Composition–activity effects of Mn–Ce–O composites on phenol catalytic wet oxidation

Mn–Ce–O composite catalysts have been widely used in sub- and supercritical catalytic wet oxidation of toxic organics contained in aqueous streams. In order to investigate their composition–activity relationship, 11 samples with Ce/(Mn+Ce) atomic bulk ratios ranging from 0 to 100% were prepared by co-precipitation. Phenol was selected as a model pollutant and the catalytic oxidation was carried out in a batch slurry reactor using oxygen as the oxidizing agent under mild reaction conditions. The results showed that the catalytic activity was greatly influenced by the catalyst composition. The catalyst with Mn/Ce ratio=6/4 was found to be the most active in reducing both phenol concentration and total organic carbon (TOC). All catalysts were characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), temperature programmed reduction (TPR) and nitrogen adsorption techniques. Systematic shifts in binding energy, diffraction angle, and reduction temperature were observed in the XPS, XRD and TPR spectra, respectively. XPS and XRD data revealed the occurrence of significant interactions between Mn and Ce oxides, resulting in the evolution of textural, structural and oxidation state with composition. TPR analysis showed that the interaction between Mn and Ce greatly improved the oxygen storage capacity of manganese and cerium oxides as well as oxygen mobility on the surface of catalyst. Catalytic active sites have been ascribed to manganese oxide species exhibiting higher oxidation state. Furthermore, XPS revealed that the most active catalyst, i.e. Mn/Ce 6/4, exhibits an electron-rich surface which may be very important in the activation of adsorbed oxygen.