Abstract

Kinetic studies and isotopic exchange measurements (CH4–CD4 and 16O2–18O2) of the oxidative coupling of methane over stoichiometric LiNiO2 indicate a redox mechanism involving lattice oxygen atoms. The formation of C2 products is second-order in methane, both in the presence and absence of gaseous oxygen. Methane is dissociatively adsorbed on Ni3+—O2– sites, and the rate-determining step is the coupling of adsorbed CH3. Reduction of the catalyst by methane forms NiO, over which deep oxidation occurs. Adsorbed oxygen or gaseous oxygen is responsible for the deep oxidation.

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