Oxidative Functionalization of Long-Chain Liquid Alkanes by Pulsed Plasma Discharges at Atmospheric Pressure

Nguyen, Darien K.
Dimitrakellis, Panagiotis
Talley, Michael R.
O'Dea, Robert M.
Epps, Thomas H. III
Watson, Mary P.
Vlachos, Dionisios G.
Journal Title
Journal ISSN
Volume Title
ACS Sustainable Chemistry and Engineering
We introduce the oxidation of long aliphatic alkanes using non-thermal, atmospheric plasma processing as an eco-friendly route for organic synthesis. A pulsed dielectric barrier discharge in He/O2 gas mixtures was employed to functionalize n-octadecane. C18 secondary alcohols and ketones were the main products, with an optimal molar yield of ∼29.2%. Prolonged treatment resulted in the formation of dialcohols, diketones, and higher molecular weight oxygenates. Lighter hydrocarbon products and decarboxylation to CO2 were also observed at longer treatment times and higher power inputs. A maximum energy yield of 5.48 × 10–8 mol/J was achieved at short treatment times and high powers, associated with higher selectivity to primary oxygenates. Direct hydroxylation of alkyl radicals, as well as disproportionation reactions, are proposed as the main pathways to alcohols and ketones. The results hold promise for functionalizing long hydrocarbon molecules at ambient conditions using catalyst-free plasma discharges.
This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Sustainable Chemistry and Engineering, copyright © 2022 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acssuschemeng.2c04269. This article will be embargoed until 11/17/2023.
oxidation , functionalization , liquid alkane , atmospheric plasma , dielectric barrier discharge , octadecane
Nguyen, Darien K., Panagiotis Dimitrakellis, Michael R. Talley, Robert M. O’Dea, Thomas H. III Epps, Mary P. Watson, and Dionisios G. Vlachos. “Oxidative Functionalization of Long-Chain Liquid Alkanes by Pulsed Plasma Discharges at Atmospheric Pressure.” ACS Sustainable Chemistry & Engineering 10, no. 48 (December 5, 2022): 15749–59. https://doi.org/10.1021/acssuschemeng.2c04269.