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

Title: Photoinduced Electron Transfer in a Chromophore–Catalyst Assembly Anchored to TiO 2

Abstract

Photoinduced formation, separation, and buildup of multiple redox equivalents are an integral part of cycles for producing solar fuels in dye-sensitized photoelectrosynthesis cells (DSPECs). Excitation wavelength-dependent electron injection, intra-assembly electron transfer, and pH-dependent back electron transfer on TiO2 were investigated for the molecular assembly [((PO3H2-CH2)-bpy)2Rua(bpy-NH-CO-trpy)Rub(bpy)(OH2)]4+ ([TiO2–RuaII–RubII–OH2]4+; ((PO3H2-CH2)2-bpy = ([2,2'-bipyridine]-4,4'-diylbis(methylene))diphosphonic acid); bpy-ph-NH-CO-trpy = 4-([2,2':6',2''-terpyridin]-4'-yl)-N-((4'-methyl-[2,2'-bipyridin]-4-yl)methyl) benzamide); bpy = 2,2'-bipyridine). This assembly combines a light-harvesting chromophore and a water oxidation catalyst linked by a synthetically flexible saturated bridge designed to enable long-lived charge-separated states. Following excitation of the chromophore, rapid electron injection into TiO2 and intra-assembly electron transfer occur on the subnanosecond time scale followed by microsecond–millisecond back electron transfer from the semiconductor to the oxidized catalyst, [TiO2(e–)–RuaII–RubIII–OH2]4+→[TiO2–RuaII–RubII–OH2]4+.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1]
  1. Department of Chemistry, University of North Carolina at Chapel Hill, CB 3290, Chapel Hill, North Carolina 27599-3290, United States
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Solar Fuels (UNC EFRC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1387015
DOE Contract Number:  
SC0001011
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 134; Journal Issue: 46; 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 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (homogeneous), catalysis (heterogeneous), solar (photovoltaic), solar (fuels), photosynthesis (natural and artificial), hydrogen and fuel cells, electrodes - solar, charge transport, materials and chemistry by design, synthesis (novel materials), synthesis (self-assembly)

Citation Formats

Ashford, Dennis L., Song, Wenjing, Concepcion, Javier J., Glasson, Christopher R. K., Brennaman, M. Kyle, Norris, Michael R., Fang, Zhen, Templeton, Joseph L., and Meyer, Thomas J. Photoinduced Electron Transfer in a Chromophore–Catalyst Assembly Anchored to TiO 2. United States: N. p., 2012. Web. doi:10.1021/ja3084362.
Ashford, Dennis L., Song, Wenjing, Concepcion, Javier J., Glasson, Christopher R. K., Brennaman, M. Kyle, Norris, Michael R., Fang, Zhen, Templeton, Joseph L., & Meyer, Thomas J. Photoinduced Electron Transfer in a Chromophore–Catalyst Assembly Anchored to TiO 2. United States. doi:10.1021/ja3084362.
Ashford, Dennis L., Song, Wenjing, Concepcion, Javier J., Glasson, Christopher R. K., Brennaman, M. Kyle, Norris, Michael R., Fang, Zhen, Templeton, Joseph L., and Meyer, Thomas J. Fri . "Photoinduced Electron Transfer in a Chromophore–Catalyst Assembly Anchored to TiO 2". United States. doi:10.1021/ja3084362.
@article{osti_1387015,
title = {Photoinduced Electron Transfer in a Chromophore–Catalyst Assembly Anchored to TiO 2},
author = {Ashford, Dennis L. and Song, Wenjing and Concepcion, Javier J. and Glasson, Christopher R. K. and Brennaman, M. Kyle and Norris, Michael R. and Fang, Zhen and Templeton, Joseph L. and Meyer, Thomas J.},
abstractNote = {Photoinduced formation, separation, and buildup of multiple redox equivalents are an integral part of cycles for producing solar fuels in dye-sensitized photoelectrosynthesis cells (DSPECs). Excitation wavelength-dependent electron injection, intra-assembly electron transfer, and pH-dependent back electron transfer on TiO2 were investigated for the molecular assembly [((PO3H2-CH2)-bpy)2Rua(bpy-NH-CO-trpy)Rub(bpy)(OH2)]4+ ([TiO2–RuaII–RubII–OH2]4+; ((PO3H2-CH2)2-bpy = ([2,2'-bipyridine]-4,4'-diylbis(methylene))diphosphonic acid); bpy-ph-NH-CO-trpy = 4-([2,2':6',2''-terpyridin]-4'-yl)-N-((4'-methyl-[2,2'-bipyridin]-4-yl)methyl) benzamide); bpy = 2,2'-bipyridine). This assembly combines a light-harvesting chromophore and a water oxidation catalyst linked by a synthetically flexible saturated bridge designed to enable long-lived charge-separated states. Following excitation of the chromophore, rapid electron injection into TiO2 and intra-assembly electron transfer occur on the subnanosecond time scale followed by microsecond–millisecond back electron transfer from the semiconductor to the oxidized catalyst, [TiO2(e–)–RuaII–RubIII–OH2]4+→[TiO2–RuaII–RubII–OH2]4+.},
doi = {10.1021/ja3084362},
journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 46,
volume = 134,
place = {United States},
year = {2012},
month = {11}
}