skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Covalent surface modification of gallium arsenide photocathodes for water splitting in highly acidic electrolyte

Abstract

Efficient water splitting using light as the only energy input requires stable semiconductor electrodes with favorable energetics for the water-oxidation and proton-reduction reactions. Strategies to tune electrode potentials using molecular dipoles adsorbed to the semiconductor surface have been pursued for decades but are often based on weak interactions and quickly react to desorb the molecule under conditions relevant to sustained photoelectrolysis. Here, we show that covalent attachment of fluorinated, aromatic molecules to p-GaAs(1 0 0) surfaces can be employed to tune the photocurrent onset potentials of p-GaAs(1 0 0) photocathodes and reduce the external energy required for water splitting. Results indicate that initial photocurrent onset potentials can be shifted by nearly 150 mV in pH -0.5 electrolyte under 1 Sun (1000 W m-2) illumination resulting from the covalently bound surface dipole. Furthermore, X-ray photoelectron spectroscopy analysis reveals that the covalent molecular dipole attachment is not robust under extended 50 h photoelectrolysis, the modified surface delays arsenic oxide formation that results in a p-GaAs(1 0 0) photoelectrode operating at a sustained photocurrent density of -20.5 mA cm-2 within -0.5 V of the reversible hydrogen electrode.

Authors:
 [1];  [2];  [1];  [1];  [1];  [3];  [1];  [2];  [1]; ORCiD logo [1]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  2. National Renewable Energy Lab. (NREL), Golden, CO (United States); Colorado School of Mines, Golden, CO (United States)
  3. Colorado School of Mines, Golden, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Fuel Cell Technologies Office (EE-3F)
OSTI Identifier:
1352131
Report Number(s):
NREL/JA-5900-67024
Journal ID: ISSN 1864-5631
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
ChemSusChem
Additional Journal Information:
Journal Volume: 10; Journal Issue: 4; Journal ID: ISSN 1864-5631
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; covalent surface attachment; gallium arsenide; photoelectrochemistry; surface dipole; water splitting

Citation Formats

Garner, Logan E., Steirer, K. Xerxes, Young, James L., Anderson, Nicholas C., Miller, Elisa M., Tinkham, Jonathan S., Deutsch, Todd G., Sellinger, Alan, Turner, John A., and Neale, Nathan R. Covalent surface modification of gallium arsenide photocathodes for water splitting in highly acidic electrolyte. United States: N. p., 2016. Web. doi:10.1002/cssc.201601408.
Garner, Logan E., Steirer, K. Xerxes, Young, James L., Anderson, Nicholas C., Miller, Elisa M., Tinkham, Jonathan S., Deutsch, Todd G., Sellinger, Alan, Turner, John A., & Neale, Nathan R. Covalent surface modification of gallium arsenide photocathodes for water splitting in highly acidic electrolyte. United States. doi:10.1002/cssc.201601408.
Garner, Logan E., Steirer, K. Xerxes, Young, James L., Anderson, Nicholas C., Miller, Elisa M., Tinkham, Jonathan S., Deutsch, Todd G., Sellinger, Alan, Turner, John A., and Neale, Nathan R. Mon . "Covalent surface modification of gallium arsenide photocathodes for water splitting in highly acidic electrolyte". United States. doi:10.1002/cssc.201601408. https://www.osti.gov/servlets/purl/1352131.
@article{osti_1352131,
title = {Covalent surface modification of gallium arsenide photocathodes for water splitting in highly acidic electrolyte},
author = {Garner, Logan E. and Steirer, K. Xerxes and Young, James L. and Anderson, Nicholas C. and Miller, Elisa M. and Tinkham, Jonathan S. and Deutsch, Todd G. and Sellinger, Alan and Turner, John A. and Neale, Nathan R.},
abstractNote = {Efficient water splitting using light as the only energy input requires stable semiconductor electrodes with favorable energetics for the water-oxidation and proton-reduction reactions. Strategies to tune electrode potentials using molecular dipoles adsorbed to the semiconductor surface have been pursued for decades but are often based on weak interactions and quickly react to desorb the molecule under conditions relevant to sustained photoelectrolysis. Here, we show that covalent attachment of fluorinated, aromatic molecules to p-GaAs(1 0 0) surfaces can be employed to tune the photocurrent onset potentials of p-GaAs(1 0 0) photocathodes and reduce the external energy required for water splitting. Results indicate that initial photocurrent onset potentials can be shifted by nearly 150 mV in pH -0.5 electrolyte under 1 Sun (1000 W m-2) illumination resulting from the covalently bound surface dipole. Furthermore, X-ray photoelectron spectroscopy analysis reveals that the covalent molecular dipole attachment is not robust under extended 50 h photoelectrolysis, the modified surface delays arsenic oxide formation that results in a p-GaAs(1 0 0) photoelectrode operating at a sustained photocurrent density of -20.5 mA cm-2 within -0.5 V of the reversible hydrogen electrode.},
doi = {10.1002/cssc.201601408},
journal = {ChemSusChem},
number = 4,
volume = 10,
place = {United States},
year = {2016},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 4 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Solar conversion efficiency of photovoltaic and photoelectrolysis cells with carrier multiplication absorbers
journal, October 2006

