Catalytic activity of porous manganese oxides for benzene oxidation improved via citric acid solution combustion synthesis

Various manganese oxides (MnO_x) prepared via citric acid solution combustion synthesis were applied for catalytic oxidation of benzene. The results showed the ratios of citric acid/manganese nitrate in synthesizing process positively affected the physicochemical properties of MnO_x, e.g., BET (Brunauer-Emmett-Teller) surface area, porous structure, reducibility and so on, which were in close relationship with their catalytic performance. Of all the catalysts, the sample prepared at a citric acid/manganese nitrate ratio of 2:1 (C2M1) displayed the best catalytic activity with T₉₀ (the temperature when 90% of benzene was catalytically oxidized) of 212℃. Further investigation showed that C2M1 was Mn₂O₃ with abundant nano-pores, the largest surface area and the proper ratio of surface Mn⁴⁺/Mn³⁺, resulting in preferable low-temperature reducibility and abundant surface active adsorbed oxygen species. The analysis results of the in-situ Fourier transform infrared spectroscopy (in-situ FTIR) revealed that the benzene was successively oxidized to phenolate, o-benzoquinone, small molecules (such as maleates, acetates, and vinyl), and finally transformed to CO₂ and H₂O.