibits excellent catalytic activity and stability.•TiO2 (001) afforded the rich surface hydroxyls as catalytic active sites.•The energy barriers for the N-H oxidation on (001) are lower than those of (101).•The energy barriers for the N-H cleavage are lower than those of C-H on TiO2 (001).•This work offers an insight into the design of active sites for amines oxidation.