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The electronic, chemical and electrocatalytic processes and intermediates on iron oxide surfaces during photoelectrochemical water splitting

Type of publication Peer-reviewed
Publikationsform Original article (peer-reviewed)
Author Braun Artur, Hu Yelin, Boudoire Florent, Bora Debajeet K., Sarma D. D., Graetzel Michael, Eggleston Carrick M.,
Project Fundamental Aspects of Photocatalysis and Photoelectrochemistry / Basic Research Instrumentation for Functional Characterization
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Original article (peer-reviewed)

Volume (Issue) 260
Page(s) 72 - 81
Title of proceedings CATALYSIS TODAY
DOI 10.1016/j.cattod.2015.07.024


We re-assess experimental soft X-ray absorption spectra of the oxygen K-shell which we recorded operando from iron oxide during photoelectrochemical water splitting in KOH electrolyte. In particular, we refer to recently reported transitional electron hole states which originate within the charge carrier depletion layer of the iron oxide and on the iron oxide surface. For the latter we find that an intermediate oxy-peroxo species is formed on the iron oxide with increasing bias potential, which disappears upon further polarization of the electrode, concomitantly with the evolution and disappearance of the aforementioned surface state. The oxygen spectra contain also the spectroscopic signatures of the electrolyte water, the position of which changes with increasing bias potential towards lower X-ray energies, revealing the breaking and formation of hydrogen bonds in the water during the experiment. Combined with potential dependent impedance spectroscopy data we are able to sketch the molecular structure of chemical intermediates and their charge carrier dynamics. (C) 2015 Elsevier B.V. All rights reserved.