Effect of promoter in the oxidative coupling of methane over synthesized Mn/SiO2 nanocatalysts via incipient wetness impregnation

The M–Na–Mn/SiO₂ nanocatalysts (M = W, Mo, Nb, V, Cr) were synthesized with the size of 12–92 nm by incipient wetness impregnation method to study the effect of different promoters on the catalytic performance in the oxidative coupling of methane. The results at 1 atm, 1048 K, 2500 ml h^?1 g^?1, and CH₄/O₂/N₂ = 2/2/1 revealed that C₂ selectivity was significantly increased (31.6%) in the order of W > Mo > Nb > Cr > V whereas moderate enhancement (12.6%) was observed in the CH₄ conversion in the order of W > Cr > Nb > Mo > V. The results of the characterization techniques (Raman, FT-IR, BET, TGA/DTA and XRD) demonstrated that Mn₂O₃ and α-cristobalite were the predominant species and active sites in the nanocatalyst surface and Na₂MoO₄, Na₂WO₄ and Mn₂O₃ crystalline phases contributed to achieving high selectivity of C₂ products. The redox mechanism involving two metal sites such as Mn^3+/2+ and W^6+/5+ or Mn^3+/2+ and Mo^6+/5+ was found to be the most compatible route with the OCM reaction path in which CH₄ and O₂ adsorption was the controlling step.