"Soft" oxidative coupling of methane to ethylene: Mechanistic insights from combined experiment and theory.

Abstract

The oxidative coupling of methane to ethylene using gaseous disulfur (2CH₄ + S₂ → C₂H₄ + 2H₂S) as an oxidant (SOCM) proceeds with promising selectivity. Here, we report detailed experimental and theoretical studies that examine the mechanism for the conversion of CH₄ to C₂H₄ over an Fe₃O₄-derived FeS₂ catalyst achieving a promising ethylene selectivity of 33%. We compare and contrast these results with those for the highly exothermic oxidative coupling of methane (OCM) using O₂ (2CH₄ + O₂ → C₂H₄ + 2H₂O). SOCM kinetic/mechanistic analysis, along with density functional theory results, indicate that ethylene is produced as a primary product of methane activation, proceeding predominantly via CH₂ coupling over dimeric S-S moieties that bridge Fe surface sites, and to a lesser degree, on heavily sulfided mononuclear sites. In contrast to and unlike OCM, the overoxidized CS₂ by-product forms predominantly via CH₄ oxidation, rather than from C₂ products, through a series of C-H activation and S-addition steps at adsorbed sulfur sites on the FeS₂ surface. The experimental rates for methane conversion are first order in both CH₄ and S₂, consistent with the involvement of two S sites in the rate-determining methane C-H activation step, with a CD₄/CH₄ kinetic isotope effect of 1.78. The experimental apparent activation energy for methane conversion is 66 ± 8 kJ/mol, significantly lower than for CH₄ oxidative coupling with O₂ The computed methane activation barrier, rate orders, and kinetic isotope values are consistent with experiment. All evidence indicates that SOCM proceeds via a very different pathway than that of OCM.