Chemical Activity of the Peroxide/Oxide Redox Couple: Case Study of Ba(5)Ru(2)O(11) in Aqueous and Organic Solvents

[Image: see text] The finding that triggering the redox activity of oxygen ions within the lattice of transition metal oxides can boost the performances of materials used in energy storage and conversion devices such as Li-ion batteries or oxygen evolution electrocatalysts has recently spurred intensive and innovative research in the field of energy. While experimental and theoretical efforts have been critical in understanding the role of oxygen nonbonding states in the redox activity of oxygen ions, a clear picture of the redox chemistry of the oxygen species formed upon this oxidation process is still missing. This can be, in part, explained by the complexity in stabilizing and studying these species once electrochemically formed. In this work, we alleviate this difficulty by studying the phase Ba(5)Ru(2)O(11), which contains peroxide O(2)(2–) groups, as oxygen evolution reaction electrocatalyst and Li-ion battery material. Combining physical characterization and electrochemical measurements, we demonstrate that peroxide groups can easily be oxidized at relatively low potential, leading to the formation of gaseous dioxygen and to the instability of the oxide. Furthermore, we demonstrate that, owing to the stabilization at high energy of peroxide, the high-lying energy of the empty σ* antibonding O–O states limits the reversibility of the electrochemical reactions when the O(2)(2–)/O(2–) redox couple is used as redox center for Li-ion battery materials or as OER redox active sites. Overall, this work suggests that the formation of true peroxide O(2)(2–) states are detrimental for transition metal oxides used as OER catalysts and Li-ion battery materials. Rather, oxygen species with O–O bond order lower than 1 would be preferred for these applications.