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Carbon dioxide reduction in tandem with light-alkane dehydrogenation

Nature Reviews Chemistry volume 3, pages 638–649 (2019)Cite this article

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Abstract

A greenhouse gas and mild oxidant, CO2 can effect the oxidative dehydrogenation (CO2-ODH) of light alkanes over heterogeneous catalysts. These catalysts are bifunctional in that they mediate CO2 reduction while oxidizing the alkanes, most notably the C2–C4 components in shale gas. In this way, one obtains CO and alkenes as value-added products. Although desirable, this transformation has proven challenging in terms of catalyst design, with most catalysts for the CO2-ODH being metal oxides that typically undergo rapid deactivation. More recently, bimetallic catalysts have been identified as promising systems to activate alkanes by either selectively cleaving C–H bonds to produce alkenes or breaking all the C–C and C–H bonds to produce the dry reforming products CO and H2. This Review describes general trends in the CO2-ODH of light alkanes. We will also outline how to use a combined approach involving flow reactor experiments, in operando characterization and density functional theory to determine whether a catalyst is intrinsically active for CO2-ODH or dry reforming.

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Fig. 1: Thermodynamics of CO2-effected oxidative dehydrogenation and direct dehydrogenation of alkanes.
Fig. 2: Oxidative dehydrogenation of alkanes proceeds over metal-oxide catalysts.
Fig. 3: Flow reactions of C2H6 with CO2 over FexNiy/CeO2 catalysts.
Fig. 4: In situ XANES provides information on catalyst oxidation state and bonding.
Fig. 5: ADF-STEM and EELS of FexNiy/CeO2 catalysts reveal the active sites.
Fig. 6: Conversion of C2H6 and CO2 occurs at interfacial sites of FexNiy/CeO2 catalysts.
Fig. 7: Energetics of C2H6 and CO2 reactions over FexNiy catalysts.
Fig. 8: CO2 reacts with C3H8 over bimetallic catalysts supported on CeO2.

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Acknowledgements

The work is sponsored by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Biosciences, and Geosciences, under contract no. DE-SC0012704. E.G. acknowledges the U.S. National Science Foundation Graduate Research Fellowship Program: DGE-16-44869 and the Gates Millennium Scholarship Foundation.

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Authors and Affiliations

  1. Department of Chemical Engineering, Columbia University, New York, NY, USA

    Elaine Gomez, Shyam Kattel & Jingguang G. Chen

  2. Chemistry Division, Brookhaven National Laboratory, Upton, NY, USA

    Binhang Yan & Jingguang G. Chen

  3. Department of Chemical Engineering, Tsinghua University, Beijing, China

    Binhang Yan

  4. Department of Physics, Florida A&M University, Tallahassee, FL, USA

    Shyam Kattel

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  2. Binhang Yan
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Contributions

E.G. and J.G.C. prepared the manuscript with contributions from Y.B.H and S.K. E.G. conducted thermodynamic calculations with contributions from Y.B.H.

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Correspondence to Jingguang G. Chen.

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Gomez, E., Yan, B., Kattel, S. et al. Carbon dioxide reduction in tandem with light-alkane dehydrogenation. Nat Rev Chem 3, 638–649 (2019). https://doi.org/10.1038/s41570-019-0128-9

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