A Molecular Silane-Derivatized Ru(II) Catalyst for Photoelectrochemical Water Oxidation

doi:https://doi.org/10.1021/jacs.8b10132

Title: A Molecular Silane-Derivatized Ru(II) Catalyst for Photoelectrochemical Water Oxidation

Abstract

Photoanodes in dye-sensitized photoelectrosynthesis cells integrate molecular chromophore/catalyst assemblies on mesoporous n-type metal oxide electrodes for light-driven water oxidation. One limitation for sustainable photoanodes is the stability of chromophore/catalyst assembly on electrode surfaces for long periods. Progress has been made in stabilizing chromophores based on atomic layer deposition, polymer dip coating, C–C cross-coupling by electropolymerization, and silane surface binding, but little progress has been made on catalyst stabilization. We report here the silane-derivatized catalyst, Ru(bda)(L) ₂ (bda = 2,2'-bipyridine-6,6'-dicarboxylate, L = 4-(6-(triethoxysilyl)hexyl)pyridine), catalyst 1, which is stabilized on metal oxide electrode surfaces over an extended pH range. A surface stabilization study shows that it maintains its reactivity on the electrode surface toward electrochemical oxidation over a wide range of conditions. Its electrochemical stability on electrode surfaces has been systematically evaluated, and its role as a catalyst for water oxidation has been explored. On surfaces of mesoporous nanostructured core/shell SnO ₂/TiO ₂, with a TiO ₂ stabilized inner layer of the Ru(II) polypyridyl chromophore, [Ru(4,4'-(PO ₃H ₂) ₂bpy)(bpy) ₂] ²⁺ (RuP ²⁺; bpy = 2,2'-bipyridine), highly efficient photoelectrochemical water oxidation catalysis occurs to produce O ₂ with a maximum efficiency of ~1.25 mA/cm ². Furthermore, long-term loss of catalytic activity occursmore »« less

Authors:

Wu, Lei ^[1]; Eberhart, Michael ^[1]; Nayak, Animesh ^[1]; Brennaman, M. Kyle ^[1]; Shan, Bing ^[1];

^[1]

Univ. of North Carolina at Chapel Hill, Chapel Hill, NC (United States)

Publication Date:: 2018-10-16

Research Org.:: Energy Frontier Research Centers (EFRC) (United States). Alliance for Molecular PhotoElectrode Design for Solar Fuels (AMPED); Univ. of North Carolina, Chapel Hill, NC (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1566591

Grant/Contract Number:: SC0001011

Resource Type:: Journal Article: Accepted Manuscript

Journal Name:: Journal of the American Chemical Society

Additional Journal Information:: Journal Volume: 140; Journal Issue: 44; Journal ID: ISSN 0002-7863

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 25 ENERGY STORAGE; catalysis (homogeneous); catalysis (heterogeneous); electrocatalysis; solar (fuels); photosynthesis (natural and artificial); defects; charge transport; materials and chemistry by design; mesostructured materials; synthesis (novel materials); synthesis (self-assembly)

Citation Formats


                    Wu, Lei, Eberhart, Michael, Nayak, Animesh, Brennaman, M. Kyle, Shan, Bing, and Meyer, Thomas J. A Molecular Silane-Derivatized Ru(II) Catalyst for Photoelectrochemical Water Oxidation.  United States: N. p., 2018. 
        Web.  doi:10.1021/jacs.8b10132.

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                    Wu, Lei, Eberhart, Michael, Nayak, Animesh, Brennaman, M. Kyle, Shan, Bing, & Meyer, Thomas J. A Molecular Silane-Derivatized Ru(II) Catalyst for Photoelectrochemical Water Oxidation.  United States.  https://doi.org/10.1021/jacs.8b10132

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                    Wu, Lei, Eberhart, Michael, Nayak, Animesh, Brennaman, M. Kyle, Shan, Bing, and Meyer, Thomas J. Tue .  
        "A Molecular Silane-Derivatized Ru(II) Catalyst for Photoelectrochemical Water Oxidation".  United States.  https://doi.org/10.1021/jacs.8b10132.  https://www.osti.gov/servlets/purl/1566591.

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@article{osti_1566591,

  title        = {A Molecular Silane-Derivatized Ru(II) Catalyst for Photoelectrochemical Water Oxidation},

  author       = {Wu, Lei and Eberhart, Michael and Nayak, Animesh and Brennaman, M. Kyle and Shan, Bing and Meyer, Thomas J.},

  abstractNote = {Photoanodes in dye-sensitized photoelectrosynthesis cells integrate molecular chromophore/catalyst assemblies on mesoporous n-type metal oxide electrodes for light-driven water oxidation. One limitation for sustainable photoanodes is the stability of chromophore/catalyst assembly on electrode surfaces for long periods. Progress has been made in stabilizing chromophores based on atomic layer deposition, polymer dip coating, C–C cross-coupling by electropolymerization, and silane surface binding, but little progress has been made on catalyst stabilization. We report here the silane-derivatized catalyst, Ru(bda)(L)2 (bda = 2,2'-bipyridine-6,6'-dicarboxylate, L = 4-(6-(triethoxysilyl)hexyl)pyridine), catalyst 1, which is stabilized on metal oxide electrode surfaces over an extended pH range. A surface stabilization study shows that it maintains its reactivity on the electrode surface toward electrochemical oxidation over a wide range of conditions. Its electrochemical stability on electrode surfaces has been systematically evaluated, and its role as a catalyst for water oxidation has been explored. On surfaces of mesoporous nanostructured core/shell SnO2/TiO2, with a TiO2 stabilized inner layer of the Ru(II) polypyridyl chromophore, [Ru(4,4'-(PO3H2)2bpy)(bpy)2]2+ (RuP2+; bpy = 2,2'-bipyridine), highly efficient photoelectrochemical water oxidation catalysis occurs to produce O2 with a maximum efficiency of ~1.25 mA/cm2. Furthermore, long-term loss of catalytic activity occurs with time owing to catalyst loss from the electrode surface by axial ligand dissociation in the high oxidation states of the catalyst.},

  doi          = {10.1021/jacs.8b10132},

  url          = {https://www.osti.gov/biblio/1566591},
  journal      = {Journal of the American Chemical Society},

  issn         = {0002-7863},

  number       = 44,

  volume       = 140,

  place        = {United States},

  year         = {2018},

  month        = {10}

}

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Works referencing / citing this record:

Fighting Deactivation: Classical and Emerging Strategies for Efficient Stabilization of Molecular Electrocatalysts
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https://doi.org/10.1002/cssc.201802795

Early photophysical events of a ruthenium( ii ) molecular dyad capable of performing photochemical water oxidation and of its model compounds
journal, January 2019

Nastasi, Francesco; Santoro, Antonio; Serroni, Scolastica
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https://doi.org/10.1039/c8pp00530c

Crossing the bridge from molecular catalysis to a heterogenous electrode in electrocatalytic water oxidation
journal, May 2019

Wu, Lei; Nayak, Animesh; Shao, Jing
Proceedings of the National Academy of Sciences, Vol. 116, Issue 23
https://doi.org/10.1073/pnas.1902455116

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Title: A Molecular Silane-Derivatized Ru(II) Catalyst for Photoelectrochemical Water Oxidation

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Citation Formats

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