Direct in Situ Measurement of Charge Transfer Processes During Photoelectrochemical Water Oxidation on Catalyzed Hematite
Abstract
Electrocatalysts improve the efficiency of light-absorbing semiconductor photoanodes driving the oxygen evolution reaction, but the precise function(s) of the electrocatalysts remains unclear. We directly measure, for the first time, the interface carrier transport properties of a prototypical visible-light-absorbing semiconductor, α-Fe2O3, in contact with one of the fastest known water oxidation catalysts, Ni0.8Fe0.2Ox, by directly measuring/controlling the current and/or voltage at the Ni0.8Fe0.2Ox catalyst layer using a second working electrode. The measurements demonstrate that the majority of photogenerated holes in α-Fe2O3 directly transfer to the catalyst film over a wide range of conditions and that the Ni0.8Fe0.2Ox is oxidized by photoholes to an operating potential sufficient to drive water oxidation at rates that match the photocurrent generated by the α-Fe2O3. The Ni0.8Fe0.2Ox therefore acts as both a hole-collecting contact and a catalyst for the photoelectrochemical water oxidation process. Separate measurements show that the illuminated junction photovoltage across the α-Fe2O3|Ni0.8Fe0.2Ox interface is significantly decreased by the oxidation of Ni2+ to Ni3+ and the associated increase in the Ni0.8Fe0.2Ox electrical conductivity. Finally, in sum, the results illustrate the underlying operative charge-transfer and photovoltage generation mechanisms of catalyzed photoelectrodes, thus guiding their continued improvement.
- Authors:
-
[2];
[1]
- Department of Chemistry and Biochemistry, Materials Science Institute, University of Oregon, Eugene, Oregon 97403, United States
- Department of Chemistry, Michigan State University, East Lansing, Michigan 48824, United States
- Publication Date:
- Research Org.:
- Univ. of Oregon, Eugene, OR (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1375497
- Alternate Identifier(s):
- OSTI ID: 1421383
- Grant/Contract Number:
- SC0014279
- Resource Type:
- Published Article
- Journal Name:
- ACS Central Science
- Additional Journal Information:
- Journal Name: ACS Central Science Journal Volume: 3 Journal Issue: 9; Journal ID: ISSN 2374-7943
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Qiu, Jingjing, Hajibabaei, Hamed, Nellist, Michael R., Laskowski, Forrest A. L., Hamann, Thomas W., and Boettcher, Shannon W. Direct in Situ Measurement of Charge Transfer Processes During Photoelectrochemical Water Oxidation on Catalyzed Hematite. United States: N. p., 2017.
Web. doi:10.1021/acscentsci.7b00310.
Qiu, Jingjing, Hajibabaei, Hamed, Nellist, Michael R., Laskowski, Forrest A. L., Hamann, Thomas W., & Boettcher, Shannon W. Direct in Situ Measurement of Charge Transfer Processes During Photoelectrochemical Water Oxidation on Catalyzed Hematite. United States. https://doi.org/10.1021/acscentsci.7b00310
Qiu, Jingjing, Hajibabaei, Hamed, Nellist, Michael R., Laskowski, Forrest A. L., Hamann, Thomas W., and Boettcher, Shannon W. Thu .
"Direct in Situ Measurement of Charge Transfer Processes During Photoelectrochemical Water Oxidation on Catalyzed Hematite". United States. https://doi.org/10.1021/acscentsci.7b00310.
@article{osti_1375497,
title = {Direct in Situ Measurement of Charge Transfer Processes During Photoelectrochemical Water Oxidation on Catalyzed Hematite},
author = {Qiu, Jingjing and Hajibabaei, Hamed and Nellist, Michael R. and Laskowski, Forrest A. L. and Hamann, Thomas W. and Boettcher, Shannon W.},
abstractNote = {Electrocatalysts improve the efficiency of light-absorbing semiconductor photoanodes driving the oxygen evolution reaction, but the precise function(s) of the electrocatalysts remains unclear. We directly measure, for the first time, the interface carrier transport properties of a prototypical visible-light-absorbing semiconductor, α-Fe2O3, in contact with one of the fastest known water oxidation catalysts, Ni0.8Fe0.2Ox, by directly measuring/controlling the current and/or voltage at the Ni0.8Fe0.2Ox catalyst layer using a second working electrode. The measurements demonstrate that the majority of photogenerated holes in α-Fe2O3 directly transfer to the catalyst film over a wide range of conditions and that the Ni0.8Fe0.2Ox is oxidized by photoholes to an operating potential sufficient to drive water oxidation at rates that match the photocurrent generated by the α-Fe2O3. The Ni0.8Fe0.2Ox therefore acts as both a hole-collecting contact and a catalyst for the photoelectrochemical water oxidation process. Separate measurements show that the illuminated junction photovoltage across the α-Fe2O3|Ni0.8Fe0.2Ox interface is significantly decreased by the oxidation of Ni2+ to Ni3+ and the associated increase in the Ni0.8Fe0.2Ox electrical conductivity. Finally, in sum, the results illustrate the underlying operative charge-transfer and photovoltage generation mechanisms of catalyzed photoelectrodes, thus guiding their continued improvement.},
doi = {10.1021/acscentsci.7b00310},
journal = {ACS Central Science},
number = 9,
volume = 3,
place = {United States},
year = {Thu Aug 17 00:00:00 EDT 2017},
month = {Thu Aug 17 00:00:00 EDT 2017}
}
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https://doi.org/10.1021/acscentsci.7b00310
https://doi.org/10.1021/acscentsci.7b00310
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Cited by: 46 works
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Works referencing / citing this record:
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