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Title: Stabilization of Ruthenium(II) Polypyridyl Chromophores on Mesoporous TiO 2 Electrodes: Surface Reductive Electropolymerization and Silane Chemistry

Abstract

Stabilization is a critical issue in the long term operation of dye-sensitized photoelectrosynthesis cells (DSPECs) for water splitting or CO 2 reduction. The cells require a stable binding of the robust molecular chromophores, catalysts, and chromophore/catalyst assemblies on metal oxide semiconductor electrodes under the corresponding (photoelectro)chemical conditions. Here, an efficient stabilization strategy is presented based on functionalization of FTO|nanoTiO 2 (mesoporous, nanostructured TiO 2 deposited on fluorine-doped tin oxide (FTO) glass) electrodes with a vinylsilane followed by surface reductive electropolymerization of a vinyl-derivatized Ru(II) polypyridyl chromophore. The surface electropolymerization was dominated by a grafting-through mechanism, and rapidly completed within minutes. Chromophore surface coverages were controlled up to three equivalent monolayers by the number of electropolymerization cycles. The silane immobilization and cross-linked polymer network produced highly (photo)stabilized chromophore-grafted FTO|nanoTiO 2 electrodes. The electrodes showed significant improvements over structures based on atomic layer deposition and polymer dip-coating stabilization methods in a wide pH range from pH ≈ 1 to pH ≈ 12.5 under both dark and light conditions. Under illumination, with hydroquinone added as a sacrificial electron transfer donor, a photoresponse for sustained electron transfer mediation occurred for at least ~20 h in a pH ≈ 7.5 phosphate buffer (0.1 M NaHmore » 2PO 4/Na 2HPO 4, with 0.5 M NaClO 4). The overall procedure provides an efficient way to fabricate highly stabilized molecular assemblies on electrode surfaces with potential applications for DSPECs in solar fuels.« less

Authors:
 [1];  [1];  [1];  [1];  [1]; ORCiD logo [1]
  1. Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Univ. of North Carolina, Chapel Hill, NC (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
OSTI Identifier:
1503394
Alternate Identifier(s):
OSTI ID: 1508797
Grant/Contract Number:  
SC0015739; SC0001011; ECCS-1542015
Resource Type:
Published Article
Journal Name:
ACS Central Science
Additional Journal Information:
Journal Volume: 5; Journal Issue: 3; Journal ID: ISSN 2374-7943
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Wu, Lei, Brennaman, M. Kyle, Nayak, Animesh, Eberhart, Michael, Miller, Alexander J. M., and Meyer, Thomas J. Stabilization of Ruthenium(II) Polypyridyl Chromophores on Mesoporous TiO2 Electrodes: Surface Reductive Electropolymerization and Silane Chemistry. United States: N. p., 2019. Web. doi:10.1021/acscentsci.8b00914.
Wu, Lei, Brennaman, M. Kyle, Nayak, Animesh, Eberhart, Michael, Miller, Alexander J. M., & Meyer, Thomas J. Stabilization of Ruthenium(II) Polypyridyl Chromophores on Mesoporous TiO2 Electrodes: Surface Reductive Electropolymerization and Silane Chemistry. United States. doi:10.1021/acscentsci.8b00914.
Wu, Lei, Brennaman, M. Kyle, Nayak, Animesh, Eberhart, Michael, Miller, Alexander J. M., and Meyer, Thomas J. Fri . "Stabilization of Ruthenium(II) Polypyridyl Chromophores on Mesoporous TiO2 Electrodes: Surface Reductive Electropolymerization and Silane Chemistry". United States. doi:10.1021/acscentsci.8b00914.
@article{osti_1503394,
title = {Stabilization of Ruthenium(II) Polypyridyl Chromophores on Mesoporous TiO2 Electrodes: Surface Reductive Electropolymerization and Silane Chemistry},
author = {Wu, Lei and Brennaman, M. Kyle and Nayak, Animesh and Eberhart, Michael and Miller, Alexander J. M. and Meyer, Thomas J.},
abstractNote = {Stabilization is a critical issue in the long term operation of dye-sensitized photoelectrosynthesis cells (DSPECs) for water splitting or CO2 reduction. The cells require a stable binding of the robust molecular chromophores, catalysts, and chromophore/catalyst assemblies on metal oxide semiconductor electrodes under the corresponding (photoelectro)chemical conditions. Here, an efficient stabilization strategy is presented based on functionalization of FTO|nanoTiO2 (mesoporous, nanostructured TiO2 deposited on fluorine-doped tin oxide (FTO) glass) electrodes with a vinylsilane followed by surface reductive electropolymerization of a vinyl-derivatized Ru(II) polypyridyl chromophore. The surface electropolymerization was dominated by a grafting-through mechanism, and rapidly completed within minutes. Chromophore surface coverages were controlled up to three equivalent monolayers by the number of electropolymerization cycles. The silane immobilization and cross-linked polymer network produced highly (photo)stabilized chromophore-grafted FTO|nanoTiO2 electrodes. The electrodes showed significant improvements over structures based on atomic layer deposition and polymer dip-coating stabilization methods in a wide pH range from pH ≈ 1 to pH ≈ 12.5 under both dark and light conditions. Under illumination, with hydroquinone added as a sacrificial electron transfer donor, a photoresponse for sustained electron transfer mediation occurred for at least ~20 h in a pH ≈ 7.5 phosphate buffer (0.1 M NaH2PO4/Na2HPO4, with 0.5 M NaClO4). The overall procedure provides an efficient way to fabricate highly stabilized molecular assemblies on electrode surfaces with potential applications for DSPECs in solar fuels.},
doi = {10.1021/acscentsci.8b00914},
journal = {ACS Central Science},
number = 3,
volume = 5,
place = {United States},
year = {2019},
month = {2}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1021/acscentsci.8b00914

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