An apparent ensemble effect in the oxidative coupling of methane on hydroxyapatites with incorporated lead

Abstract

The introduction of small quantities of lead into calcium hydroxyapatite catalysts produces marked increases in the selectivity to C2+ hydrocarbons, while the conversion of methane remains relatively constant. Small surface concentrations of lead are sufficient to achieve C2+ selectivities of 80 and 90%, with oxygen and nitrous oxide, respectively, in contrast with 18 and 46%, respectively, obtained in the absence of lead. Since surface concentration of lead species sufficient to stabilize pairs of methyl radicals in close proximity to each other would be expected to facilitate the formation of C2 hydrocarbons, an ensemble effect appears to be extant.