Structure-Controlled Oxygen Concentration in Fe₂O₃ and FeO₂

Solid-solid reaction, particularly in the Fe-O binary system, has been extensively studied in the past decades because of its various applications in chemistry and materials and earth sciences. The recently synthesized pyrite-FeO₂ at high pressure suggested a novel oxygen-rich stoichiometry that extends the achievable O-Fe ratio in iron oxides by 33%. Although FeO₂ was synthesized from Fe₂O₃ and O₂, the underlying solid reaction mechanism remains unclear. Herein, combining in situ X-ray diffraction experiments and first-principles calculations, we identified that two competing phase transitions starting from Fe₂O₃: (1) without O₂, perovskite-Fe₂O₃ transits to the post-perovskite structure above 50 GPa; (2) if free oxygen is present, O diffuses into the perovskite-type lattice of Fe₂O₃ leading to the pyrite-type FeO₂ phase. We found the O-O bonds in FeO₂ are formed by the insertion of oxygen into the Pv lattice via the external stress and such O-O bonding is only kinetically stable under high pressure. This may provide a general mechanism of adding extra oxygen to previous known O saturated oxides to produce unconventional stoichiometries. Our results also shed light on how O is enriched in mantle minerals under pressure.