Critical Surface Parameters for the Oxidative Coupling of Methane over the Mn–Na–W/SiO₂ Catalyst

The work here presents a thorough evaluation of the effect of Mn–Na–W/SiO₂ catalyst surface parameters on its performance in the oxidative coupling of methane (OCM). To do so, we used microporous dealuminated β-zeolite (Zeo), or mesoporous SBA-15 (SBA), or macroporous fumed silica (Fum) as precursors for catalyst preparation, together with Mn nitrate, Mn acetate and Na₂WO₄. Characterizing the catalysts by inductively coupled plasma–optical emission spectroscopy, N₂ physisorption, X-ray diffraction, high-resolution scanning electron microscopy–energy-dispersive spectroscopy, X-ray photoelectron spectroscopy, and catalytic testing enabled us to identify critical surface parameters that govern the activity and C₂ selectivity of the Mn–Na–W/SiO₂ catalyst. Although the current paradigm views the phase transition of silica to α-cristobalite as the critical step in obtaining dispersed and stable metal sites, we show that the choice of precursors is equally or even more important with respect to tailoring the right surface properties. Specifically, the SBA-based catalyst, characterized by relatively closed surface porosity, demonstrated low activity and low C₂ selectivity. By contrast, for the same composition, the Zeo-based catalyst showed an open surface pore structure, which translated up to fourfold higher activity and enhanced selectivity. By varying the overall composition of the Zeo catalysts, we show that reducing the overall W concentration reduces the size of the Na₂WO₄ species and increases the catalytic activity linearly as much as fivefold higher than the SBA catalyst. This linear dependence correlates well to the number of interfaces between the Na₂WO₄ and Mn₂O₃ species. Our results combined with prior studies lead us to single out the interface between Na₂WO₄ and Mn₂O₃ as the most probable active site for OCM using this catalyst. Synergistic interactions between the various precursors used and the phase transition are discussed in detail, and the conclusions are correlated to surface properties and catalysis