摘要
A metal-free catalytic system combining oxidized carbon nanotubes (oCNTs) and ionic liquids (ILs) is presented for the oxidation of aromatic thiophene compounds with H2O2 as an oxidant. The oCNTs exhibit impressively high activity and stability in the system, which show an even better performance than those of some reported metal catalysts. The ILs are proved to have indispensable influence on the enhanced catalytic performance of the oCNTs. Detailed characterization by TG-MS and XPS demonstrates that the carbonyl groups are the active sites for the oxidation process, which is further supported by the deactivation and the model catalysts experiments. The quantitative analysis of different oxygen groups in oCNTs could be achieved by an isothermal temperature programmed TG-MS method. The concentration of carbonyl groups is 1.46 mmol per 1 g oCNTs and the tuiriover frequency of oCNTs could also be obtained (10.7 h^-1 in the presence of OmimPF6). H2O2 decomposition experiments combined with the EPR results reveal that the presence of OmimPF6 can avoid the intermediate HO· to form O2 and then improve the catalytic performance of oCNTs for the oxidation of dibenzothiophene.
A metal-free catalytic system combining oxidized carbon nanotubes（oCNTs） and ionic liquids（ILs） is presented for the oxidation of aromatic thiophene compounds with H2O2 as an oxidant. The oCNTs exhibit impressively high activity and stability in the system, which show an even better performance than those of some reported metal catalysts. The ILs are proved to have indispensable influence on the enhanced catalytic performance of the oCNTs. Detailed characterization by TG-MS and XPS demonstrates that the carbonyl groups are the active sites for the oxidation process, which is further supported by the deactivation and the model catalysts experiments. The quantitative analysis of different oxygen groups in oCNTs could be achieved by an isothermal temperature programmed TG-MS method. The concentration of carbonyl groups is 1.46 mmol per 1 g oCNTs and the turnover frequency of oCNTs could also be obtained（10.7 h-1 in the presence of OmimPF6）. H2O2 decomposition experiments combined with the EPR results reveal that the presence of OmimPF6 can avoid the intermediate HO· to form O2 and then improve the catalytic performance of oCNTs for the oxidation of dibenzothiophene.
基金
provided by the National Natural Science Foundation of China(No.21503241,21133010,21261160487,51221264,21411130120,21473223,91545119,91545110)
the“Strategic Priority Research Program” of the Chinese Academy of Sciences(CAS)(No.XDA09030103)
CAS/State Administration for Foreign Experts Affairs(SAFEA)International Partnership Program for Creative Research Teams and the Doctoral Starting up Foundation of Liaoning Province,China(No.20121068)
the financial support from Max Planck Society and China Scholarship Council
