Selective Chemical Looping Combustion of Terminal Alkynes in Mixtures with Alkenes

The selective combustion of terminal alkynes in mixtures with alkenes is demonstrated during anaerobic reduction half-cycles on bulk bismuth oxide (Bi₂O₃) as an approach to remove alkynes, which act as inhibitors in olefin polymerization. Bi₂O₃ combusts phenylacetylene in styrene, 3-methylphenylacetylene in 3-methylstyrene, propyne in propylene, 1-hexyne in 1-hexene, and 1-octyne in 1-octene, with alkyne combustion selectivities exceeding 96%. Near unity reaction orders for hydrocarbon consumption during reduction half-cycles are consistent with combustion pathways initiated by rate-determining initial C–H activation, which drive selective alkyne combustion through intrinsic differences in the first-order rate constants for alkyne and alkene combustion rather than preferential adsorption of alkynes on Bi₂O₃ surfaces. Computational assessments of initial C–H activation pathways for alkynes and alkenes on (010) α-Bi₂O₃ surfaces using density functional theory illustrate that heterolytic transition states which form proton-carbanion pairs on Bi–O sites kinetically favor the activation of alkynes rather than alkenes due to differences in C–H bond acidity, and the barrier for heterolytic C–H activation is dictated in part by the sum of the molecular deprotonation energy and the energy to bind an R^– carbanion to a Bi site in its transition-state geometry. These heterolytic reactivity channels during selective chemical looping combustion present novel routes for purifying olefin gas streams containing alkyne impurities.