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Title: Crossing the bridge from molecular catalysis to a heterogenous electrode in electrocatalytic water oxidation

Abstract

Significant progress has been made in designing single-site molecular Ru(II)-polypyridyl-aqua catalysts for homogenous catalytic water oxidation. Surface binding and transfer of the catalytic reactivity onto conductive substrates provides a basis for heterogeneous applications in electrolytic cells and dye-sensitized photoelectrosynthesis cells (DSPECs). Earlier efforts have focused on phosphonic acid (-PO3H2) or carboxylic acid (-CO2H) bindings on oxide surfaces. However, issues remain with limited surface stabilities, especially in aqueous solutions at higher pH under conditions that favor water oxidation by reducing the thermodynamic barrier and accelerating the catalytic rate using atom-proton transfer (APT) pathways. Here, we address the problem by combining silane surface functionalization and surface reductive electropolymerization on mesoporous, nanofilms of indium tin oxide (ITO) on fluorine-doped tin oxide (FTO) substrates (FTO|nanoITO). FTO|nanoITO electrodes were functionalized with vinyltrimethoxysilane (VTMS) to introduce vinyl groups on the electrode surfaces by silane attachment, followed by surface electropolymerization of the vinyl-derivatized complex, [RuII(Mebimpy)(dvbpy)(OH2)]2+(12+; Mebimpy: 2,6-bis(1-methyl-1H-benzo[d]imidazol-2-yl)pyridine; dvbpy: 5,5'-divinyl-2,2'-bipyridine), in a mechanism dominated by a grafting-through method. The surface coverage of catalyst 12+ was controlled by the number of electropolymerization cycles. The combined silane attachment/cross-linked polymer network stabilized 12+on the electrode surface under a variety of conditions especially at pH > ~6. Surface-grafted poly12+ was stable towardmore » redox cycling at pH ~ 7.5 over an ~4-h period. Finally, sustained heterogeneous electrocatalytic water oxidation by the electrode gave steady-state currents for at least ~6 h with a Faradaic efficiency of ~68% for O2 production.« less

Authors:
 [1];  [2];  [1]; ORCiD logo [2]
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  1. Shenzhen Univ. (China)
  2. Univ. of North Carolina, Chapel Hill, NC (United States)
Publication Date:
Research Org.:
University of North Carolina, Chapel Hill, NC (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Natural Science Foundation of China (NSFC)
OSTI Identifier:
1610481
Grant/Contract Number:  
SC0001011; SC0015739; 51702221
Resource Type:
Accepted Manuscript
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 116; Journal Issue: 23; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; electrocatalytic water oxidation; homogenous and heterogenous; silane surface; functionalization; surface electropolymerization; grafting-through

Citation Formats

Wu, Lei, Nayak, Animesh, Shao, Jing, and Meyer, Thomas J. Crossing the bridge from molecular catalysis to a heterogenous electrode in electrocatalytic water oxidation. United States: N. p., 2019. Web. doi:10.1073/pnas.1902455116.
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Wu, Lei, Nayak, Animesh, Shao, Jing, & Meyer, Thomas J. Crossing the bridge from molecular catalysis to a heterogenous electrode in electrocatalytic water oxidation. United States. https://doi.org/10.1073/pnas.1902455116
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Wu, Lei, Nayak, Animesh, Shao, Jing, and Meyer, Thomas J. Thu . "Crossing the bridge from molecular catalysis to a heterogenous electrode in electrocatalytic water oxidation". United States. https://doi.org/10.1073/pnas.1902455116. https://www.osti.gov/servlets/purl/1610481.
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@article{osti_1610481,
title = {Crossing the bridge from molecular catalysis to a heterogenous electrode in electrocatalytic water oxidation},
author = {Wu, Lei and Nayak, Animesh and Shao, Jing and Meyer, Thomas J.},
abstractNote = {Significant progress has been made in designing single-site molecular Ru(II)-polypyridyl-aqua catalysts for homogenous catalytic water oxidation. Surface binding and transfer of the catalytic reactivity onto conductive substrates provides a basis for heterogeneous applications in electrolytic cells and dye-sensitized photoelectrosynthesis cells (DSPECs). Earlier efforts have focused on phosphonic acid (-PO3H2) or carboxylic acid (-CO2H) bindings on oxide surfaces. However, issues remain with limited surface stabilities, especially in aqueous solutions at higher pH under conditions that favor water oxidation by reducing the thermodynamic barrier and accelerating the catalytic rate using atom-proton transfer (APT) pathways. Here, we address the problem by combining silane surface functionalization and surface reductive electropolymerization on mesoporous, nanofilms of indium tin oxide (ITO) on fluorine-doped tin oxide (FTO) substrates (FTO|nanoITO). FTO|nanoITO electrodes were functionalized with vinyltrimethoxysilane (VTMS) to introduce vinyl groups on the electrode surfaces by silane attachment, followed by surface electropolymerization of the vinyl-derivatized complex, [RuII(Mebimpy)(dvbpy)(OH2)]2+(12+; Mebimpy: 2,6-bis(1-methyl-1H-benzo[d]imidazol-2-yl)pyridine; dvbpy: 5,5'-divinyl-2,2'-bipyridine), in a mechanism dominated by a grafting-through method. The surface coverage of catalyst 12+ was controlled by the number of electropolymerization cycles. The combined silane attachment/cross-linked polymer network stabilized 12+on the electrode surface under a variety of conditions especially at pH > ~6. Surface-grafted poly12+ was stable toward redox cycling at pH ~ 7.5 over an ~4-h period. Finally, sustained heterogeneous electrocatalytic water oxidation by the electrode gave steady-state currents for at least ~6 h with a Faradaic efficiency of ~68% for O2 production.},
doi = {10.1073/pnas.1902455116},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 23,
volume = 116,
place = {United States},
year = {Thu May 16 00:00:00 EDT 2019},
month = {Thu May 16 00:00:00 EDT 2019}
}
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https://doi.org/10.1073/pnas.1902455116
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