Light‐Driven Water Splitting Mediated by Photogenerated Bromine

Light‐Driven Water Splitting Mediated by Photogenerated Bromine Light‐driven water splitting was achieved 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 demonstrated 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 potential 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. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Angewandte Chemie International Edition Wiley

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Publisher
Wiley Subscription Services, Inc., A Wiley Company
Copyright
© 2018 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim
ISSN
1433-7851
eISSN
1521-3773
D.O.I.
10.1002/anie.201708879
Publisher site
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Abstract

Light‐driven water splitting was achieved 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 demonstrated 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 potential 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.

Journal

Angewandte Chemie International EditionWiley

Published: Jan 19, 2018

Keywords: ; ; ; ;

References

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