Increased Ir–Ir Interaction in Iridium Oxide during the Oxygen Evolution Reaction at High Potentials Probed by Operando Spectroscopy

The structure of IrO₂ during the oxygen evolution reaction (OER) was studied by operando X-ray absorption spectroscopy (XAS) at the Ir L₃-edge to gain insight into the processes that occur during the electrocatalytic reaction at the anode during water electrolysis. For this purpose, calcined and uncalcined IrO₂ nanoparticles were tested in an operando spectroelectrochemical cell. In situ XAS under different applied potentials uncovered strong structural changes when changing the potential. Modulation excitation spectroscopy combined with XAS enhanced the information on the dynamic changes significantly. Principal component analysis (PCA) of the resulting spectra as well as FEFF9 calculations uncovered that both the Ir L₃-edge energy and the white line intensity changed due to the formation of oxygen vacancies and lower oxidation state of iridium at higher potentials, respectively. The deconvoluted spectra and their components lead to two different OER modes. It was observed that at higher OER potentials, the well-known OER mechanisms need to be modified, which is also associated with the stabilization of the catalyst, as confirmed by in situ inductively coupled plasma mass spectrometry (ICP-MS). At these elevated OER potentials above 1. 5 V, stronger Ir–Ir interactions were observed. They were more dominant in the calcined IrO₂ samples than in the uncalcined ones. The stronger Ir–Ir interaction upon vacancy formation is also supported by theoretical studies. We propose that this may be a crucial factor in the increased dissolution stability of the IrO₂ catalyst after calcination. The results presented here provide additional insights into the OER in acid media and demonstrate a powerful technique for quantifying the differences in mechanisms on different OER electrocatalysts. Furthermore, insights into the OER at a fundamental level are provided, which will contribute to further understanding of the reaction mechanisms in water electrolysis.