  • Hanna, M. C.; Nozik, A. J.
  • Journal of Applied Physics, Vol. 100, Issue 7
  • DOI: 10.1063/1.2356795

Heterogeneous photocatalyst materials for water splitting
journal, January 2009

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

Overall Water Splitting on (Ga 1 - x Zn x )(N 1 - x O x ) Solid Solution Photocatalyst:  Relationship between Physical Properties and Photocatalytic Activity
journal, November 2005

  • Maeda, Kazuhiko; Teramura, Kentaro; Takata, Tsuyoshi
  • The Journal of Physical Chemistry B, Vol. 109, Issue 43
  • DOI: 10.1021/jp053499y

Photoelectrochemical Tandem Cells for Solar Water Splitting
journal, July 2013

  • Prévot, Mathieu S.; Sivula, Kevin
  • The Journal of Physical Chemistry C, Vol. 117, Issue 35
  • DOI: 10.1021/jp405291g

Chemical and Electrical Passivation of Single-Crystal Silicon(100) Surfaces through a Two-Step Chlorination/Alkylation Process
journal, August 2006

  • Nemanick, E. Joseph; Hurley, Patrick T.; Webb, Lauren J.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 30
  • DOI: 10.1021/jp056773x

Wireless Solar Water Splitting Using Silicon-Based Semiconductors and Earth-Abundant Catalysts
journal, September 2011


Dual Oxygen and Tungsten Vacancies on a WO 3 Photoanode for Enhanced Water Oxidation
journal, August 2016


Heck Coupling of Olefins to Mixed Methyl/Thienyl Monolayers on Si(111) Surfaces
journal, June 2013

  • O’Leary, Leslie E.; Rose, Michael J.; Ding, Tina X.
  • Journal of the American Chemical Society, Vol. 135, Issue 27
  • DOI: 10.1021/ja402495e

The hydrogen economy: Its history
journal, February 2013


Modification of the Surface Properties of Indium Tin Oxide with Benzylphosphonic Acids: A Joint Experimental and Theoretical Study
journal, November 2009

  • Hotchkiss, Peter J.; Li, Hong; Paramonov, Pavel B.
  • Advanced Materials, Vol. 21, Issue 44
  • DOI: 10.1002/adma.200900502

Highly efficient water splitting by a dual-absorber tandem cell
journal, November 2012


Photo-electrochemical hydrogen generation from water using solar energy. Materials-related aspects
journal, October 2002


Inorganic Materials as Catalysts for Photochemical Splitting of Water
journal, January 2008


Heterojunction band offset engineering
journal, January 1996


Water photolysis at 12.3% efficiency via perovskite photovoltaics and Earth-abundant catalysts
journal, September 2014


Solar-to-hydrogen efficiency: shining light on photoelectrochemical device performance
journal, January 2016

  • Döscher, H.; Young, J. L.; Geisz, J. F.
  • Energy & Environmental Science, Vol. 9, Issue 1
  • DOI: 10.1039/C5EE03206G

Fluorinated Reduced Graphene Oxide as an Interlayer in Li–S Batteries
journal, October 2015


Efficient solar water splitting by enhanced charge separation in a bismuth vanadate-silicon tandem photoelectrode
journal, July 2013

  • Abdi, Fatwa F.; Han, Lihao; Smets, Arno H. M.
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3195

Potential importance of hydrogen as a future solution to environmental and transportation problems
journal, August 2008


Dual Oxygen and Tungsten Vacancies on a WO 3 Photoanode for Enhanced Water Oxidation
journal, August 2016

  • Ma, Ming; Zhang, Kan; Li, Ping
  • Angewandte Chemie International Edition, Vol. 55, Issue 39
  • DOI: 10.1002/anie.201605247

Phosphonic Acid Modification of GaInP 2 Photocathodes Toward Unbiased Photoelectrochemical Water Splitting
journal, May 2015

  • MacLeod, Bradley A.; Steirer, K. Xerxes; Young, James L.
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 21
  • DOI: 10.1021/acsami.5b01814

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

Remarkable stability of unmodified GaAs photocathodes during hydrogen evolution in acidic electrolyte
journal, January 2016

  • Young, J. L.; Steirer, K. X.; Dzara, M. J.
  • Journal of Materials Chemistry A, Vol. 4, Issue 8
  • DOI: 10.1039/C5TA07648J

Sunlight absorption in water – efficiency and design implications for photoelectrochemical devices
journal, January 2014

  • Döscher, H.; Geisz, J. F.; Deutsch, T. G.
  • Energy Environ. Sci., Vol. 7, Issue 9
  • DOI: 10.1039/C4EE01753F