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Title: Light-Driven Water Oxidation Using Polyelectrolyte Layer-by-Layer Chromophore–Catalyst Assemblies

Abstract

Layer-by-Layer (LbL) polyelectrolyte self-assembly occurs by the alternate exposure of a substrate to solutions of oppositely charged polyelectrolytes or polyions. Here, we report the application of LbL to construct chromophore–catalyst assemblies consisting of a cationic polystyrene-based Ru polychromophore (PS-Ru) and a [Ru(tpy)(2-pyridyl-N-methylbenzimidazole) (OH2)]2+ water oxidation catalyst (RuC), codeposited with poly(acrylic acid) (PAA) as an inert polyanion. These assemblies are deposited onto planar indium tin oxide (ITO, Sn:In2O3) substrates for electrochemical characterization and onto mesoporous substrates consisting of a SnO2/TiO2 core/shell structure atop fluorine doped tin oxide (FTO) for application to light-driven water oxidation in a dye-sensitized photoelectrosynthesis cell. Cyclic voltammetry and ultraviolet–visible absorption spectroscopy reveal that multilayer deposition progressively increases the film thickness on ITO glass substrates. Under an applied bias, photocurrent measurements of the (PAA/PS-Ru)5/(PAA/RuC)5 LbL films formed on FTO//SnO2/TiO2 mesoporous core–shell electrodes demonstrate a clear anodic photocurrent response. Prolonged photoelectrolysis experiments, with the use of a dual working electrode collector–generator cell, reveal production of O2 from the illuminated photoanode with a Faradaic efficiency of 22%. Finally, this is the first report to demonstrate the use of polyelectrolyte LbL to construct chromophore–catalyst assemblies for water oxidation.

Authors:
 [1];  [2];  [1];  [2];  [2];  [2];  [2];  [1]
+ Show Author Affiliations
  1. Univ. of Florida, Gainesville, FL (United States)
  2. Univ. of North Carolina, Chapel Hill, NC (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Solar Fuels (UNC EFRC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1387883
Grant/Contract Number:  
SC0001011
Resource Type:
Accepted Manuscript
Journal Name:
ACS Energy Letters
Additional Journal Information:
Journal Volume: 1; Journal Issue: 2; 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 2380-8195
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
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

Leem, Gyu, Sherman, Benjamin D., Burnett, Alex J., Morseth, Zachary A., Wee, Kyung-Ryang, Papanikolas, John M., Meyer, Thomas J., and Schanze, Kirk S. Light-Driven Water Oxidation Using Polyelectrolyte Layer-by-Layer Chromophore–Catalyst Assemblies. United States: N. p., 2016. Web. doi:10.1021/acsenergylett.6b00171.
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Leem, Gyu, Sherman, Benjamin D., Burnett, Alex J., Morseth, Zachary A., Wee, Kyung-Ryang, Papanikolas, John M., Meyer, Thomas J., & Schanze, Kirk S. Light-Driven Water Oxidation Using Polyelectrolyte Layer-by-Layer Chromophore–Catalyst Assemblies. United States. https://doi.org/10.1021/acsenergylett.6b00171
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Leem, Gyu, Sherman, Benjamin D., Burnett, Alex J., Morseth, Zachary A., Wee, Kyung-Ryang, Papanikolas, John M., Meyer, Thomas J., and Schanze, Kirk S. Tue . "Light-Driven Water Oxidation Using Polyelectrolyte Layer-by-Layer Chromophore–Catalyst Assemblies". United States. https://doi.org/10.1021/acsenergylett.6b00171. https://www.osti.gov/servlets/purl/1387883.
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@article{osti_1387883,
title = {Light-Driven Water Oxidation Using Polyelectrolyte Layer-by-Layer Chromophore–Catalyst Assemblies},
author = {Leem, Gyu and Sherman, Benjamin D. and Burnett, Alex J. and Morseth, Zachary A. and Wee, Kyung-Ryang and Papanikolas, John M. and Meyer, Thomas J. and Schanze, Kirk S.},
abstractNote = {Layer-by-Layer (LbL) polyelectrolyte self-assembly occurs by the alternate exposure of a substrate to solutions of oppositely charged polyelectrolytes or polyions. Here, we report the application of LbL to construct chromophore–catalyst assemblies consisting of a cationic polystyrene-based Ru polychromophore (PS-Ru) and a [Ru(tpy)(2-pyridyl-N-methylbenzimidazole) (OH2)]2+ water oxidation catalyst (RuC), codeposited with poly(acrylic acid) (PAA) as an inert polyanion. These assemblies are deposited onto planar indium tin oxide (ITO, Sn:In2O3) substrates for electrochemical characterization and onto mesoporous substrates consisting of a SnO2/TiO2 core/shell structure atop fluorine doped tin oxide (FTO) for application to light-driven water oxidation in a dye-sensitized photoelectrosynthesis cell. Cyclic voltammetry and ultraviolet–visible absorption spectroscopy reveal that multilayer deposition progressively increases the film thickness on ITO glass substrates. Under an applied bias, photocurrent measurements of the (PAA/PS-Ru)5/(PAA/RuC)5 LbL films formed on FTO//SnO2/TiO2 mesoporous core–shell electrodes demonstrate a clear anodic photocurrent response. Prolonged photoelectrolysis experiments, with the use of a dual working electrode collector–generator cell, reveal production of O2 from the illuminated photoanode with a Faradaic efficiency of 22%. Finally, this is the first report to demonstrate the use of polyelectrolyte LbL to construct chromophore–catalyst assemblies for water oxidation.},
doi = {10.1021/acsenergylett.6b00171},
journal = {ACS Energy Letters},
number = 2,
volume = 1,
place = {United States},
year = {Tue Jun 21 00:00:00 EDT 2016},
month = {Tue Jun 21 00:00:00 EDT 2016}
}
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https://doi.org/10.1021/acsenergylett.6b00171
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    Works referencing / citing this record:

    Layer-by-layer assembly for photoelectrochemical nanoarchitectonics
    journal, January 2019

    • Kim, Dongseok; Gu, Minsu; Park, Minju
    • Molecular Systems Design & Engineering, Vol. 4, Issue 1
    • DOI: 10.1039/c8me00067k

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

    • Sousa, Sinval F.; Souza, Breno L.; Barros, Cristiane L.
    • International Journal of Photoenergy, Vol. 2019
    • DOI: 10.1155/2019/9624092

    Polymer-based chromophore–catalyst assemblies for solar energy conversion
    journal, December 2017

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