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Title: Chromophore-Catalyst Assembly for Water Oxidation Prepared by Atomic Layer Deposition

Abstract

Visible-light-driven water splitting was explored in a dye sensitized photoelectrosynthesis cell (DSPEC) based on a photoanode with a phosphonic acid-derivatized donor–π–acceptor (D–π–A) organic chromophore, 1, and the water oxidation catalyst [Ru(bda)(4-O(CH2)3P(O3H2)2-pyr)2], 2, (pyr = pyridine; bda = 2,2'-bipyridine-6,6'-dicarboxylate). The photoanode was prepared by using a layering strategy beginning with the organic dye anchored to an FTO|core/shell electrode, atomic layer deposition (ALD) of a thin layer (<1 nm) of TiO2, and catalyst binding through phosphonate linkage to the TiO2 layer. Device performance was evaluated by photocurrent measurements for core/shell photoanodes, with either SnO2 or nanoITO core materials, in acetate-buffered, aqueous solutions at pH 4.6 or 5.7. The absolute magnitudes of photocurrent changes with the core material, TiO2 spacer layer thickness, or pH, observed photocurrents were 2.5-fold higher in the presence of catalyst. The findings of transient absorption measurements and DFT calculations reflect that electron injection by the photoexcited organic dye is ultrafast promoted by electronic interactions enabled by orientation of the dye’s molecular orbitals on the electrode surface. Rapid injection is followed by recombination with the oxidized dye which is 95% complete by 1.5 ns. While chromophore decomposition limits the efficiency of the DSPEC devices toward O2 production, the flexibility ofmore » the strategy presented here offers a new approach to photoanode design.« less

Authors:
 [1];  [1];  [1];  [1];  [2];  [1]; ORCiD logo [1]; ORCiD logo [1]
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  1. Univ. of North Carolina, Chapel Hill, NC (United States)
  2. Univ. of North Carolina, Chapel Hill, NC (United States); Daegu Univ. (Korea)
Publication Date:
Research Org.:
Univ. of North Carolina, Chapel Hill, NC (United States). Energy Frontier Research Center (EFRC) Center for Solar Fuels (UNC EFRC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1469971
Grant/Contract Number:  
SC0001011
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 9; Journal Issue: 44; 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 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; 42 ENGINEERING; 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; D−π−A organic dye; core/shell; dye sensitized photoelectrosynthesis cell; electron transfer; transient absorption; water splitting; artificial photosynthesis

Citation Formats

Alibabaei, Leila, Dillon, Robert J., Reilly, Caroline E., Brennaman, M. Kyle, Wee, Kyung-Ryang, Marquard, Seth L., Papanikolas, John M., and Meyer, Thomas J. Chromophore-Catalyst Assembly for Water Oxidation Prepared by Atomic Layer Deposition. United States: N. p., 2017. Web. doi:10.1021/acsami.7b11905.
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Alibabaei, Leila, Dillon, Robert J., Reilly, Caroline E., Brennaman, M. Kyle, Wee, Kyung-Ryang, Marquard, Seth L., Papanikolas, John M., & Meyer, Thomas J. Chromophore-Catalyst Assembly for Water Oxidation Prepared by Atomic Layer Deposition. United States. https://doi.org/10.1021/acsami.7b11905
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Alibabaei, Leila, Dillon, Robert J., Reilly, Caroline E., Brennaman, M. Kyle, Wee, Kyung-Ryang, Marquard, Seth L., Papanikolas, John M., and Meyer, Thomas J. Mon . "Chromophore-Catalyst Assembly for Water Oxidation Prepared by Atomic Layer Deposition". United States. https://doi.org/10.1021/acsami.7b11905. https://www.osti.gov/servlets/purl/1469971.
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@article{osti_1469971,
title = {Chromophore-Catalyst Assembly for Water Oxidation Prepared by Atomic Layer Deposition},
author = {Alibabaei, Leila and Dillon, Robert J. and Reilly, Caroline E. and Brennaman, M. Kyle and Wee, Kyung-Ryang and Marquard, Seth L. and Papanikolas, John M. and Meyer, Thomas J.},
abstractNote = {Visible-light-driven water splitting was explored in a dye sensitized photoelectrosynthesis cell (DSPEC) based on a photoanode with a phosphonic acid-derivatized donor–π–acceptor (D–π–A) organic chromophore, 1, and the water oxidation catalyst [Ru(bda)(4-O(CH2)3P(O3H2)2-pyr)2], 2, (pyr = pyridine; bda = 2,2'-bipyridine-6,6'-dicarboxylate). The photoanode was prepared by using a layering strategy beginning with the organic dye anchored to an FTO|core/shell electrode, atomic layer deposition (ALD) of a thin layer (<1 nm) of TiO2, and catalyst binding through phosphonate linkage to the TiO2 layer. Device performance was evaluated by photocurrent measurements for core/shell photoanodes, with either SnO2 or nanoITO core materials, in acetate-buffered, aqueous solutions at pH 4.6 or 5.7. The absolute magnitudes of photocurrent changes with the core material, TiO2 spacer layer thickness, or pH, observed photocurrents were 2.5-fold higher in the presence of catalyst. The findings of transient absorption measurements and DFT calculations reflect that electron injection by the photoexcited organic dye is ultrafast promoted by electronic interactions enabled by orientation of the dye’s molecular orbitals on the electrode surface. Rapid injection is followed by recombination with the oxidized dye which is 95% complete by 1.5 ns. While chromophore decomposition limits the efficiency of the DSPEC devices toward O2 production, the flexibility of the strategy presented here offers a new approach to photoanode design.},
doi = {10.1021/acsami.7b11905},
journal = {ACS Applied Materials and Interfaces},
number = 44,
volume = 9,
place = {United States},
year = {Mon Oct 16 00:00:00 EDT 2017},
month = {Mon Oct 16 00:00:00 EDT 2017}
}
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https://doi.org/10.1021/acsami.7b11905
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    Works referencing / citing this record:

    A Noble-Metal-Free Heterogeneous Photosensitizer-Relay Catalyst Triad That Catalyzes Water Oxidation under Visible Light
    journal, December 2018

    • Ulusoy Ghobadi, T. Gamze; Akhuseyin Yildiz, Elif; Buyuktemiz, Muhammed
    • Angewandte Chemie, Vol. 130, Issue 52
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    Ultrathin oxide layers for nanoscale integration of molecular light absorbers, catalysts, and complete artificial photosystems
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    Inorganic Photochemistry and Solar Energy Harvesting: Current Developments and Challenges to Solar Fuel Production
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    • Ulusoy Ghobadi, T. Gamze; Ghobadi, Amir; Buyuktemiz, Muhammed
    • Angewandte Chemie, Vol. 132, Issue 10
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    A Robust, Precious‐Metal‐Free Dye‐Sensitized Photoanode for Water Oxidation: A Nanosecond‐Long Excited‐State Lifetime through a Prussian Blue Analogue
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    • Ulusoy Ghobadi, T. Gamze; Ghobadi, Amir; Buyuktemiz, Muhammed
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    A Noble‐Metal‐Free Heterogeneous Photosensitizer‐Relay Catalyst Triad That Catalyzes Water Oxidation under Visible Light
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    • Ulusoy Ghobadi, T. Gamze; Akhuseyin Yildiz, Elif; Buyuktemiz, Muhammed
    • Angewandte Chemie International Edition, Vol. 57, Issue 52
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