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Title: Direct Mapping of Band Positions in Doped and Undoped Hematite during Photoelectrochemical Water Splitting

Abstract

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. Here, 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.

Authors:
 [1];  [2];  [1];  [2];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [4];  [4]; ORCiD logo [4];  [5]; ORCiD logo [2]; ORCiD logo [6]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  2. Stanford Univ., CA (United States). Material Science and Engineering Division
  3. Forschungszentrum Julich (Germany). Peter-Grunberg-Inst.
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
  6. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1440006
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 8; Journal Issue: 22; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 14 SOLAR ENERGY

Citation Formats

Shavorskiy, Andrey, Ye, Xiaofei, Karslgolu, Osman, Poletayev, Andrey D., Hartl, Matthias, Zegkinoglou, Ioannis, Trotochaud, Lena, Nemsak, Slavomir, Schneider, Claus M., Crumlin, Ethan J., Axnanda, Stephanus, Liu, Zhi, Ross, Philip N., Chueh, William, and Bluhm, Hendrik. Direct Mapping of Band Positions in Doped and Undoped Hematite during Photoelectrochemical Water Splitting. United States: N. p., 2017. Web. https://doi.org/10.1021/acs.jpclett.7b02548.
Shavorskiy, Andrey, Ye, Xiaofei, Karslgolu, Osman, Poletayev, Andrey D., Hartl, Matthias, Zegkinoglou, Ioannis, Trotochaud, Lena, Nemsak, Slavomir, Schneider, Claus M., Crumlin, Ethan J., Axnanda, Stephanus, Liu, Zhi, Ross, Philip N., Chueh, William, & Bluhm, Hendrik. Direct Mapping of Band Positions in Doped and Undoped Hematite during Photoelectrochemical Water Splitting. United States. https://doi.org/10.1021/acs.jpclett.7b02548
Shavorskiy, Andrey, Ye, Xiaofei, Karslgolu, Osman, Poletayev, Andrey D., Hartl, Matthias, Zegkinoglou, Ioannis, Trotochaud, Lena, Nemsak, Slavomir, Schneider, Claus M., Crumlin, Ethan J., Axnanda, Stephanus, Liu, Zhi, Ross, Philip N., Chueh, William, and Bluhm, Hendrik. Mon . "Direct Mapping of Band Positions in Doped and Undoped Hematite during Photoelectrochemical Water Splitting". United States. https://doi.org/10.1021/acs.jpclett.7b02548. https://www.osti.gov/servlets/purl/1440006.
@article{osti_1440006,
title = {Direct Mapping of Band Positions in Doped and Undoped Hematite during Photoelectrochemical Water Splitting},
author = {Shavorskiy, Andrey and Ye, Xiaofei and Karslgolu, Osman and Poletayev, Andrey D. and Hartl, Matthias and Zegkinoglou, Ioannis and Trotochaud, Lena and Nemsak, Slavomir and Schneider, Claus M. and Crumlin, Ethan J. and Axnanda, Stephanus and Liu, Zhi and Ross, Philip N. and Chueh, William and Bluhm, Hendrik},
abstractNote = {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. Here, 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.},
doi = {10.1021/acs.jpclett.7b02548},
journal = {Journal of Physical Chemistry Letters},
number = 22,
volume = 8,
place = {United States},
year = {2017},
month = {10}
}

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