We use microkinetic modeling to examine the potential of plasma-catalytic partial oxidation (POX) of CH 4 as a promising new approach to produce oxygenates. We study how different plasma species affect POX of CH 4 on the Pt(111) surface, and we discuss the associated kinetic and mechanistic changes. We discuss the effect of vibrationally excited CH 4 and O 2 , as well as plasma-generated radicals and stable intermediates. Our results show that vibrational excitation enhances the turnover frequency (TOF) of catalytic CH 4 dissociation and has good potential for improving the selectivities toward CH 3 OH, HCOOH, and C 2 hydrocarbons. Nevertheless, when also considering plasma-generated radicals, we find that these species mainly govern the surface chemistry. Additionally, we find that plasma-generated radicals and stable intermediates enhance the TOFs of CO x and oxygenates, increase the selectivity toward oxygenates, and make the formation of HCOOH more significant on Pt(111). We also briefly illustrate the potential impact of Eley− Rideal reactions that involve plasma-generated radicals. Finally, we reveal how various radicals affect the catalyst surface chemistry and we link this to the formation of different products. This allows us to make suggestions on how the plasma composition should be altered to improve the formation of desired products.
Upgrading ethane with CO2 as a soft oxidant represents
a desirable means of obtaining oxygenated hydrocarbons. This reaction
is not thermodynamically feasible under mild conditions and has not
been previously achieved as a one-step process. Nonthermal plasma
was implemented as an alternative means of supplying energy to overcome
activation barriers, leading to the production of alcohols, aldehydes,
and acids as well as C1–C5+ hydrocarbons
under ambient pressure, with a maximum total oxygenate selectivity
of 12%. A plasma chemical kinetic computational model was developed
and found to be in good agreement with the experimental trends. Results
from this study illustrate the potential to use plasma for the direct
synthesis of value-added alcohols, acids, and aldehydes from ethane
and CO2 under mild conditions.
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