The electronic structure of iridium oxide electrodes active in water splitting. Issue 4 (24th December 2015)

• Record Type: Journal Article
• Authors: Pfeifer, V.; Jones, T. E.; Velasco Vélez, J. J.; Massué, C.; Greiner, M. T.; Arrigo, R.; Teschner, D.; Girgsdies, F.; Scherzer, M.; Allan, J.; Hashagen, M.; Weinberg, G.; Piccinin, S.; Hävecker, M.; Knop-Gericke, A.; Schlögl, R.
• Is Part Of: Physical chemistry chemical physics. Volume 18:Issue 4(2016)
• Page Start: 2292
• Page End: 2296
• Publication Date: 2015-12-24
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/c5cp06997a
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : Combining XPS, NEXAFS, and DFT reveals anionic and cationic defects in OER-active iridium oxides give rise to electrophilic oxygen species. Abstract : Iridium oxide based electrodes are among the most promising candidates for electrocatalyzing the oxygen evolution reaction, making it imperative to understand their chemical/electronic structure. However, the complexity of iridium oxide's electronic structure makes it particularly difficult to experimentally determine the chemical state of the active surface species. To achieve an accurate understanding of the electronic structure of iridium oxide surfaces, we have combined synchrotron-based X-ray photoemission and absorption spectroscopies with ab initio calculations. Our investigation reveals a pre-edge feature in the O K-edge of highly catalytically active X-ray amorphous iridium oxides that we have identified as O 2p hole states forming in conjunction with Ir III . These electronic defects in the near-surface region of the anionic and cationic framework are likely critical for the enhanced activity of amorphous iridium oxides relative to their crystalline counterparts.