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

Title: Visible photoelectrochemical water splitting into H 2 and O 2 in a dye-sensitized photoelectrosynthesis cell

Abstract

A hybrid strategy for solar water splitting is exploited here based on a dye-sensitized photoelectrosynthesis cell (DSPEC) with a mesoporous SnO 2/TiO 2 core/shell nanostructured electrode derivatized with a surface-bound Ru(II) polypyridyl-based chromophore–catalyst assembly. The assembly, [(4,4’-(PO 3H 2) 2bpy) 2Ru(4-Mebpy-4’-bimpy)Ru(tpy)(OH 2)] 4+ ([RuaII-RubII-OH 2] 4+, combines both a light absorber and a water oxidation catalyst in a single molecule. It was attached to the TiO 2 shell by phosphonate-surface oxide binding. The oxide-bound assembly was further stabilized on the surface by atomic layer deposition (ALD) of either Al 2O 3 or TiO 2 overlayers. Illumination of the resulting fluorine-doped tin oxide (FTO)|SnO 2/TiO 2|-[Ru a II-Ru b II-OH 2] 4+(Al 2O 3 or TiO 2) 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 H 2 and O 2. The performance of the resulting DSPECs varies with shell thickness and the nature and extent of the oxide overlayer. Use of the SnO 2/TiO 2 core/shell compared with nanoITO/TiO 2 with the same assembly results in photocurrent enhancements of ~5. In conclusion, systematic variations in shell thickness and ALD overlayer lead to photocurrentmore » densities as high as 1.97 mA/cm 2 with 445-nm, ~90-mW/cm 2 illumination in a phosphate buffer at pH 7.« less

Authors:
 [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
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC). Center for Solar Fuels (UNC EFRC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Contributing Org.:
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
OSTI Identifier:
1210802
Grant/Contract Number:  
SC0001011
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 112; Journal Issue: 19; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Country of Publication:
United States
Language:
English
Subject:
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)

Citation Formats

Alibabaei, Leila, Sherman, Benjamin D., Norris, Michael R., Brennaman, M. Kyle, and Meyer, Thomas J. Visible photoelectrochemical water splitting into H2 and O2 in a dye-sensitized photoelectrosynthesis cell. United States: N. p., 2015. Web. doi:10.1073/pnas.1506111112.
Alibabaei, Leila, Sherman, Benjamin D., Norris, Michael R., Brennaman, M. Kyle, & Meyer, Thomas J. Visible photoelectrochemical water splitting into H2 and O2 in a dye-sensitized photoelectrosynthesis cell. United States. https://doi.org/10.1073/pnas.1506111112
Alibabaei, Leila, Sherman, Benjamin D., Norris, Michael R., Brennaman, M. Kyle, and Meyer, Thomas J. Mon . "Visible photoelectrochemical water splitting into H2 and O2 in a dye-sensitized photoelectrosynthesis cell". United States. https://doi.org/10.1073/pnas.1506111112. https://www.osti.gov/servlets/purl/1210802.
@article{osti_1210802,
title = {Visible photoelectrochemical water splitting into H2 and O2 in a dye-sensitized photoelectrosynthesis cell},
author = {Alibabaei, Leila and Sherman, Benjamin D. and Norris, Michael R. and Brennaman, M. Kyle and Meyer, Thomas J.},
abstractNote = {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.},
doi = {10.1073/pnas.1506111112},
url = {https://www.osti.gov/biblio/1210802}, journal = {Proceedings of the National Academy of Sciences of the United States of America},
issn = {0027-8424},
number = 19,
volume = 112,
place = {United States},
year = {2015},
month = {4}
}

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

Citation Metrics:
Cited by: 59 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Chemical approaches to artificial photosynthesis
journal, September 2012


Chemical Approaches to Artificial Photosynthesis. 2
journal, October 2005


Solar Water Splitting Cells
journal, November 2010


Powering the planet: Chemical challenges in solar energy utilization
journal, October 2006


Energy and environment policy case for a global project on artificial photosynthesis
journal, January 2013


Applications of metal oxide materials in dye sensitized photoelectrosynthesis cells for making solar fuels: let the molecules do the work
journal, January 2013


Visible Region Photooxidation on TiO 2 with a Chromophore−Catalyst Molecular Assembly
journal, October 1999


