Interfacial Dynamics within an Organic Chromophore-Based Water Oxidation Molecular Assembly
Abstract
Photoinduced electron injection, intra-assembly electron transfer, and back-electron transfer are investigated in a single-site molecular assembly formed by covalently linking a phosphonated terthiophene (T3) chromophore to a Ru(terpyridine)(bipyridine)(L)2+ (L = MeCN or H2O) water oxidation catalyst adsorbed onto a mesoporous metal-oxide (MOx) film. Density functional theory calculations of the T3-trpy-Ru-L assembly indicate that the molecular components are strongly coupled with enhanced low-energy absorptions owing to the presence of an intraligand charge transfer (ILCT) transition between the T3 and trpy moieties. Ultrafast spectroscopy of the MOx//T3-trpy-Ru-L assemblies reveals that excitation of the surface-bound T3 chromophore results in ps–ns electron injection into the metal-oxide conduction band. Electron injection is followed by rapid (<35 ps) intra-assembly electron transfer from the RuII catalyst to regenerate the T3 chromophore with subsequent back-electron transfer on the microsecond time scale.
- Authors:
-
- Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry
- Georgia Inst. of Technology, Atlanta, GA (United States). School of Chemistry and Biochemistry, School of Materials Science and Engineering, Center for Organic Photonics and Electronics, and Georgia Tech Polymer Network
- Univ. of Texas at San Antonio, TX (United States). Dept. of Chemistry
- 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)
- OSTI Identifier:
- 1388213
- Grant/Contract Number:
- SC0001011
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Applied Materials and Interfaces
- Additional Journal Information:
- Journal Volume: 9; Journal Issue: 19; 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 1944-8244
- 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
Morseth, Zachary A., Pho, Toan V., Sheridan, Matthew V., Meyer, Thomas J., Schanze, Kirk S., Reynolds, John R., and Papanikolas, John M. Interfacial Dynamics within an Organic Chromophore-Based Water Oxidation Molecular Assembly. United States: N. p., 2017.
Web. doi:10.1021/acsami.7b02713.
Morseth, Zachary A., Pho, Toan V., Sheridan, Matthew V., Meyer, Thomas J., Schanze, Kirk S., Reynolds, John R., & Papanikolas, John M. Interfacial Dynamics within an Organic Chromophore-Based Water Oxidation Molecular Assembly. United States. https://doi.org/10.1021/acsami.7b02713
Morseth, Zachary A., Pho, Toan V., Sheridan, Matthew V., Meyer, Thomas J., Schanze, Kirk S., Reynolds, John R., and Papanikolas, John M. Wed .
"Interfacial Dynamics within an Organic Chromophore-Based Water Oxidation Molecular Assembly". United States. https://doi.org/10.1021/acsami.7b02713. https://www.osti.gov/servlets/purl/1388213.
@article{osti_1388213,
title = {Interfacial Dynamics within an Organic Chromophore-Based Water Oxidation Molecular Assembly},
author = {Morseth, Zachary A. and Pho, Toan V. and Sheridan, Matthew V. and Meyer, Thomas J. and Schanze, Kirk S. and Reynolds, John R. and Papanikolas, John M.},
abstractNote = {Photoinduced electron injection, intra-assembly electron transfer, and back-electron transfer are investigated in a single-site molecular assembly formed by covalently linking a phosphonated terthiophene (T3) chromophore to a Ru(terpyridine)(bipyridine)(L)2+ (L = MeCN or H2O) water oxidation catalyst adsorbed onto a mesoporous metal-oxide (MOx) film. Density functional theory calculations of the T3-trpy-Ru-L assembly indicate that the molecular components are strongly coupled with enhanced low-energy absorptions owing to the presence of an intraligand charge transfer (ILCT) transition between the T3 and trpy moieties. Ultrafast spectroscopy of the MOx//T3-trpy-Ru-L assemblies reveals that excitation of the surface-bound T3 chromophore results in ps–ns electron injection into the metal-oxide conduction band. Electron injection is followed by rapid (<35 ps) intra-assembly electron transfer from the RuII catalyst to regenerate the T3 chromophore with subsequent back-electron transfer on the microsecond time scale.},
doi = {10.1021/acsami.7b02713},
journal = {ACS Applied Materials and Interfaces},
number = 19,
volume = 9,
place = {United States},
year = {Wed Apr 26 00:00:00 EDT 2017},
month = {Wed Apr 26 00:00:00 EDT 2017}
}
Web of Science