The effect of oxidant species on direct, non-syngas conversion of methane to methanol over an FePO4 catalyst material

Abstract

The effect of the phase transformation of a FePO₄ catalyst material from the tridymite-like (tdm) FePO₄ to the α-domain (α-Fe₃(P₂O₇)₂) during the direct selective oxidation of methane to methanol was studied using oxidant species O₂, H₂O and N₂O. The main reaction products were CH₃OH, carbon dioxide and carbon monoxide, whereas formaldehyde was produced in rather minute amounts. Results showed that the single-step non-syngas activation of CH₄ to oxygenate(s) on a solid FePO₄ phase-specific catalyst was influenced by the nature of the oxidizer used for the CH₄ turnover. Fresh and activated FePO₄ powder samples and their modified physicochemical surface and bulk properties, which affected the conversion and selectivity in the partial oxidation (POX) mechanism of CH₄, were investigated. Temperature-programmed re-oxidation (TPRO) profiles indicated that the type of moieties utilised in the procedures, determined the re-oxidizing pathway of the reduced multiphase FePO₄ system. Mössbauer spectroscopy measurements along with X-ray diffraction (XRD) examination of neat, hydrogenated and spent catalytic compounds, demonstrated a variation of the phosphate into a mixture of crystallites, which depended on operating process conditions (for example time-on-stream). The Mössbauer spectra revealed the change of the initial ferric orthophosphate, FePO₄ (tdm), to the divalent metal form, iron(II) pyrophosphate (Fe₂P₂O₇); thereafter, reactivity was governed by the interaction (strength) with individual oxidizing agents. The Fe³⁺ ↔ Fe²⁺ chemical redox cycle can play a key mechanistic role in tailored multistep design, while the advantage of iron-based heterogeneous catalysis primarily lies in being inexpensive and comprising non-critical raw resources. When compared to the other catalysts reported in the literature, the FePO₄-tdm phase catalysts showed in this work exhibited a high activity towards methanol i.e., 12.3 × 10⁻³ μmol_MeOH g_cat h⁻¹ using N₂O as an oxidant. This catalyst also showed a high activity with O₂ as an oxidant (5.3 × 10⁻³ μmol_MeOH g_cat h⁻¹). Further investigations will include continuous reactor unit engineering optimisation.