Hydrous Iridium Oxide Thin Films: Revealing the Structure of a Highly Active Model Catalyst By in-Situ Ir L 3-Edge XANES and EXAFS

Currently, only iridium oxide shows favourable activity and stability under the harsh oxygen evolution reaction (OER) conditions for application in proton exchange membrane water electrolysis (PEM-WE) [1-3]. There is a well established inverse relationship between OER activity and stability of iridium oxide-based OER catalysts given its degree of crystallinity and hydration [4-6]. Crystalline, anhydrous iridium oxides are more stable but have diminished OER activity compared to amorphous, hydrous iridium oxides, which are more active. Different OER mechanisms have been theorized to occur on these materials, explaining their difference in performance [6]. Several spectroscopic investigations have been performed to explore the properties of such different iridium oxides, in particular to identify the chemical and electronic state of their active sites. However, a consensus regarding the active site structure and OER mechanism has yet to be reached [7-10]. Using scanning electron microscopy, x-ray photoelectron spectroscopy, and combining in-situ Ir L 3 -edge x-ray absorption spectroscopy with density functional theory (DFT) calculations and ab initio thermodynamics, we have investigated in-situ electrochemically grown porous hydrous iridium oxide thin films (HIROF) as a model system to examine the chemical and electronic structure of the highly active, hydrous iridium oxide species. In-situ extended x-ray absorption fine structure(EXAFS) results show that HIROF grows preferentially in a form most often associated with the OER catalytically active site of hydrous iridium oxides. Calculations over different possible structures allowed us to identify a unique structural group with enhanced hydrogenation that best fits the EXAFS data. In-situ x-ray absorption near edge structure (XANES) results reveal a lower onset potential for the redox behaviour of HIROF compared to rutile IrO 2 . Based on this study, we propose a new structural model explaining the high activity and poorer stability of hydrous iridium oxides compared to crystalline IrO 2 . References: [1] A. Buttler and H. Spliethoff, Renew. Sustain. Energy Rev., 2018, 82, pp. 2440-2454. [2] Schlögl, ChemSusChem, 2010, 3, pp. 209-222. [3] M. Schalenbach, J. Electrochem. Soc., 2016, 163, pp. F3197-P3208. [4] S. Cherevko, Electrochem. Commun., 2014, 48, pp. 81-85. [5] S. Cherevko, J. Electroanal. Chem., 2016(1), 773, pp 69-78. [6] S. Cherevko, J. Electroanal. Chem., 2016(2), 774, pp 102-110. [7] V. Pfeifer. Su