Direct mapping of band positions in doped and undoped hematite during photoelectrochemical water splitting

A Shavorskiy, X Ye, O Karslıoğlu… - The Journal of …, 2017 - ACS Publications
The Journal of Physical Chemistry Letters, 2017ACS Publications
Photoelectrochemical water splitting is a promising pathway for the direct conversion of
renewable solar energy to easy to store and use chemical energy. The performance of a
photoelectrochemical device is determined in large part by the heterogeneous interface
between the photoanode and the electrolyte, which we here characterize directly under
operating conditions using interface-specific probes. Utilizing X-ray photoelectron
spectroscopy as a noncontact probe of local electrical potentials, we demonstrate direct …
Photoelectrochemical water splitting is a promising pathway for the direct conversion of renewable solar energy to easy to store and use chemical energy. The performance of a photoelectrochemical device is determined in large part by the heterogeneous interface between the photoanode and the electrolyte, which we here characterize directly under operating conditions using interface-specific probes. Utilizing X-ray photoelectron spectroscopy as a noncontact probe of local electrical potentials, we demonstrate direct measurements of the band alignment at the semiconductor/electrolyte interface of an operating hematite/KOH photoelectrochemical cell as a function of solar illumination, applied potential, and doping. We provide evidence for the absence of in-gap states in this system, which is contrary to previous measurements using indirect methods, and give a comprehensive description of shifts in the band positions and limiting processes during the photoelectrochemical reaction.
ACS Publications
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