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Direct observation of two electron holes in a hematite photoanode during photoelectrochemical water splitting

Type of publication Peer-reviewed
Publikationsform Original article (peer-reviewed)
Author Braun Artur, Sivula Kevin, Bora Debajeet K., Zhu JunFa, Zhang Liang, Grätzel Michaël, Guo Jinghua, Constable Edwin C.,
Project Fundamental Aspects of Photocatalysis and Photoelectrochemistry / Basic Research Instrumentation for Functional Characterization
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Original article (peer-reviewed)

Journal Journal of Physical Chemistry C
Volume (Issue) 116(32)
Page(s) 16870 - 16875
Title of proceedings Journal of Physical Chemistry C
DOI 10.1021/jp304254k


Visible light active photoelectrodes for hydrogen generation by solar photoelectrochemical water splitting have been under scrutiny for many decades. In particular, the role of electron holes and charge transfer remains controversial. We have investigated the oxygen evolution of hematite in alkaline aqueous electrolyte under a bias potential during visible light illumination in a photoelectrochemical cell operando with soft X-ray (O 1s) spectroscopy. Only under these conditions, two new spectral signatures evolve in the valence band, which we identify as an O 2p hole transition into the charge transfer band and an Fe 3d type hole into the upper Hubbard band. Quantitative analysis of their spectral weight and comparison with the photocurrent reveals that both types of holes, contrary to earlier speculations and common perception, contribute to the photocurrent. © 2012 American Chemical Society.