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A Theoretical Study on the Mechanism of Small Carbon Clusters Growth in Low-Temperature Plasma

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Abstract

Understanding the interaction between small alkane radical ions and methane could lead to more efficient ways of hydrogen production, which is an essential component in the field of green energy. It can contribute to the development of new plasma processing methods for natural gas utilization and conversion into other useful products. In this study, using first-principles calculations we analyzed interactions between small alkane radical ions and methane molecules in low-temperature plasma resulting in formation of carbon clusters and hydrogen molecules. We found that anion-methane interaction initiates after C–H bond rupture in CH4 with the lowest activation barrier observed for negative ions C3H7− and C2H5− undergoing a hydrogen transfer reaction. Positive alkane ion radicals C3H7+ and C2H5+ demonstrated a different initial step in the clustering process where CH3 and H transfer reactions occur simultaneously. The activation barrier for the reaction between positive ethyl ion C2H5+ and methane is ~ 0.4 eV in accordance with experimental studies. Our calculations showed that both negative and positive ethyl ions readily react with methane, forming hydrogen molecules and propyl ion radicals C3H7−/ C3H7+. However, the continued growth of these radicals encounters increasing activation barriers, suggesting a slowdown in the carbon ion clustering rate and hydrogen production. Estimated rate constants of the considered ion-neutral reactions are in reasonable agreement with experimental values for a wide range of temperatures. These findings are crucial for understanding of carbon nanoparticle generation and hydrogen production using plasma catalysis.

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Data Availability

The data that support the findings of this study are available on request from the corresponding author, Yegor M. Kedalo.

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Acknowledgements

This work has been carried out using computing resources of the federal collective usage center Complex for Simulation and Data Processing for Mega-science Facilities at NRC “Kurchatov Institute”, http://ckp.nrcki.ru/ and was supported by the Research Center “Kurchatov Institute (order No. 1569 of July 16, 2019).

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Authors and Affiliations

  1. Kintech Lab Ltd, Moscow, Russia

    Yulia G. Polynskaya, Nikita A. Matsokin, Yegor M. Kedalo, Andrey A. Knizhnik, Alex S. Sinitsa & Boris V. Potapkin

  2. M. V. Lomonosov Moscow State University, Moscow, Russia

    Nikita A. Matsokin

  3. Moscow Institute of Physics and Technology, Dolgoprudny, Russia

    Yegor M. Kedalo

  4. National Research Center “Kurchatov Institute”, Moscow, Russia

    Yegor M. Kedalo, Andrey A. Knizhnik, Alex S. Sinitsa & Boris V. Potapkin

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  1. Yulia G. Polynskaya
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Contributions

NM: methodology, investigation, writing. YP: writing, methodology, validation, investigation, visualization. YK: validation, investigation, writing, visualization. AK: writing, supervision, project administration. AS: review & editing. BP: supervision, funding acquisition.

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Correspondence to Yegor M. Kedalo.

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Polynskaya, Y.G., Matsokin, N.A., Kedalo, Y.M. et al. A Theoretical Study on the Mechanism of Small Carbon Clusters Growth in Low-Temperature Plasma. Plasma Chem Plasma Process 44, 193–209 (2024). https://doi.org/10.1007/s11090-023-10390-3

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