Ir metal nanoparticles and IrO2 for acidic oxygen evolution reaction: Insight from Raman spectroscopy

Abstract

Due to their high activity and stability, Ir-based materials are state-of-the-art electrocatalysts for oxygen evolution reaction (OER) under acidic conditions. However, many factors such as the influence of the activation/conditioning protocol and the resulting oxidation state or the effect of electrolyte adsorption on activity are still debated or overlooked. Herein, Raman spectroscopy was performed on commercial Ir black and IrO2 nanopowders to reveal differences in the samples after activation, as well as adsorption of perchlorates. Specifically, three different activation protocols were performed, 0.05 to 1.45 VRHE (activated), 0.05 to 1.6 VRHE (activated-long range (l.r.)), and 1.1 to 1.6 VRHE (activated-short range (s.r.)), resulting in different OER activity as well as different Raman spectra. However, only Ir(IV) bands remain visible in the ex situ Raman experiments, which was not sufficient to reveal the hydrated phases in the iridium samples. Therefore, mimicked in situ experiments were performed, which allowed the observation of the hydrated phase, particularly for Ir black, but also showed adsorption of perchlorate anions. In addition, the influence of solvation on Raman band shifts is revealed - along with DFT calculations. Overall, this work paves the way for our future in situ Raman spectroscopy experiments with iridium-based electrocatalysts during activation and OER.