Photoelectrochemical oxidation of anions by WO3 in aqueous and nonaqueous electrolytes

Qixi Mi, Robert H. Coridan, Bruce S. Brunschwig, Harry B. Gray, Nathan S Lewis

Research output: Contribution to journalArticle

42 Citations (Scopus)

Abstract

The behavior of WO3 photoanodes has been investigated in contact with a combination of four anions (Cl-, CH3SO 3-, HSO4-, and ClO4 -) and three solvents (water, acetonitrile, and propylene carbonate), to elucidate the role of the semiconductor surface, the electrolyte, and redox kinetics on the current density vs. potential properties of n-type WO 3. In 1.0 M aqueous strong acids, although the flat-band potential (Efb) of WO3 was dominated by electrochemical intercalation of protons into WO3, the nature of the electrolyte influenced the onset potential (Eon) of the anodic photocurrent. In aprotic solvents, the electrolyte anion shifted both Efb and E on, but did not significantly alter the overall profile of the voltammetric data. For 0.50 M tetra(n-butyl)ammonium perchlorate in propylene carbonate, the internal quantum yield exceeded unity at excitation wavelengths of 300-390 nm, indicative of current doubling. A regenerative photoelectrochemical cell based on the reversible redox couple B 10Br10-/2- in acetonitrile, with a solution potential of ∼1.7 V vs. the normal hydrogen electrode, exhibited an open-circuit photovoltage of 1.32 V under 100 mW cm-2 of simulated Air Mass 1.5 global illumination.

Original languageEnglish
Pages (from-to)2646-2653
Number of pages8
JournalEnergy and Environmental Science
Volume6
Issue number9
DOIs
Publication statusPublished - Sep 2013

Fingerprint

electrolyte
Electrolytes
Anions
anion
Negative ions
Acetonitrile
oxidation
Oxidation
Propylene
Carbonates
Photoelectrochemical cells
carbonate
perchlorate
Quantum yield
Intercalation
Photocurrents
air mass
Protons
Hydrogen
electrode

ASJC Scopus subject areas

  • Renewable Energy, Sustainability and the Environment
  • Environmental Chemistry
  • Pollution
  • Nuclear Energy and Engineering

Cite this

Photoelectrochemical oxidation of anions by WO3 in aqueous and nonaqueous electrolytes. / Mi, Qixi; Coridan, Robert H.; Brunschwig, Bruce S.; Gray, Harry B.; Lewis, Nathan S.

In: Energy and Environmental Science, Vol. 6, No. 9, 09.2013, p. 2646-2653.

Research output: Contribution to journalArticle

Mi, Qixi ; Coridan, Robert H. ; Brunschwig, Bruce S. ; Gray, Harry B. ; Lewis, Nathan S. / Photoelectrochemical oxidation of anions by WO3 in aqueous and nonaqueous electrolytes. In: Energy and Environmental Science. 2013 ; Vol. 6, No. 9. pp. 2646-2653.
@article{46140f622d0341e39860a46a93a2876d,
title = "Photoelectrochemical oxidation of anions by WO3 in aqueous and nonaqueous electrolytes",
abstract = "The behavior of WO3 photoanodes has been investigated in contact with a combination of four anions (Cl-, CH3SO 3-, HSO4-, and ClO4 -) and three solvents (water, acetonitrile, and propylene carbonate), to elucidate the role of the semiconductor surface, the electrolyte, and redox kinetics on the current density vs. potential properties of n-type WO 3. In 1.0 M aqueous strong acids, although the flat-band potential (Efb) of WO3 was dominated by electrochemical intercalation of protons into WO3, the nature of the electrolyte influenced the onset potential (Eon) of the anodic photocurrent. In aprotic solvents, the electrolyte anion shifted both Efb and E on, but did not significantly alter the overall profile of the voltammetric data. For 0.50 M tetra(n-butyl)ammonium perchlorate in propylene carbonate, the internal quantum yield exceeded unity at excitation wavelengths of 300-390 nm, indicative of current doubling. A regenerative photoelectrochemical cell based on the reversible redox couple B 10Br10-/2- in acetonitrile, with a solution potential of ∼1.7 V vs. the normal hydrogen electrode, exhibited an open-circuit photovoltage of 1.32 V under 100 mW cm-2 of simulated Air Mass 1.5 global illumination.",
author = "Qixi Mi and Coridan, {Robert H.} and Brunschwig, {Bruce S.} and Gray, {Harry B.} and Lewis, {Nathan S}",
year = "2013",
month = "9",
doi = "10.1039/c3ee40712h",
language = "English",
volume = "6",
pages = "2646--2653",
journal = "Energy and Environmental Science",
issn = "1754-5692",
publisher = "Royal Society of Chemistry",
number = "9",

