Isotopic Oxygen Exchange and EPR Studies of Superoxide Species on the SrF₂/La₂O₃ Catalyst

Abstract

By using the in situ IR spectroscopy, the superoxide species (O ⁻₂ ), characterized by the O–O stretching peak at 1130 cm⁻¹, was detected on the SrF₂/La₂O₃ catalyst at temperatures up to 973 K. The introduction of ¹⁸O₂ isotope caused the 1130 cm⁻¹ peak to shift to lower wavenumbers (1095 and 1064 cm⁻¹), consistent with the assignment of the spectra to the superoxide species. A good correlation between the rate of the disappearance of the O ⁻₂ species and that of the formation of C₂H₄ was observed, suggesting that O ⁻₂ was the active oxygen species responsible for the oxidative coupling of methane (OCM) on the SrF₂/La₂O₃ catalyst. This conclusion was reinforced by the EPR experiments (g_xx = 2.0001, g_yy = 2.0045, g_zz  = 2.0685), showing that O ⁻₂ was the only paramagnetic oxygen species detectable on the O₂-preadsorbed SrF₂/La₂O₃ catalyst. These results suggest that superoxide O ⁻₂ can be a stable active oxygen species, whose role in the OCM reaction cannot be overlooked.