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Sulfur as a selective ‘soft’ oxidant for catalytic methane conversion probed by experiment and theory

Nature Chemistry volume 5, pages 104–109 (2013)Cite this article

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Abstract

Developing efficient catalytic processes to convert methane into useful feedstocks relies critically upon devising new coupling processes that use abundant, thermodynamically ‘mild’ oxidants together with selective catalysts. We report here on elemental sulfur as a promising ‘soft’ oxidant for selective methane conversion to ethylene over MoS2, RuS2, TiS2, PdS and Pd/ZrO2 catalysts. Experiments and density functional theory reveal that methane conversion is directly correlated with surface metal–sulfur bond strengths. Surfaces with weakly bound sulfur are more basic and activate methane C–H bonds more readily. In contrast, experimental and theoretical selectivities scale inversely with surface metal–sulfur bond strengths, and surfaces with the strongest metal–sulfur bonds afford the highest ethylene selectivities. High CH4/S ratios, short contact times and the provision of a support maximizes the coupling of CHx intermediates and selectivity to ethylene, because these conditions yield surfaces with stronger metal–sulfur bonding (for example, Pd16S7), which suppresses the over-oxidation of methane.

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Figure 1: Thermodynamic calculations show that using gaseous sulfur (S2) as a ‘soft’ oxidant can hinder the over-oxidation of methane when compared with using O2 as the oxidant.
Figure 2: Unsupported metal sulfides are effective catalysts for the conversion of methane to ethylene using gaseous sulfur as a ‘soft’ oxidant.
Figure 3: Ab initio DFT calculations shows the characteristic reactant, transition state and product structures for the catalytic conversion of methane to ethylene using gaseous sulfur as the oxidant.
Figure 4: Calculations reveal a correlation between both C–H activation and CH2 coupling with M–S bond strength.
Figure 5: Markedly altered PdS-catalysed methane conversion and ethylene selectivity are observed by varying the CH4:S feed ratios and WHSVs over the catalyst surface.
Figure 6: A ZrO2-supported palladium sulfide catalyst exhibits significantly enhanced catalytic performance compared with an unsupported catalyst in the conversion of methane to ethylene using gaseous sulfur as the oxidant.

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Acknowledgements

The authors thank the Dow Chemical Company for support as part of the Methane Challenge project. The authors thank S. Domke, P. Nickias, D. Barton and M. Kaminsky for stimulating discussions.

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Authors and Affiliations

  1. Department of Chemistry and the Center for Catalysis and Surface Science, Northwestern University, Evanston, 60208-3113, Illinois, USA

    Qingjun Zhu, Staci L. Wegener, Chao Xie & Tobin J. Marks

  2. Departments of Chemical Engineering and Chemistry University of Virginia, Charlottesville, 22904-4741, Virginia, USA

    Obioma Uche & Matthew Neurock

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  1. Qingjun Zhu
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Contributions

Q.Z., S.L.W. and C.X. performed the experiments, analysed the data, and wrote portions of the manuscript. O.U. and M.N. performed DFT calculations and wrote portions of the manuscript. All authors contributed to writing and revising the manuscript.

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Correspondence to Matthew Neurock or Tobin J. Marks.

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Zhu, Q., Wegener, S., Xie, C. et al. Sulfur as a selective ‘soft’ oxidant for catalytic methane conversion probed by experiment and theory. Nature Chem 5, 104–109 (2013). https://doi.org/10.1038/nchem.1527

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