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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]
+ Show Author Affiliations
  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. doi:10.1021/acs.jpclett.7b02548.
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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
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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.
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@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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Works referenced in this record:

Electrochemical Photolysis of Water at a Semiconductor Electrode
journal, July 1972

  • Fujishima, Akira; Honda, Kenichi
  • Nature, Vol. 238, Issue 5358, p. 37-38
  • DOI: 10.1038/238037a0

Photoelectrochemical cells
journal, November 2001

Heterogeneous photocatalyst materials for water splitting
journal, January 2009

  • Kudo, Akihiko; Miseki, Yugo
  • Chem. Soc. Rev., Vol. 38, Issue 1
  • DOI: 10.1039/B800489G

Solar Water Splitting Cells
journal, November 2010

  • Walter, Michael G.; Warren, Emily L.; McKone, James R.
  • Chemical Reviews, Vol. 110, Issue 11, p. 6446-6473
  • DOI: 10.1021/cr1002326

Titanium incorporation into hematite photoelectrodes: theoretical considerations and experimental observations
journal, January 2014

  • Kronawitter, C. X.; Zegkinoglou, I.; Shen, S. -H.
  • Energy Environ. Sci., Vol. 7, Issue 10
  • DOI: 10.1039/C4EE01066C

Enhancement of Photoelectrochemical Hydrogen Production from Hematite Thin Films by the Introduction of Ti and Si
journal, November 2007

  • Glasscock, Julie A.; Barnes, Piers R. F.; Plumb, Ian C.
  • The Journal of Physical Chemistry C, Vol. 111, Issue 44
  • DOI: 10.1021/jp074556l

Photoelectrochemical Performance of Nanostructured Ti- and Sn-Doped α-Fe 2 O 3 Photoanodes
journal, December 2010

  • Hahn, Nathan T.; Mullins, C. Buddie
  • Chemistry of Materials, Vol. 22, Issue 23
  • DOI: 10.1021/cm1026078

Facile Synthesis of Highly Photoactive α-Fe 2 O 3 -Based Films for Water Oxidation
journal, August 2011

  • Wang, Gongming; Ling, Yichuan; Wheeler, Damon A.
  • Nano Letters, Vol. 11, Issue 8
  • DOI: 10.1021/nl202316j

A transparent Ti4+ doped hematite photoanode protectively grown by a facile hydrothermal method
journal, January 2013

  • Cao, Dapeng; Luo, Wenjun; Li, Mingxue
  • CrystEngComm, Vol. 15, Issue 13
  • DOI: 10.1039/c3ce26811j

Micro-Nano-Structured Fe 2 O 3 :Ti/ZnFe 2 O 4 Heterojunction Films for Water Oxidation
journal, July 2012

  • Miao, Chunhui; Ji, Shulin; Xu, Guoping
  • ACS Applied Materials & Interfaces, Vol. 4, Issue 8
  • DOI: 10.1021/am3011466

Physical and photoelectrochemical characterization of Ti-doped hematite photoanodes prepared by solution growth
journal, January 2013

  • Shen, Shaohua; Kronawitter, Coleman X.; Wheeler, Damon A.
  • Journal of Materials Chemistry A, Vol. 1, Issue 46
  • DOI: 10.1039/c3ta13453a

Visible Light Driven Photoelectrochemical Water Oxidation by Zn- and Ti-Doped Hematite Nanostructures
journal, April 2014

  • Mirbagheri, Naghmehalsadat; Wang, Degao; Peng, Cheng
  • ACS Catalysis, Vol. 4, Issue 6
  • DOI: 10.1021/cs500372v

Facile post-growth doping of nanostructured hematite photoanodes for enhanced photoelectrochemical water oxidation
journal, January 2013

  • Franking, Ryan; Li, Linsen; Lukowski, Mark A.
  • Energy Environ. Sci., Vol. 6, Issue 2
  • DOI: 10.1039/C2EE23837C

Charge carrier trapping, recombination and transfer in hematite (α-Fe2O3) water splitting photoanodes
journal, January 2013

  • Barroso, Monica; Pendlebury, Stephanie R.; Cowan, Alexander J.
  • Chemical Science, Vol. 4, Issue 7
  • DOI: 10.1039/c3sc50496d

Back Electron–Hole Recombination in Hematite Photoanodes for Water Splitting
journal, January 2014

  • Le Formal, Florian; Pendlebury, Stephanie R.; Cornuz, Maurin
  • Journal of the American Chemical Society, Vol. 136, Issue 6
  • DOI: 10.1021/ja412058x

Water Oxidation on Hematite Photoelectrodes: Insight into the Nature of Surface States through In Situ Spectroelectrochemistry
journal, May 2014

  • Klahr, Benjamin; Hamann, Thomas
  • The Journal of Physical Chemistry C, Vol. 118, Issue 19
  • DOI: 10.1021/jp500543z

