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.