In the present study CeO2, MnO2 and CeMnOx mixed oxide (with molar ratio Ce/Mn = 1) were prepared by sol-gel method using citric acid as a chelating agent and calcined at 500 °C. The silver catalysts (1 wt.% Ag) over the obtained supports were synthesized by the incipient wetness impregnation method with [Ag(NH3)2]NO3 aqueous solution. The selective catalytic reduction of NO by C3H6 was investigated in a fixed-bed quartz reactor using a reaction mixture composed of 1000 ppm NO, 3600 ppm C3H6, 10 vol.% O2, 2.9 vol.% H2 and He as a balance gas, at WHSV of 25,000 mL g−1 h−1.The physical-chemical properties of the as-prepared catalysts were studied by several characterization techniques, such as X-ray fluorescence analysis, nitrogen adsorption/desorption, X-ray analysis, Raman spectroscopy, transmission electron microscopy with analysis of the surface composition by X-ray energy dispersive spectroscopy and X-ray photo-electron spectroscopy. Silver oxidation state and its distribution on the catalysts surface as well as the support microstructure are the main factors determining the low temperature activity in NO selective catalytic reduction. The most active Ag/CeMnOx catalyst (NO conversion at 300 °C is 44% and N2 selectivity is ~90%) is characterized by the presence of the fluorite-type phase with high dispersion and distortion. The characteristic “patchwork” domain microstructure of the mixed oxide along with the presence of dispersed Ag+/Agnδ+ species improve the low-temperature catalyst of NO reduction by C3H6 performance compared to Ag/CeO2 and Ag/MnOx systems.
FePО4/SiO2supported catalysts with a different content of iron phosphate are prepared. The properties of the catalyst are changed by the introduction of alkali metal compounds (Na or Cs) on its...
Currently, catalytic processing of biorenewable raw materials into valuable products attracts more and more attention. In the present work, silica-supported FePO4 and Fe-Mo-O catalysts are prepared, their phase composition, and catalytic properties are studied in the process of selective oxidation of propylene glycol into valuable mono- and bicarbonyl compounds, namely, hydroxyacetone and methylglyoxal. A comparative analysis of the main routes of propylene glycol adsorption with its subsequent oxidative conversion into carbonyl products is carried out. The DFT calculations show that in the presence of adsorbed oxygen atom, the introduction of the phosphate moiety to the Fe-containing site strengthens the alcohol adsorption on the catalyst surface with the formation of the 1,2-propanedioxy (–OCH(CH3)CH2O–) intermediate at the active site. The introduction of the molybdenum moiety to the Fe-containing site in the presence of the adsorbed oxygen atom is also energetically favorable, however, the interaction energy is found by 100 kJ/mol higher compared to the case with phosphate moiety that leads to an increase in the propylene glycol conversion while maintaining high selectivity towards C3 products. The catalytic properties of the synthesized iron-containing catalysts are experimentally compared with those of Ag/SiO2 sample. The synthesized FePO4/SiO2 and Fe-Mo-O/SiO2 catalysts are not inferior to the silver-containing catalyst and provide ~70% selectivity towards C3 products, while the main part of propylene glycol is converted into methylglyoxal in contrast to the Ag/SiO2 catalyst featuring the selective transformation of only the secondary C-OH group in the substrate molecule under the studied conditions with the formation of hydroxyacetone. Thus, supported Fe-Mo-O/SiO2 catalysts are promising for the selective oxidation of polyatomic alcohols under low-temperature conditions.