In order to enhance the catalytic activity and improve the stability of Mn-Al oxides in acetone oxidation, it is interesting to have found that modulating and accelerating the rate-limiting step by Al substitution rather than just mixing of Mn and Al is crucial for hydrocarbon efficient catalytic destruction. Here, a series of Mn-Al oxides with different Al substitution ratios were prepared by a scalable and facile hydrothermal-redox strategy. The reaction rate, selectivity, and stability of the representative α-MnO2 catalyst in acetone oxidation can be remarkably promoted by simple replacing of the partial framework Mn with Al, which changes the rate-limiting step from acetic acid dissociation to ethanol decomposition accelerated by H2O molecules. Among them, MnAl0.5 displays the best catalytic performance with 90% of acetone converted at just 165 °C and a remarkable CO2 yield. DFT results suggest that the py and px orbitals of the O element take part in the formation of the carbonyl group when the intermediate of removing H* from ethanol reacts with the hydroxyl group of H2O. The dxz orbital of Mn with p-electron of Al plays a vital role in the rate-limiting step. The work provides new insights into engineering catalysts for industrial VOC efficient and economical mineralization.
Keywords: DFT calculation; Mn−Al binary oxides; acetone oxidation; rate-limiting step; stability.