| Autor: |
Shan YD; Tianjin Key Laboratory of Chemical Process Safety and Equipment Technology, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, P.R. China., Wu SH; Tianjin Key Laboratory of Chemical Process Safety and Equipment Technology, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, P.R. China., Wang YL; Tianjin Key Laboratory of Chemical Process Safety and Equipment Technology, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, P.R. China., Wang C; Heibei Key Laboratory of Hazardous Chemicals Safety and Control Technology, School of Chemical and Environmental Engineering, North China Institute of Science and Technology, Langfang, Hebei 065201, China., Zhi SQ; Tianjin Key Laboratory of Chemical Process Safety and Equipment Technology, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, P.R. China., Liu Y; School of Chemistry and Chemical Engineering, Tianjin University of Technology, Tianjin 300384, P.R. China., Han X; Tianjin Key Laboratory of Chemical Process Safety and Equipment Technology, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, P.R. China. |
| Abstrakt: |
Selective oxidation of cyclohexane to cyclohexanol/cyclohexanone (KA-oil) is an important chemical process, which is still constrained by low conversion and selectivity and high energy consumption. In this study, Cu-doped mesoporous TiO 2 (Cu-MT) has been successfully synthesized via calcinating MIL-125(Ti) doped with copper acetylacetonate, which shows high reactivity in selective oxidation of cyclohexane to KA-oil by persulfate (PS) with the desirable cyclohexane conversion of 16.8% and a selectivity of 98.0% under mild conditions and the low ratio of PS/cyclohexane of 1:1. A series of characterizations and density functional theory calculations reveal that the doped Cu(I,II) on Cu-MT is the reactive site for non-radical activation of PS with the moderate elongation of the O-O bond in PS, which then abstracts 1H (1H + + 1 e - ) from cyclohexane to form Cy • and eventually KA-oil. This study gives new insight on the importance of moderately activated PS in selective oxidation of C-H. |
