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

Leem, Gyu; Sherman, Benjamin D.; Burnett, Alex J.; Morseth, Zachary A.; Wee, Kyung-Ryang; Papanikolas, John M.; Meyer, Thomas J.; Schanze, Kirk S.

doi:10.1021/acsenergylett.6b00171

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

Journal Article · Tue Jun 21 04:00:00 EDT 2016 · ACS Energy Letters

DOI:https://doi.org/10.1021/acsenergylett.6b00171· OSTI ID:1387883

Leem, Gyu ^[1]; Sherman, Benjamin D. ^[2]; Burnett, Alex J. ^[1]; Morseth, Zachary A. ^[2]; Wee, Kyung-Ryang ^[2]; Papanikolas, John M. ^[2]; Meyer, Thomas J. ^[2]; Schanze, Kirk S. ^[1]

Univ. of Florida, Gainesville, FL (United States)
Univ. of North Carolina, Chapel Hill, NC (United States)

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.

View Accepted Manuscript (DOE)

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) (SC-22)

Grant/Contract Number:: SC0001011

OSTI ID:: 1387883

Journal Information:: ACS Energy Letters, Journal Name: ACS Energy Letters Journal Issue: 2 Vol. 1; ISSN 2380-8195

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (23)

Low-Overpotential Water Oxidation by a Surface-Bound Ruthenium-Chromophore-Ruthenium-Catalyst Assembly Norris, Michael R.; Concepcion, Javier J.; Fang, Zhen Angewandte Chemie International Edition, Vol. 52, Issue 51 https://doi.org/10.1002/anie.201305951	journal	November 2013
Polymer-Based Ruthenium(II) Polypyridyl Chromophores on TiO ₂ for Solar Energy Conversion Leem, Gyu; Morseth, Zachary A.; Wee, Kyung-Ryang Chemistry - An Asian Journal, Vol. 11, Issue 8 https://doi.org/10.1002/asia.201501384	journal	March 2016
Molecular Chromophore–Catalyst Assemblies for Solar Fuel Applications Ashford, Dennis L.; Gish, Melissa K.; Vannucci, Aaron K. Chemical Reviews, Vol. 115, Issue 23 https://doi.org/10.1021/acs.chemrev.5b00229	journal	August 2015
Visible Photoelectrochemical Water Splitting Based on a Ru(II) Polypyridyl Chromophore and Iridium Oxide Nanoparticle Catalyst Michaux, Katherine E.; Gambardella, Alessa A.; Alibabaei, Leila The Journal of Physical Chemistry C, Vol. 119, Issue 29 https://doi.org/10.1021/acs.jpcc.5b05711	journal	July 2015
Light-Driven Water Splitting with a Molecular Electroassembly-Based Core/Shell Photoanode Sherman, Benjamin D.; Ashford, Dennis L.; Lapides, Alexander M. The Journal of Physical Chemistry Letters, Vol. 6, Issue 16 https://doi.org/10.1021/acs.jpclett.5b01370	journal	July 2015
Efficient Light-Driven Oxidation of Alcohols Using an Organic Chromophore–Catalyst Assembly Anchored to TiO ₂ Pho, Toan V.; Sheridan, Matthew V.; Morseth, Zachary A. ACS Applied Materials & Interfaces, Vol. 8, Issue 14 https://doi.org/10.1021/acsami.6b00932	journal	March 2016
Oxidative electropolymerization of polypyridyl complexes of ruthenium Ellis, Charles D.; Margerum, Lawrence D.; Murray, Royce W. Inorganic Chemistry, Vol. 22, Issue 9 https://doi.org/10.1021/ic00151a005	journal	April 1983
Self-Assembled Bilayers on Indium–Tin Oxide (SAB-ITO) Electrodes: A Design for Chromophore–Catalyst Photoanodes Glasson, Christopher R. K.; Song, Wenjing; Ashford, Dennis L. Inorganic Chemistry, Vol. 51, Issue 16 https://doi.org/10.1021/ic300636w	journal	August 2012
Redox Mediator Effect on Water Oxidation in a Ruthenium-Based Chromophore–Catalyst Assembly Norris, Michael R.; Concepcion, Javier J.; Harrison, Daniel P. Journal of the American Chemical Society, Vol. 135, Issue 6 https://doi.org/10.1021/ja311645d	journal	January 2013
Visible Light Driven Water Splitting in a Molecular Device with Unprecedentedly High Photocurrent Density Gao, Yan; Ding, Xin; Liu, Jianhui Journal of the American Chemical Society, Vol. 135, Issue 11 https://doi.org/10.1021/ja400402d	journal	March 2013
