Balance of activation and ring-breaking for toluene oxidation over CuO-MnO_x bimetallic oxides

摘要

CuMn oxides have been studied for many years to catalytic degradation of toluene, but there are still many divergences on the essence of their great catalytic activity and reaction mechanism. A series of CuMn bimetallic oxides were synthesized for the catalytic oxidation of toluene in this study. Cu2Mn1 exhibited the highest toluene oxidation rate per specific surface area, which was approximately 4 times that of monometallic CuO and Mn3O4. Benzoic acid was the only intermediates which could be observed during toluene oxidation. Between monometallic CuO and Mn3O4, toluene was more difficult to be activated by Mn3O4 to generate benzoic acid (toluene activation), whereas benzoic acid was oxidized (ring-breaking) by CuO with more difficulty. As for CuMn, the superior reducibility combined with the balance between ring-breaking of benzoic acid and activation of toluene-to-benzoic acid determined the high toluene oxidation rate. DFT simulations exhibited that in O-Cu-O-Mn-O structure, the Mn-O site was a more effective activation site for toluene-to-benzoic acid oxidation, whereas Cu-O mainly performed as an adsorption site for toluene. This work identifies the different roles of Cu and Mn entities in toluene oxidation and provides the novel design strategy for toluene removal catalysts.