Making solar fuels by artificial photosynthesis
journal, March 2011


Fast Transporting ZnO–TiO 2 Coaxial Photoanodes for Dye-Sensitized Solar Cells Based on ALD-Modified SiO 2 Aerogel Frameworks
journal, June 2012


Radial Electron Collection in Dye-Sensitized Solar Cells
journal, September 2008


Visible Light Driven Benzyl Alcohol Dehydrogenation in a Dye-Sensitized Photoelectrosynthesis Cell
journal, June 2014


Atomic Layer Deposition of TiO 2 on Mesoporous nanoITO: Conductive Core–Shell Photoanodes for Dye-Sensitized Solar Cells
journal, May 2014


Low-Temperature Crystalline Titanium Dioxide by Atomic Layer Deposition for Dye-Sensitized Solar Cells
journal, January 2013


Solar water splitting in a molecular photoelectrochemical cell
journal, November 2013


A visible light water-splitting cell with a photoanode formed by codeposition of a high-potential porphyrin and an iridium water-oxidation catalyst
journal, January 2011


Polyoxometalate water oxidation catalysts and the production of green fuel
journal, January 2012


Visible Light Driven Water Splitting in a Molecular Device with Unprecedentedly High Photocurrent Density
journal, March 2013


Solar Driven Water Oxidation by a Bioinspired Manganese Molecular Catalyst
journal, March 2010


Photoassisted Overall Water Splitting in a Visible Light-Absorbing Dye-Sensitized Photoelectrochemical Cell
journal, January 2009

  • Youngblood, W. Justin; Lee, Seung-Hyun Anna; Kobayashi, Yoji
  • Journal of the American Chemical Society, Vol. 131, Issue 3, p. 926-927
  • https://doi.org/10.1021/ja809108y

Concerted O atom-proton transfer in the O--O bond forming step in water oxidation
journal, April 2010


Crossing the divide between homogeneous and heterogeneous catalysis in water oxidation
journal, November 2013


One-Electron Activation of Water Oxidation Catalysis
journal, May 2014


Stabilization of [Ru(bpy) 2 (4,4′-(PO 3 H 2 )bpy)] 2+ on Mesoporous TiO 2 with Atomic Layer Deposition of Al 2 O 3
journal, December 2012


Stabilizing Small Molecules on Metal Oxide Surfaces Using Atomic Layer Deposition
journal, September 2013


Low-Overpotential Water Oxidation by a Surface-Bound Ruthenium-Chromophore-Ruthenium-Catalyst Assembly
journal, November 2013


Effects of Electron Trapping and Protonation on the Efficiency of Water-Splitting Dye-Sensitized Solar Cells
journal, July 2014


Improving the efficiency of water splitting in dye-sensitized solar cells by using a biomimetic electron transfer mediator
journal, April 2012


Electrochemical Instability of Phosphonate-Derivatized, Ruthenium(III) Polypyridyl Complexes on Metal Oxide Surfaces
journal, May 2015


    Works referencing / citing this record:

    A Million Turnover Molecular Anode for Catalytic Water Oxidation
    journal, November 2016


    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


    Spectroscopic signatures of ligand field states in {Ru II (imine)} complexes
    journal, January 2016


    A Million Turnover Molecular Anode for Catalytic Water Oxidation
    journal, November 2016


    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


    Spectroscopic signatures of ligand field states in {Ru II (imine)} complexes
    journal, January 2016


    A Million Turnover Molecular Anode for Catalytic Water Oxidation
    journal, November 2016


    Recent Advances in Sensitized Photocathodes: From Molecular Dyes to Semiconducting Quantum Dots
    journal, January 2018


    Photoelectrocatalytic Materials for Solar Water Splitting
    journal, May 2018


    Light-Driven Water Splitting Mediated by Photogenerated Bromine
    journal, March 2018


    Directly Photoexcited Oxides for Photoelectrochemical Water Splitting
    journal, September 2019


    An aqueous, organic dye derivatized SnO 2 /TiO 2 core/shell photoanode
    journal, January 2016


    Long-lived charge separation in dye–semiconductor assemblies: a pathway to multi-electron transfer reactions
    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


    Ultrathin oxide layers for nanoscale integration of molecular light absorbers, catalysts, and complete artificial photosystems
    journal, January 2019


    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


    Inorganic Photochemistry and Solar Energy Harvesting: Current Developments and Challenges to Solar Fuel Production
    journal, January 2019