Accumulation of Multiple Oxidative Equivalents at a Single Site by Cross-Surface Electron Transfer on TiO ₂ Song, Wenjing; Ito, Akitaka; Binstead, Robert A. Journal of the American Chemical Society, Vol. 135, Issue 31 https://doi.org/10.1021/ja4032538	journal	July 2013
Photoassisted Overall Water Splitting in a Visible Light-Absorbing Dye-Sensitized Photoelectrochemical Cell 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	journal	January 2009
Single-Site, Catalytic Water Oxidation on Oxide Surfaces Chen, Zuofeng; Concepcion, Javier J.; Jurss, Jonah W. Journal of the American Chemical Society, Vol. 131, Issue 43, p. 15580-15581 https://doi.org/10.1021/ja906391w	journal	November 2009
Watching Photoactivation in a Ru(II) Chromophore–Catalyst Assembly on TiO ₂ by Ultrafast Spectroscopy Wang, Li; Ashford, Dennis L.; Thompson, David W. The Journal of Physical Chemistry C, Vol. 117, Issue 46 https://doi.org/10.1021/jp410571x	journal	November 2013
Light Harvesting and Charge Separation in a π-Conjugated Antenna Polymer Bound to TiO ₂ Leem, Gyu; Morseth, Zachary A.; Puodziukynaite, Egle The Journal of Physical Chemistry C, Vol. 118, Issue 49 https://doi.org/10.1021/jp5113558	journal	November 2014
Multilayer Assemblies of Redox Polyelectrolytes Laurent, Delphine; Schlenoff, Joseph B. Langmuir, Vol. 13, Issue 6 https://doi.org/10.1021/la960959t	journal	March 1997
pH-Dependent Thickness Behavior of Sequentially Adsorbed Layers of Weak Polyelectrolytes Shiratori, S. S.; Rubner, M. F. Macromolecules, Vol. 33, Issue 11 https://doi.org/10.1021/ma991645q	journal	May 2000
Ru(bpy) ₃ ²⁺ derivatized polystyrenes constructed by nitroxide-mediated radical polymerization. Relationship between polymer chain length, structure and photophysical properties Leem, Gyu; Keinan, Shahar; Jiang, Junlin Polymer Chemistry, Vol. 6, Issue 47 https://doi.org/10.1039/C5PY01289A	journal	January 2015
Synthesis, characterization, and water oxidation by a molecular chromophore-catalyst assembly prepared by atomic layer deposition. The “mummy” strategy Lapides, A. M.; Sherman, B. D.; Brennaman, M. K. Chemical Science, Vol. 6, Issue 11 https://doi.org/10.1039/C5SC01752A	journal	January 2015
An aqueous, organic dye derivatized SnO ₂ /TiO ₂ core/shell photoanode Wee, Kyung-Ryang; Sherman, Benjamin D.; Brennaman, M. Kyle Journal of Materials Chemistry A, Vol. 4, Issue 8 https://doi.org/10.1039/C5TA06678F	journal	January 2016
Visible photoelectrochemical water splitting into H ₂ and O ₂ in a dye-sensitized photoelectrosynthesis cell Alibabaei, Leila; Sherman, Benjamin D.; Norris, Michael R. Proceedings of the National Academy of Sciences, Vol. 112, Issue 19 https://doi.org/10.1073/pnas.1506111112	journal	April 2015
Fuzzy Nanoassemblies: Toward Layered Polymeric Multicomposites Decher, G. Science, Vol. 277, Issue 5330 https://doi.org/10.1126/science.277.5330.1232	journal	August 1997
Organic and Inorganic Dyes in Polyelectrolyte Multilayer Films Ball, Vincent Materials, Vol. 5, Issue 12 https://doi.org/10.3390/ma5122681	journal	December 2012

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Polymer-based chromophore–catalyst assemblies for solar energy conversion Leem, Gyu; Sherman, Benjamin D.; Schanze, Kirk S. Nano Convergence, Vol. 4, Issue 1 https://doi.org/10.1186/s40580-017-0132-z	journal	December 2017
Layer-by-layer assembly for photoelectrochemical nanoarchitectonics Kim, Dongseok; Gu, Minsu; Park, Minju Molecular Systems Design & Engineering, Vol. 4, Issue 1 https://doi.org/10.1039/c8me00067k	journal	January 2019
Inorganic Photochemistry and Solar Energy Harvesting: Current Developments and Challenges to Solar Fuel Production Sousa, Sinval F.; Souza, Breno L.; Barros, Cristiane L. International Journal of Photoenergy, Vol. 2019 https://doi.org/10.1155/2019/9624092	journal	January 2019

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