Interfacial Dynamics within an Organic Chromophore-Based Water Oxidation Molecular Assembly

Morseth, Zachary A.; Pho, Toan V.; Sheridan, Matthew V.; Meyer, Thomas J.; Schanze, Kirk S.; Reynolds, John R.; Papanikolas, John M.

doi:10.1021/acsami.7b02713

Title: Interfacial Dynamics within an Organic Chromophore-Based Water Oxidation Molecular Assembly

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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 (MO_x) 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 MO_x//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 Ru^II catalyst to regenerate the T₃ chromophore with subsequent back-electron transfer on the microsecond time scale.

Authors:

Morseth, Zachary A. ^[1]; Pho, Toan V. ^[2]; Sheridan, Matthew V. ^[1];

^[1];

^[3];

^[2];

^[1]

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:: Wed Apr 26 00:00:00 EDT 2017

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.

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                    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

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                    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.

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@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}

}

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