}

TY - JOUR

T1 - Photoelectrochemical oxidation of anions by WO3 in aqueous and nonaqueous electrolytes

AU - Mi, Qixi

AU - Coridan, Robert H.

AU - Brunschwig, Bruce S.

AU - Gray, Harry B.

AU - Lewis, Nathan S

PY - 2013/9

Y1 - 2013/9

N2 - The behavior of WO3 photoanodes has been investigated in contact with a combination of four anions (Cl-, CH3SO 3-, HSO4-, and ClO4 -) and three solvents (water, acetonitrile, and propylene carbonate), to elucidate the role of the semiconductor surface, the electrolyte, and redox kinetics on the current density vs. potential properties of n-type WO 3. In 1.0 M aqueous strong acids, although the flat-band potential (Efb) of WO3 was dominated by electrochemical intercalation of protons into WO3, the nature of the electrolyte influenced the onset potential (Eon) of the anodic photocurrent. In aprotic solvents, the electrolyte anion shifted both Efb and E on, but did not significantly alter the overall profile of the voltammetric data. For 0.50 M tetra(n-butyl)ammonium perchlorate in propylene carbonate, the internal quantum yield exceeded unity at excitation wavelengths of 300-390 nm, indicative of current doubling. A regenerative photoelectrochemical cell based on the reversible redox couple B 10Br10-/2- in acetonitrile, with a solution potential of ∼1.7 V vs. the normal hydrogen electrode, exhibited an open-circuit photovoltage of 1.32 V under 100 mW cm-2 of simulated Air Mass 1.5 global illumination.

AB - The behavior of WO3 photoanodes has been investigated in contact with a combination of four anions (Cl-, CH3SO 3-, HSO4-, and ClO4 -) and three solvents (water, acetonitrile, and propylene carbonate), to elucidate the role of the semiconductor surface, the electrolyte, and redox kinetics on the current density vs. potential properties of n-type WO 3. In 1.0 M aqueous strong acids, although the flat-band potential (Efb) of WO3 was dominated by electrochemical intercalation of protons into WO3, the nature of the electrolyte influenced the onset potential (Eon) of the anodic photocurrent. In aprotic solvents, the electrolyte anion shifted both Efb and E on, but did not significantly alter the overall profile of the voltammetric data. For 0.50 M tetra(n-butyl)ammonium perchlorate in propylene carbonate, the internal quantum yield exceeded unity at excitation wavelengths of 300-390 nm, indicative of current doubling. A regenerative photoelectrochemical cell based on the reversible redox couple B 10Br10-/2- in acetonitrile, with a solution potential of ∼1.7 V vs. the normal hydrogen electrode, exhibited an open-circuit photovoltage of 1.32 V under 100 mW cm-2 of simulated Air Mass 1.5 global illumination.

UR - http://www.scopus.com/inward/record.url?scp=84882352486&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84882352486&partnerID=8YFLogxK

U2 - 10.1039/c3ee40712h

DO - 10.1039/c3ee40712h

M3 - Article

VL - 6

SP - 2646

EP - 2653

JO - Energy and Environmental Science

JF - Energy and Environmental Science

SN - 1754-5692

IS - 9

ER -