Plasma-Enhanced CO₂ Hydrogenation over Co-Based Catalysts: Surface and Gas-Phase Insights

ORAL

Abstract

The electrification of chemical processes for industrial and energy applications is growing with the availability of low-cost electricity from nuclear and renewable sources. Among emerging technologies, non-thermal plasma (NTP) enables CO₂ hydrogenation to hydrocarbons by energizing electrons and promoting bond activation at low bulk temperatures. This work investigates NTP-assisted CO₂ hydrogenation over Co/Al₂O₃ and K-Co/Al₂O₃ catalysts, with the hypothesis that conversion under plasma occurs via an alternative mechanism driven by vibrational excitation, molecular dissociation, and electron–molecule collisions; in this context, Co facilitates CHₓ formation while potassium promotes C–C coupling. Surface intermediates and products were monitored using operando and in-situ DRIFTS with a custom NTP cell to compare with thermal reactions. Under thermal conditions, Co/Al₂O₃ formed bicarbonate, formate, and CO linked to CH₄ formation, while K-Co/Al₂O₃ showed additional carbonate species associated with K⁺, indicating stronger surface carbon bonding. Plasma-assisted DRIFTS revealed fewer stable intermediates on Co/Al₂O₃ but enhanced carbonate and methoxy species on K-Co/Al₂O₃. Molecular beam mass spectrometry (MBMS) was employed and complemented by computational modeling to support mechanistic insights. NTP enabled intermediate formation at low temperature, revealing alternative pathways and underscoring plasma–catalyst synergy in hydrocarbon synthesis.

*This work was authored [in part] by the National Renewable Energy Laboratory (NREL) for the U.S. Department of Energy (DOE) under Contract No. DE-AC36-08GO28308. This work was supported by the Laboratory Directed Research and Development (LDRD) Program at NREL. The views expressed in the article do not necessarily represent the views of the DOE or the U.S. Government. The U.S. Government retains and the publisher, by accepting the article for publication, acknowledges that the U.S. Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this work, or allow others to do so, for U.S. Government purposes. In addition, the PPPL PCRF is supported by the US Department of Energy, Office of Science, Fusion Energy Sciences, under contract DE-AC02-09CH11466. Furtrmore, the SNL PRF is supported by US Department of Energy, Office of Science, Fusion Energy Sciences. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525. SAND2022-14422 O

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Presenters

  • Stefano Dell'Orco

    • National Renewable Energy Laboratory (NREL)

Authors

  • Stefano Dell'Orco

    • National Renewable Energy Laboratory (NREL)

  • Roxanne Walker

    • National Renewable Energy Laboratory
    • National Renewable Energy Laboratory (NREL)

  • Jeffrey Alleman

    • National Renewable Energy Laboratory (NREL)

  • Chae Jeong-Potter

    • National Renewable Energy Laboratory (NREL)

  • Susan Habas

    • National Renewable Energy Laboratory (NREL)

  • Noemi Leick

    • National Renewable Energy Laboratory (NREL)

  • Nicholas Deak

    • National Renewable Energy Laboratory (NREL)

  • Hariswaran Sitaraman

    • National Renewable Energy Laboratory (NREL)

  • Nils Hansen

    • Sandia National Laboratories (SNL)
    • Sandia National Laboratories

  • Sophia Gershman

    • Princeton Plasma Physics Laboratory (PPPL)

  • Calvin Mukarakate

    • National Renewable Energy Laboratory (NREL)