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The use of alternative oxidants for the oxidative dehydrogenation of propane (ODHP) is a promising strategy to suppress the facile overoxidation to CO x that occurs with O 2 . Gaseous disulfur (S 2 ) represents a thermodynamically “softer” oxidant that has been underexplored and yet offers a potential route to more selective propylene formation. Here we describe a system for sulfur-ODHP (SODHP). We demonstrate that various metal sulfide catalysts generate unique reaction product distributions, and that propylene selectivities as high as 86% can be achieved at 450–550 °C. For a group of 6 metal sulfide catalysts, apparent activation energies for propylene formation range from 72–134 kJ mol −1 and parallel the corresponding catalyst XPS sulfur binding energies, indicating that M–S bond strength plays a key role in SODHP activity. Kinetic data over a sulfided ZrO 2 catalyst indicate a rate law which is first-order in propane and zero-order in sulfur, suggesting that SODHP may occur via a mechanism analogous to the Mars van Krevelen cycle of traditional ODHP. The present results should motivate further studies of SODHP as a route to the selective and efficient oxidative production of propylene. 

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 CH₄to C₂H₄over an Fe₃O₄-derived FeS₂catalyst 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 CH₂coupling 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 CS₂by-product forms predominantly via CH₄oxidation, rather than from C₂products, through a series of C–H activation and S-addition steps at adsorbed sulfur sites on the FeS₂surface. The experimental rates for methane conversion are first order in both CH₄and S₂, consistent with the involvement of two S sites in the rate-determining methane C–H activation step, with a CD₄/CH₄kinetic isotope effect of 1.78. The experimental apparent activation energy for methane conversion is 66 ± 8 kJ/mol, significantly lower than for CH₄oxidative 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.