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Title: Light-Driven Water Splitting Mediated by Photogenerated Bromine

Abstract

Light-driven water splitting was attained using a dye-sensitized mesoporous oxide film and the oxidation of bromide (Br–) to bromine (Br 2) or tribromide (Br 3–). The chemical oxidant (Br 2 or Br 3–) is formed during illumination at the photoanode and used as a sacrificial oxidant to drive a water oxidation catalyst (WOC), here shown using [Ru(bda)(pic) 2], (1; pic=picoline, bda=2,2'-bipyridine-6,6'-dicarboxylate). The photochemical oxidation of bromide produces a chemical oxidant with a possibility of 1.09 V vs. NHE for the Br 2/Br– couple or 1.05 V vs. NHE for the Br 3–/Br– couple, which is sufficient to drive water oxidation at 1 (Ru V/IV≈1.0 V vs. NHE at pH 5.6). At pH 5.6, using a 0.2 M acetate buffer containing 40 mm LiBr and the [Ru(4,4'-PO3H2-bpy)(bpy) 2] 2+ (RuP 2+, bpy=2,2'-bipyridine) chromophore dye on a SnO 2/TiO 2 core–shell electrode resulted in a photocurrent density of around 1.2 mA cm –2 under approximately 1 Sun illumination and a Faradaic efficiency upon addition of 1 of 77 % for oxygen evolution.

Authors:
ORCiD logo [1];  [2];  [2]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [2]
  1. Florida International Univ., Miami, FL (United States)
  2. Univ. of North Carolina, Chapel Hill, NC (United States)
  3. Texas Christian Univ. (TCU), Fort Worth, TX (United States)
Publication Date:
Research Org.:
Univ. of North Carolina, Chapel Hill, NC (United States). Energy Frontier Research Center (EFRC) Center for Solar Fuels (UNC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1470106
Alternate Identifier(s):
OSTI ID: 1423382
Grant/Contract Number:  
SC0001011
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Volume: 57; Journal Issue: 13; Related Information: UNC partners with University of North Carolina (lead); Duke University; University of Florida; Georgia Institute of Technology; University; North Carolina Central University; Research Triangle Institute; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; energy storage; photochemistry; photoelectrochemistry; water oxidation; water splitting

Citation Formats

Sheridan, Matthew V., Wang, Ying, Wang, Degao, Troian-Gautier, Ludovic, Dares, Christopher J., Sherman, Benjamin D., and Meyer, Thomas J. Light-Driven Water Splitting Mediated by Photogenerated Bromine. United States: N. p., 2018. Web. doi:10.1002/anie.201708879.
Sheridan, Matthew V., Wang, Ying, Wang, Degao, Troian-Gautier, Ludovic, Dares, Christopher J., Sherman, Benjamin D., & Meyer, Thomas J. Light-Driven Water Splitting Mediated by Photogenerated Bromine. United States. https://doi.org/10.1002/anie.201708879
Sheridan, Matthew V., Wang, Ying, Wang, Degao, Troian-Gautier, Ludovic, Dares, Christopher J., Sherman, Benjamin D., and Meyer, Thomas J. Wed . "Light-Driven Water Splitting Mediated by Photogenerated Bromine". United States. https://doi.org/10.1002/anie.201708879. https://www.osti.gov/servlets/purl/1470106.
@article{osti_1470106,
title = {Light-Driven Water Splitting Mediated by Photogenerated Bromine},
author = {Sheridan, Matthew V. and Wang, Ying and Wang, Degao and Troian-Gautier, Ludovic and Dares, Christopher J. and Sherman, Benjamin D. and Meyer, Thomas J.},
abstractNote = {Light-driven water splitting was attained using a dye-sensitized mesoporous oxide film and the oxidation of bromide (Br–) to bromine (Br2) or tribromide (Br3–). The chemical oxidant (Br2 or Br3–) is formed during illumination at the photoanode and used as a sacrificial oxidant to drive a water oxidation catalyst (WOC), here shown using [Ru(bda)(pic)2], (1; pic=picoline, bda=2,2'-bipyridine-6,6'-dicarboxylate). The photochemical oxidation of bromide produces a chemical oxidant with a possibility of 1.09 V vs. NHE for the Br2/Br– couple or 1.05 V vs. NHE for the Br3–/Br– couple, which is sufficient to drive water oxidation at 1 (RuV/IV≈1.0 V vs. NHE at pH 5.6). At pH 5.6, using a 0.2 M acetate buffer containing 40 mm LiBr and the [Ru(4,4'-PO3H2-bpy)(bpy)2]2+ (RuP2+, bpy=2,2'-bipyridine) chromophore dye on a SnO2/TiO2 core–shell electrode resulted in a photocurrent density of around 1.2 mA cm–2 under approximately 1 Sun illumination and a Faradaic efficiency upon addition of 1 of 77 % for oxygen evolution.},
doi = {10.1002/anie.201708879},
url = {https://www.osti.gov/biblio/1470106}, journal = {Angewandte Chemie (International Edition)},
issn = {1433-7851},
number = 13,
volume = 57,
place = {United States},
year = {2018},
month = {1}
}

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