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Title: Visible Light Driven Benzyl Alcohol Dehydrogenation in a Dye-Sensitized Photoelectrosynthesis Cell

Authors:
; ; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC); Center for Solar Fuels (UNC EFRC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1167760
DOE Contract Number:
SC0001011
Resource Type:
Journal Article
Resource Relation:
Journal Name: J. Am. Chem. Soc.; Journal Volume: 136 (27); 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
Country of Publication:
United States
Language:
English
Subject:
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

Song, Wenjing, Vannucci, Aaron K., Farnum, Byron H., Lapides, Alexander M, Brennaman, M. Kyle, Kalanyan, Berç, Alibabaei, Leila, Concepcion, Javier J, Losego, Mark D., Parsons, Gregory N., and Meyer, Thomas J. Visible Light Driven Benzyl Alcohol Dehydrogenation in a Dye-Sensitized Photoelectrosynthesis Cell. United States: N. p., 2014. Web. doi:10.1021/ja505022f.
Song, Wenjing, Vannucci, Aaron K., Farnum, Byron H., Lapides, Alexander M, Brennaman, M. Kyle, Kalanyan, Berç, Alibabaei, Leila, Concepcion, Javier J, Losego, Mark D., Parsons, Gregory N., & Meyer, Thomas J. Visible Light Driven Benzyl Alcohol Dehydrogenation in a Dye-Sensitized Photoelectrosynthesis Cell. United States. doi:10.1021/ja505022f.
Song, Wenjing, Vannucci, Aaron K., Farnum, Byron H., Lapides, Alexander M, Brennaman, M. Kyle, Kalanyan, Berç, Alibabaei, Leila, Concepcion, Javier J, Losego, Mark D., Parsons, Gregory N., and Meyer, Thomas J. Wed . "Visible Light Driven Benzyl Alcohol Dehydrogenation in a Dye-Sensitized Photoelectrosynthesis Cell". United States. doi:10.1021/ja505022f.
@article{osti_1167760,
title = {Visible Light Driven Benzyl Alcohol Dehydrogenation in a Dye-Sensitized Photoelectrosynthesis Cell},
author = {Song, Wenjing and Vannucci, Aaron K. and Farnum, Byron H. and Lapides, Alexander M and Brennaman, M. Kyle and Kalanyan, Berç and Alibabaei, Leila and Concepcion, Javier J and Losego, Mark D. and Parsons, Gregory N. and Meyer, Thomas J},
abstractNote = {},
doi = {10.1021/ja505022f},
journal = {J. Am. Chem. Soc.},
number = ,
volume = 136 (27),
place = {United States},
year = {Wed Jul 09 00:00:00 EDT 2014},
month = {Wed Jul 09 00:00:00 EDT 2014}
}
  • Light-driven dehydrogenation of benzyl alcohol (BnOH) to benzaldehyde and hydrogen has been shown to occur in a dye-sensitized photoelectrosynthesis cell (DSPEC). In the DSPEC, the photoanode consists of mesoporous films of TiO2 nanoparticles or of core/shell nanoparticles with tin-doped In2O3 nanoparticle (nanoITO) cores and thin layers of TiO2 deposited by atomic layer deposition (nanoITO/TiO2). Metal oxide surfaces were coderivatized with both a ruthenium polypyridyl chromophore in excess and an oxidation catalyst. Chromophore excitation and electron injection were followed by cross-surface electron-transfer activation of the catalyst to RuIV=O2+, which then oxidizes benzyl alcohol to benzaldehyde. The injected electrons are transferred tomore » a Pt electrode for H2 production. The nanoITO/TiO2 core/shell structure causes a decrease of up to 2 orders of magnitude in back electron-transfer rate compared to TiO2. At the optimized shell thickness, sustained absorbed photon to current efficiency of 3.7% was achieved for BnOH dehydrogenation, an enhancement of ~10 compared to TiO2.« less
  • A hybrid strategy for solar water splitting is exploited here based on a dye-sensitized photoelectrosynthesis cell (DSPEC) with a mesoporous SnO 2/TiO 2 core/shell nanostructured electrode derivatized with a surface-bound Ru(II) polypyridyl-based chromophore–catalyst assembly. The assembly, [(4,4’-(PO 3H 2) 2bpy) 2Ru(4-Mebpy-4’-bimpy)Ru(tpy)(OH 2)] 4+ ([RuaII-RubII-OH 2] 4+, combines both a light absorber and a water oxidation catalyst in a single molecule. It was attached to the TiO 2 shell by phosphonate-surface oxide binding. The oxide-bound assembly was further stabilized on the surface by atomic layer deposition (ALD) of either Al 2O 3 or TiO 2 overlayers. Illumination of the resulting fluorine-dopedmore » tin oxide (FTO)|SnO 2/TiO 2|-[Ru a II-Ru b II-OH 2] 4+(Al 2O 3 or TiO 2) photoanodes in photoelectrochemical cells with a Pt cathode and a small applied bias resulted in visible-light water splitting as shown by direct measurements of both evolved H 2 and O 2. The performance of the resulting DSPECs varies with shell thickness and the nature and extent of the oxide overlayer. Use of the SnO 2/TiO 2 core/shell compared with nanoITO/TiO 2 with the same assembly results in photocurrent enhancements of ~5. In conclusion, systematic variations in shell thickness and ALD overlayer lead to photocurrent densities as high as 1.97 mA/cm 2 with 445-nm, ~90-mW/cm 2 illumination in a phosphate buffer at pH 7.« less