A series of Mn–Ce(M) solids (M = K or Na), with molar ratios 100–0, 50–50 and 0–100 were prepared by co-precipitation of manganese and cerium nitrate from NaOH or KOH solutions at pH = 11. In addition, part of the solids precipitated with NaOH were dried and impregnated with a Cu2+ salt. The solids were characterized by XRD, Specific Surface Area, XPS and EDS. The characterization analyses show the formation of Mn mixed oxides with different oxidation states (Mn3+, Mn4+), for samples without Ce or Mn–Ce(M) 50–50. In the latter solid and in the one where there is no Mn, the formation of CeO2 (fluorite type) was detected. The samples were tested in the phenol removal in water at 100 °C and at atmospheric pressure with the aim to analyze the adsorbed species in the first stage of the adsorption-oxidation mechanisms. The results indicate, on the one hand, that [MnOx] is the active species in the process and that the most active solids are those that present (i) a higher concentration of OI, (ii) a higher amount of Mn4+ ions. DRIFT spectroscopy showed a possible mechanism of phenol adsorption on two sites, in the first one by H interaction of OH (phenol) with an OH of the catalyst and in the second, by the formation of a phenolate species between an O (OH phenol) and Mnn+.
In this research, we report the preparation of doped PMo Keggin heteropolyacids where Mo is partially replaced by V, Bi, and Bi–V. These catalysts were characterized by means of ICP-AES analysis, 31P-NMR, UV–visible spectra, FT-IR spectra, thermal analysis, and textural properties. In addition, the activities of the synthesized catalysts were evaluated in the selective oxidation of sulfides to sulfoxides/sulfones. The incorporation of V, Bi and Bi–V into the structure of H3PMo12O40 increases the catalytic activity. The two most active catalysts, those with V and V–Bi were supported on aminopropyl-functionalized silica (SiO2NH2) and they were found to be and efficient heterogeneous catalysts for the selective oxidation of diphenylsulfide to the corresponding sulfoxide/sulfone.