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Title: Visible photoelectrochemical water splitting into H2 and O2 in a dye-sensitized photoelectrosynthesis cell

Journal Article · · Proceedings of the National Academy of Sciences of the United States of America
 [1];  [1];  [2];  [1];  [1]
  1. Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry
  2. Univ. of Washington, Seattle, WA (United States). Dept. of Chemistry
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A hybrid strategy for solar water splitting is exploited here based on a dye-sensitized photoelectrosynthesis cell (DSPEC) with a mesoporous SnO2/TiO2 core/shell nanostructured electrode derivatized with a surface-bound Ru(II) polypyridyl-based chromophore–catalyst assembly. The assembly, [(4,4’-(PO3H2)2bpy)2Ru(4-Mebpy-4’-bimpy)Ru(tpy)(OH2)]4+ ([RuaII-RubII-OH2]4+, combines both a light absorber and a water oxidation catalyst in a single molecule. It was attached to the TiO2 shell by phosphonate-surface oxide binding. The oxide-bound assembly was further stabilized on the surface by atomic layer deposition (ALD) of either Al2O3 or TiO2 overlayers. Illumination of the resulting fluorine-doped tin oxide (FTO)|SnO2/TiO2|-[RuaII-RubII-OH2]4+(Al2O3 or TiO2) photoanodes in photoelectrochemical cells with a Pt cathode and a small applied bias resulted in visible-light water splitting as shown by direct measurements of both evolved H2 and O2. The performance of the resulting DSPECs varies with shell thickness and the nature and extent of the oxide overlayer. Use of the SnO2/TiO2 core/shell compared with nanoITO/TiO2 with the same assembly results in photocurrent enhancements of ~5. In conclusion, systematic variations in shell thickness and ALD overlayer lead to photocurrent densities as high as 1.97 mA/cm2 with 445-nm, ~90-mW/cm2 illumination in a phosphate buffer at pH 7.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Center for Solar Fuels (UNC EFRC)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Contributing Organization:
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
Grant/Contract Number:
SC0001011
OSTI ID:
1210802
Journal Information:
Proceedings of the National Academy of Sciences of the United States of America, Vol. 112, Issue 19; ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 123 works
Citation information provided by
Web of Science

References (30)

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Cited By (26)

Solution‐Processed Self‐Powered Transparent Ultraviolet Photodetectors with Ultrafast Response Speed for High‐Performance Communication System journal February 2019
Recent Advances in Sensitized Photocathodes: From Molecular Dyes to Semiconducting Quantum Dots journal January 2018
Photoelectrocatalytic Materials for Solar Water Splitting journal May 2018
A Million Turnover Molecular Anode for Catalytic Water Oxidation journal November 2016
Light-Driven Water Splitting Mediated by Photogenerated Bromine journal March 2018
Ru-bis(pyridine)pyrazolate (bpp)-Based Water-Oxidation Catalysts Anchored on TiO 2 : The Importance of the Nature and Position of the Anchoring Group journal February 2016
Behavior of Ru-bda Water-Oxidation Catalysts in Low Oxidation States journal August 2018
Directly Photoexcited Oxides for Photoelectrochemical Water Splitting journal September 2019
Solar Energy Conversion in Photoelectrochemical Systems book July 2016
Developing a scalable artificial photosynthesis technology through nanomaterials by design journal December 2016
Spectroscopic signatures of ligand field states in {Ru II (imine)} complexes journal January 2016
Charge injection into nanostructured TiO 2 electrodes from the photogenerated reduced form of a new Ru( ii ) polypyridine compound: the “anti-biomimetic” mechanism at work journal January 2016
Production of solar chemicals: gaining selectivity with hybrid molecule/semiconductor assemblies journal January 2018
Core–shell structured titanium dioxide nanomaterials for solar energy utilization journal January 2018
Dinuclear metal complexes: multifunctional properties and applications journal January 2020
Light-driven water oxidation by a dye-sensitized photoanode with a chromophore/catalyst assembly on a mesoporous double-shell electrode journal January 2019
Ultrathin oxide layers for nanoscale integration of molecular light absorbers, catalysts, and complete artificial photosystems journal January 2019
Barriers for interfacial back-electron transfer: A comparison between TiO 2 and SnO 2 /TiO 2 core/shell structures journal January 2019
Solar photothermochemical alkane reverse combustion journal February 2016
Stabilized photoanodes for water oxidation by integration of organic dyes, water oxidation catalysts, and electron-transfer mediators journal August 2018
Dye-sensitized photoelectrochemical water oxidation through a buried junction journal June 2018
Titanium dioxide thin films by atomic layer deposition: a review journal August 2017
Inorganic Photochemistry and Solar Energy Harvesting: Current Developments and Challenges to Solar Fuel Production journal January 2019
Electronic Properties of Electron-Deficient Zn(II) Porphyrins for HBr Splitting journal July 2019
Light‐Driven Water Splitting Mediated by Photogenerated Bromine journal March 2018
A Million Turnover Molecular Anode for Catalytic Water Oxidation journal November 2016

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Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
catalysis (homogeneous)
catalysis (heterogeneous)
solar (photovoltaic)
solar (fuels)
photosynthesis (natural and artificial)
hydrogen and fuel cells
electrodes - solar
charge transport
materials and chemistry by design
synthesis (novel materials)
synthesis (self-assembly)