Plasma-Catalysis of Nonoxidative Methane Coupling: A Dynamic Investigation of Plasma and Surface Microkinetics over Ni(111).

A heterogeneous catalytic microkinetic model is developed and implemented in a zero-dimensional (0D) plasma model for the dynamic study of methane nonoxidative coupling over Ni(111) at residence times and power densities consistent with experimental reactors. The microkinetic model is thermodynamically consistent and is parameterized based on the heats of chemisorption of surface species on Ni(111). The surface network explicitly accounts for the interactions of plasma species, namely, molecules, radicals, and vibrationally excited states, with the catalyst active sites via adsorption and Eley-Rideal reactions. The Fridman-Macheret model is used to describe the enhancement of the rate of the dissociative adsorption of vibrationally excited CH, H, and CH. In combination with a previously developed detailed kinetic scheme for nonthermal methane plasma, 0D simulation results bring insights into the complex dynamic interactions between the plasma phase and the catalyst during methane nonoxidative coupling. Differential turnover frequencies achieved by plasma-catalysis are higher than those of equivalent plasma-only and catalysis-only simulations combined; however, this performance can only be sustained momentarily. Hydrogen produced from dehydrogenation of ethane via electron collisions within the plasma is found to quickly saturate the surface and even promote the conversion of surface CH* back to methane.