On the Operando Structure of Ruthenium Oxides during the Oxygen Evolution Reaction in Acidic Media

[Image: see text] In the search for rational design strategies for oxygen evolution reaction (OER) catalysts, linking the catalyst structure to activity and stability is key. However, highly active catalysts such as IrO(x) and RuO(x) undergo structural changes under OER conditions, and hence, structure–activity–stability relationships need to take into account the operando structure of the catalyst. Under the highly anodic conditions of the oxygen evolution reaction (OER), electrocatalysts are often converted into an active form. Here, we studied this activation for amorphous and crystalline ruthenium oxide using X-ray absorption spectroscopy (XAS) and electrochemical scanning electron microscopy (EC-SEM). We tracked the evolution of surface oxygen species in ruthenium oxides while in parallel mapping the oxidation state of the Ru atoms to draw a complete picture of the oxidation events that lead to the OER active structure. Our data show that a large fraction of the OH groups in the oxide are deprotonated under OER conditions, leading to a highly oxidized active material. The oxidation is centered not only on the Ru atoms but also on the oxygen lattice. This oxygen lattice activation is particularly strong for amorphous RuO(x). We propose that this property is key for the high activity and low stability observed for amorphous ruthenium oxide.