Species In Oxidation Processes Research Articles

Unraveling the impact of phosphate doping on surface properties and catalytic activity of gold supported on mixed iron-niobium oxide in gas phase methanol oxidation

In recent decades, there has been notable interest in understanding the influence of the support composition on the reactivity of gold species in oxidation processes. This study fits in with this scientific trend and investigates the effects of incorporating phosphate ions into Au catalysts supported on mixed iron-niobium oxides in methanol oxidation. All materials were thoroughly characterized using XRD, ICP-OES, DR-UV-Vis, N2 physisorption, HRTEM, HAADF-STEM, SEM-EDX, XPS, TPD-NH3, TPD-CO2, and in situ FTIR combined with adsorption of NO. Activity of the catalysts was evaluated using a fixed-bed flow reactor combined with gas chromatography and operando FTIR-MS system. It was observed that the phosphate-doped catalyst supported on mixed Fe-Nb oxide exhibited significantly higher activity than phosphate-free sample. This improvement resulted from increased electron mobility, enhanced acidity, and optimized distribution of gold nanoparticles on the former catalyst. Knowledge resulting from this work can lead to the development of more efficient gold catalysts.

Interpretation of role of methane in low-temperature oxidation processes of methane/n-heptane mixtures

• Nonlinear suppression of methane added on low-temperature oxidation of n -heptane. • Physical and chemical roles of methane in methane/ n -heptane oxidation process. • Channels for added methane influencing low-temperature oxidation of n -heptane. • Competition for radicals between methane and n -heptane during oxidation process. To understand the function of methane in low-temperature oxidation processes of methane/ n -heptane mixtures, mole fractions of various species in oxidation processes occurring in an atmospheric-pressure jet-stirred reactor were quantified at different methane contents over the temperature range of 500–750 K and equivalence ratios of 0.5, 1.0 and 2.0 with a residence time of 1.4 s. After examining the capability of the NUI model in reproducing the experimental data, physical and chemical roles of methane were separated from each other. Chemical kinetic characteristics behind the action of methane were revealed through analyses of reaction pathways and competition for radicals between methane and n -heptane. The result shows that the addition of methane inhibits nonlinearly the low-temperature oxidation of n -heptane. The physical effect of methane is equivalent to that of nitrogen under the high-dilution condition, and as the methane content reaches 50%, methane starts to show the chemical effect, leading to the decrease of the maximum conversion ratio of n -heptane. The reaction pathway analysis shows that under the studied conditions, the stable oxygenated species and olefins will be left, and the added methane mainly affects the reaction pathways of small-molecule intermediates with OH and HO 2 . At higher methane content, less ketohydroperoxides and hydroperoxyl cyclic ethers will be consumed, and the negative effect of the reaction R46 CH 4 + OH <=> CH 3 + H 2 O on the consumption of n -heptane strengthens gradually. In addition, it is found that contributions of elementary reactions related to C 7 species to generation and consumption of OH and HO 2 remain unchanged under different methane additions, and methane suppresses the low-temperature oxidation of n -heptane mainly through its subsequent reactions to compete for OH and HO 2 with small-molecule intermediates.