Preparation of amorphous copper - chromium oxides catalysts for selective oxidation of cyclohexane
Sun, L (Sun, Lei)[ 1 ] ; Liu, JH (Liu, Junhua)[ 1 ]*（刘俊华） ; Luo, W (Luo, Wei)[ 1 ] ; Yang, Y (Yang, Yue)[ 1 ] ; Wang, F (Wang, Fang)[ 2 ] ; Weerakkody, C (Weerakkody, Chandima)[ 3 ] ; Suib, SL (Suib, Steven L.)[ 3 ]
[ 1 ] Nanjing Normal Univ, Coll Chem & Mat Sci, Nanjing 210023, Jiangsu, Peoples R China
[ 2 ] Nanjing Tech Univ, Coll Chem & Mol Engn, Nanjing 211816, Jiangsu, Peoples R China
[ 3 ] Univ Connecticut, Dept Chem, Storrs, CT 06269 USA
MOLECULAR CATALYSIS, 201812,460,16-26
In this work, amorphous copper-chromium catalysts with different Cu/Cr molar ratios have been prepared by a sol-gel method and were used in the oxidation of cyclohexane to KA-oil. The catalysts have been characterized by a variety of analytical techniques including XRD, XPS, Raman, FT-IR, BET, TEM and SEM. XRD results confirmed that the formation of amorphous structure. The XPS and Raman results indicated that most of Cu species existed in well-dispersed tetrahedral coordination before calcination. After calcination, the tetrahedrally coordinated Cu ions are transformed into octahedral coordination and the activity of catalyst is significantly reduced. The results show that the tetrahedrally coordinated Cu ions play the synergistic catalytic role with Cr ions. Interestingly, oxidation of cyclohexane is more inclined to produce cyclohexanol with uncalcined catalyst due to the presence of the tetrahedrally coordinated Cu ions; however, the appearance of surface lattice oxygen makes the reaction more conducive to cyclohexanone after calcination. After optimizing conditions, Cu-Cr oxide catalyst with the molar ratio 1:1 shows the highest activity, which obtains 62.2% yield and 92.4% selectivity for KA-oil using H2O2 as oxygen source.