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The adsorption of molecular oxygen (enriched with 17O) onto high surface area MgO has been studied by electron paramagnetic resonance (EPR) spectroscopy. The oxide surface was pretreated in such a way so that surface trapped electron FS+(H) centers are produced. Subsequent dioxygen adsorption results in an electron transfer reaction from FS+(H) centers to O2, producing a surface stabilized superoxide (O2−) anion. The resulting EPR spectrum of the paramagnetic anion is complicated by the simultaneous presence of a high number of “normal” hyperfine lines along the principal axes and also by several off-axis extra features which have complicated previous interpretations of the Ayy and Azz components. By adopting a suitable adsorption procedure which suppresses the superoxide speciation, using a highly crystalline MgO material and controlling the isotopomer composition through appropriate 17O enrichments, the resolution of the EPR spectrum has been dramatically improved. Analysis of the 1H superhyperfine stru...

Continuous wave electron paramagnetic resonance investigation of the hyperfine structure of O2−17 adsorbed on the MgO surface