Water Oxidation at Hematite Photoelectrodes: The Role of Surface States
journal, February 2012

  • Klahr, Benjamin; Gimenez, Sixto; Fabregat-Santiago, Francisco
  • Journal of the American Chemical Society, Vol. 134, Issue 9
  • DOI: 10.1021/ja210755h

Detection of Intermediate Species in Oxygen Evolution on Hematite Electrodes Using Spectroelectrochemical Measurements
journal, October 2016

  • Takashima, Toshihiro; Ishikawa, Koki; Irie, Hiroshi
  • The Journal of Physical Chemistry C, Vol. 120, Issue 43
  • DOI: 10.1021/acs.jpcc.6b07978

Toward Settling the Debate on the Role of Fe 2 O 3 Surface States for Water Splitting
journal, October 2015

  • Yatom, Natav; Neufeld, Ofer; Caspary Toroker, Maytal
  • The Journal of Physical Chemistry C, Vol. 119, Issue 44
  • DOI: 10.1021/acs.jpcc.5b06128

Electrochemical and photoelectrochemical investigation of water oxidation with hematite electrodes
journal, January 2012

  • Klahr, Benjamin; Gimenez, Sixto; Fabregat-Santiago, Francisco
  • Energy & Environmental Science, Vol. 5, Issue 6
  • DOI: 10.1039/c2ee21414h

Highly photoactive Ti-doped α-Fe 2 O 3 thin film electrodes: resurrection of the dead layer
journal, January 2013

  • Zandi, Omid; Klahr, Benjamin M.; Hamann, Thomas W.
  • Energy Environ. Sci., Vol. 6, Issue 2
  • DOI: 10.1039/C2EE23620F

Energetics and kinetics of light-driven oxygen evolution at semiconductor electrodes: the example of hematite
journal, November 2012

Enhanced Water Splitting Efficiency Through Selective Surface State Removal
journal, April 2014

  • Zandi, Omid; Hamann, Thomas W.
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 9
  • DOI: 10.1021/jz500535a

Observation and Alteration of Surface States of Hematite Photoelectrodes
journal, April 2014

  • Du, Chun; Zhang, Ming; Jang, Ji-Wook
  • The Journal of Physical Chemistry C, Vol. 118, Issue 30
  • DOI: 10.1021/jp5006346

Surface treatment with Al 3+ on a Ti-doped α-Fe 2 O 3 nanorod array photoanode for efficient photoelectrochemical water splitting
journal, January 2014

  • Fu, Zewen; Jiang, Tengfei; Zhang, Lijing
  • Journal of Materials Chemistry A, Vol. 2, Issue 33
  • DOI: 10.1039/C4TA02527J

Cathodic shift in onset potential of solar oxygen evolution on hematite by 13-group oxide overlayers
journal, January 2011

  • Hisatomi, Takashi; Le Formal, Florian; Cornuz, Maurin
  • Energy & Environmental Science, Vol. 4, Issue 7
  • DOI: 10.1039/c1ee01194d

A novel strategy for surface treatment on hematite photoanode for efficient water oxidation
journal, January 2013

  • Xi, Lifei; Chiam, Sing Yang; Mak, Wai Fatt
  • Chem. Sci., Vol. 4, Issue 1
  • DOI: 10.1039/C2SC20881D

Kinetics of light-driven oxygen evolution at α-Fe 2 O 3 electrodes
journal, January 2012

  • Peter, Laurence M.; Wijayantha, K. G. Upul; Tahir, Asif A.
  • Faraday Discuss., Vol. 155
  • DOI: 10.1039/C1FD00079A

The Transient Photocurrent and Photovoltage Behavior of a Hematite Photoanode under Working Conditions and the Influence of Surface Treatments
journal, December 2012

  • Le Formal, Florian; Sivula, Kevin; Grätzel, Michael
  • The Journal of Physical Chemistry C, Vol. 116, Issue 51
  • DOI: 10.1021/jp308591k

Enhanced photoelectrochemical water-splitting performance of semiconductors by surface passivation layers
journal, January 2014

  • Liu, Rui; Zheng, Zhi; Spurgeon, Joshua
  • Energy Environ. Sci., Vol. 7, Issue 8
  • DOI: 10.1039/C4EE00450G

The Role of Cobalt Phosphate in Enhancing the Photocatalytic Activity of α-Fe 2 O 3 toward Water Oxidation
journal, September 2011

  • Barroso, Monica; Cowan, Alexander J.; Pendlebury, Stephanie R.
  • Journal of the American Chemical Society, Vol. 133, Issue 38
  • DOI: 10.1021/ja205325v

The Role of Surface States in the Oxygen Evolution Reaction on Hematite
journal, October 2014

