Samples of Li/MgO were generated by co-gelling Li2CO3 and Mg(OEt)(2), and c
haracterized with the aid of diverse spectroscopic techniques: EPR, FTIR, U
V-vis, TGA, DTA, and X-ray powder diffraction (with refinement of the cryst
alline structure). The presence of the EPR hyperfine structure of Mn4+ resu
lting from the conversion of the unintentionally present impurity Mn2+ to M
n4+, establishes clear evidence that lithium ions are present in the sol-ge
l matrix substituting for magnesium ions. Indeed, only after irradiating th
e sample with gamma rays at liquid nitrogen, the formation of [Li](0) cente
rs in a metastable fashion was possible, but further instability and annihi
lation occurred when the sample was brought back to room temperature. The s
ol-gel material described in this work proves to be active in the oxidative
coupling of methane.