skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

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 » with time owing to catalyst loss from the electrode surface by axial ligand dissociation in the high oxidation states of the catalyst.« less

Authors:
 [1];  [1];  [1];  [1];  [1]; ORCiD logo [1]
  1. Univ. of North Carolina at Chapel Hill, Chapel Hill, NC (United States)
Publication Date:
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.
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
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.
@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}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 10 works
Citation information provided by
Web of Science

Save / Share:

Works referencing / citing this record:

Fighting Deactivation: Classical and Emerging Strategies for Efficient Stabilization of Molecular Electrocatalysts
journal, January 2020


Recent Advances in the Development of Molecular Catalyst‐Based Anodes for Water Oxidation toward Artificial Photosynthesis
journal, November 2018


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


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