  • Iandolo, Beniamino; Hellman, Anders
  • Angewandte Chemie International Edition, Vol. 53, Issue 49
  • DOI: 10.1002/anie.201406800

Dynamics of photogenerated holes in surface modified  -Fe2O3 photoanodes for solar water splitting
journal, July 2012

  • Barroso, M.; Mesa, C. A.; Pendlebury, S. R.
  • Proceedings of the National Academy of Sciences, Vol. 109, Issue 39
  • DOI: 10.1073/pnas.1118326109

Correlating long-lived photogenerated hole populations with photocurrent densities in hematite water oxidation photoanodes
journal, January 2012

  • Pendlebury, Stephanie R.; Cowan, Alexander J.; Barroso, Monica
  • Energy Environ. Sci., Vol. 5, Issue 4
  • DOI: 10.1039/C1EE02567H

Photoelectron spectroscopy of surfaces under humid conditions
journal, March 2010

Using “Tender” X-ray Ambient Pressure X-Ray Photoelectron Spectroscopy as A Direct Probe of Solid-Liquid Interface
journal, May 2015

  • Axnanda, Stephanus; Crumlin, Ethan J.; Mao, Baohua
  • Scientific Reports, Vol. 5, Issue 1
  • DOI: 10.1038/srep09788

Thermally-enhanced minority carrier collection in hematite during photoelectrochemical water and sulfite oxidation
journal, January 2015

  • Ye, Xiaofei; Yang, Jing; Boloor, Madhur
  • Journal of Materials Chemistry A, Vol. 3, Issue 20
  • DOI: 10.1039/C5TA02108A

The impact of semiconductors on the concepts of electrochemistry
journal, November 1990

Direct observation of the energetics at a semiconductor/liquid junction by operando X-ray photoelectron spectroscopy
journal, January 2015

  • Lichterman, Michael F.; Hu, Shu; Richter, Matthias H.
  • Energy & Environmental Science, Vol. 8, Issue 8
  • DOI: 10.1039/C5EE01014D

Physical Chemistry of Semiconductor−Liquid Interfaces
journal, January 1996

  • Nozik, Arthur J.; Memming, Rüdiger
  • The Journal of Physical Chemistry, Vol. 100, Issue 31
  • DOI: 10.1021/jp953720e

Preparation, characterization and photoelectronic properties of germanium-substituted Fe2O3 single crystals
journal, January 1985

  • Sieber, K. D.; Sanchez, C.; Turner, J. E.
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 81, Issue 5
  • DOI: 10.1039/f19858101263

Visible Light-Induced Water Oxidation on Mesoscopic α-Fe 2 O 3 Films Made by Ultrasonic Spray Pyrolysis
journal, September 2005

  • Duret, Alexis; Grätzel, Michael
  • The Journal of Physical Chemistry B, Vol. 109, Issue 36
  • DOI: 10.1021/jp044127c

Aqueous solution/metal interfaces investigated in operando by photoelectron spectroscopy
journal, January 2015

  • Karslıoğlu, O.; Nemšák, S.; Zegkinoglou, I.
  • Faraday Discussions, Vol. 180
  • DOI: 10.1039/C5FD00003C

Unravelling the electrochemical double layer by direct probing of the solid/liquid interface
journal, August 2016

  • Favaro, Marco; Jeong, Beomgyun; Ross, Philip N.
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms12695

Surface space-charge dynamics and surface recombination on silicon (111) surfaces measured with combined laser and synchrotron radiation
journal, March 1990

Band Bending in Semiconductors: Chemical and Physical Consequences at Surfaces and Interfaces
journal, June 2012

  • Zhang, Zhen; Yates, John T.
  • Chemical Reviews, Vol. 112, Issue 10
  • DOI: 10.1021/cr3000626

Electrolytic decomposition and photodecomposition of compound semiconductors in contact with electrolytes
journal, July 1978

  • Gerischer, Heinz
  • Journal of Vacuum Science and Technology, Vol. 15, Issue 4
  • DOI: 10.1116/1.569800

Thermodynamic Oxidation and Reduction Potentials of Photocatalytic Semiconductors in Aqueous Solution
journal, September 2012

  • Chen, Shiyou; Wang, Lin-Wang
  • Chemistry of Materials, Vol. 24, Issue 18
  • DOI: 10.1021/cm302533s

Investigation of photoelectrochemical corrosion of semiconductors. 1
journal, November 1980

  • Frese, K. W.; Madou, M. J.; Morrison, S. R.
  • The Journal of Physical Chemistry, Vol. 84, Issue 24
  • DOI: 10.1021/j100461a008

Corrosion of III-V compounds; a comparative study of GaAs and InP
journal, October 1991

  • Allongue, P.; Blonkowski, S.
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 316, Issue 1-2
  • DOI: 10.1016/0022-0728(91)87036-4
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