Photoelectrochemical oxidation of a turn-on fluorescent probe mediated by a surface MnII catalyst covalently attached to TiO2 nanoparticles

Alec C. Durrell; Gonghu Li; Matthieu Koepf; Karin J. Young; Christian F.A. Negre; Laura J. Allen; William R. McNamara; Hee Eun Song; Victor S. Batista; Robert H. Crabtree; Gary W. Brudvig

doi:10.1016/j.jcat.2013.07.001

Photoelectrochemical oxidation of a turn-on fluorescent probe mediated by a surface Mn^II catalyst covalently attached to TiO₂ nanoparticles

Alec C. Durrell, Gonghu Li, Matthieu Koepf, Karin J. Young, Christian F.A. Negre, Laura J. Allen, William R. McNamara, Hee Eun Song, Victor S. Batista, Robert H. Crabtree, Gary W. Brudvig

Yale University

Research output: Contribution to journal › Article › peer-review

9 Citations (Scopus)

Abstract

A manganese complex covalently attached to a TiO₂ electrode via a light-absorbing organic linker (L) was used in the photooxidation of 20,70-dihydrodichlorofluorescein (H₂DCF). Significant and sustained photocurrent was observed upon visible-light illumination of the fully assembled anode in the presence of the substrate. The two-electron, two-proton oxidation of H₂DCF yields the fluorescent compound, 20,70- dichlorofluorescein (DCF). Our studies suggest that the Mn^II-L-TiO₂ architecture is an effective photoanode for multielectron chemistry, as production of DCF under visible-light illumination exceeds yields observed for bare TiO₂ as well as Zn^II-L-TiO₂ anodes. The turn-on fluorescent behavior of H₂DCF upon oxidation makes it an excellent substrate for the study of new photoanodes. The high fluorescence quantum yield of DCF allows for nanomolar sensitivity and real-time monitoring of substrate oxidation.

Original language	English
Pages (from-to)	37-44
Number of pages	8
Journal	Journal of Catalysis
Volume	310
DOIs	https://doi.org/10.1016/j.jcat.2013.07.001
Publication status	Published - 2014

Keywords

Dye-sensitized photoelectrochemical cell
Photoanode
Turn-on fluorescence

ASJC Scopus subject areas

Catalysis
Physical and Theoretical Chemistry

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10.1016/j.jcat.2013.07.001

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Durrell, A. C., Li, G., Koepf, M., Young, K. J., Negre, C. F. A., Allen, L. J., McNamara, W. R., Song, H. E., Batista, V. S., Crabtree, R. H., & Brudvig, G. W. (2014). Photoelectrochemical oxidation of a turn-on fluorescent probe mediated by a surface Mn^II catalyst covalently attached to TiO₂ nanoparticles. Journal of Catalysis, 310, 37-44. https://doi.org/10.1016/j.jcat.2013.07.001

Photoelectrochemical oxidation of a turn-on fluorescent probe mediated by a surface Mn^II catalyst covalently attached to TiO₂ nanoparticles. / Durrell, Alec C.; Li, Gonghu; Koepf, Matthieu; Young, Karin J.; Negre, Christian F.A.; Allen, Laura J.; McNamara, William R.; Song, Hee Eun; Batista, Victor S.; Crabtree, Robert H.; Brudvig, Gary W.

In: Journal of Catalysis, Vol. 310, 2014, p. 37-44.

Research output: Contribution to journal › Article › peer-review

Durrell, Alec C. ; Li, Gonghu ; Koepf, Matthieu ; Young, Karin J. ; Negre, Christian F.A. ; Allen, Laura J. ; McNamara, William R. ; Song, Hee Eun ; Batista, Victor S. ; Crabtree, Robert H. ; Brudvig, Gary W. / Photoelectrochemical oxidation of a turn-on fluorescent probe mediated by a surface Mn^II catalyst covalently attached to TiO₂ nanoparticles. In: Journal of Catalysis. 2014 ; Vol. 310. pp. 37-44.

@article{6b9718befc5d4f9aa544adf602b93c18,

title = "Photoelectrochemical oxidation of a turn-on fluorescent probe mediated by a surface MnII catalyst covalently attached to TiO2 nanoparticles",

abstract = "A manganese complex covalently attached to a TiO2 electrode via a light-absorbing organic linker (L) was used in the photooxidation of 20,70-dihydrodichlorofluorescein (H2DCF). Significant and sustained photocurrent was observed upon visible-light illumination of the fully assembled anode in the presence of the substrate. The two-electron, two-proton oxidation of H2DCF yields the fluorescent compound, 20,70- dichlorofluorescein (DCF). Our studies suggest that the MnII-L-TiO2 architecture is an effective photoanode for multielectron chemistry, as production of DCF under visible-light illumination exceeds yields observed for bare TiO2 as well as ZnII-L-TiO2 anodes. The turn-on fluorescent behavior of H2DCF upon oxidation makes it an excellent substrate for the study of new photoanodes. The high fluorescence quantum yield of DCF allows for nanomolar sensitivity and real-time monitoring of substrate oxidation.",

keywords = "Dye-sensitized photoelectrochemical cell, Photoanode, Turn-on fluorescence",

author = "Durrell, {Alec C.} and Gonghu Li and Matthieu Koepf and Young, {Karin J.} and Negre, {Christian F.A.} and Allen, {Laura J.} and McNamara, {William R.} and Song, {Hee Eun} and Batista, {Victor S.} and Crabtree, {Robert H.} and Brudvig, {Gary W.}",

note = "Funding Information: The authors acknowledge support from the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy (DE−FG02−07ER15909). NSF Grant CHE−0215926 provided funds to purchase the ELEXSYS E500 EPR spectrometer and the NSF ECCS # 0404191 Grant supported preliminary work. The generous donation of P25 TiO 2 by Evonik is greatly appreciated. G.L. thanks Dr. Christiaan Richter, Dr. Gerald Olack, and James D. Blakemore for their assistance in various aspects of experiments. ",

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doi = "10.1016/j.jcat.2013.07.001",

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AU - Durrell, Alec C.

AU - Li, Gonghu

AU - Koepf, Matthieu

AU - Young, Karin J.

AU - Negre, Christian F.A.

AU - Allen, Laura J.

AU - McNamara, William R.

AU - Song, Hee Eun

AU - Batista, Victor S.

AU - Crabtree, Robert H.

AU - Brudvig, Gary W.

N1 - Funding Information: The authors acknowledge support from the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy (DE−FG02−07ER15909). NSF Grant CHE−0215926 provided funds to purchase the ELEXSYS E500 EPR spectrometer and the NSF ECCS # 0404191 Grant supported preliminary work. The generous donation of P25 TiO 2 by Evonik is greatly appreciated. G.L. thanks Dr. Christiaan Richter, Dr. Gerald Olack, and James D. Blakemore for their assistance in various aspects of experiments.

PY - 2014

Y1 - 2014

N2 - A manganese complex covalently attached to a TiO2 electrode via a light-absorbing organic linker (L) was used in the photooxidation of 20,70-dihydrodichlorofluorescein (H2DCF). Significant and sustained photocurrent was observed upon visible-light illumination of the fully assembled anode in the presence of the substrate. The two-electron, two-proton oxidation of H2DCF yields the fluorescent compound, 20,70- dichlorofluorescein (DCF). Our studies suggest that the MnII-L-TiO2 architecture is an effective photoanode for multielectron chemistry, as production of DCF under visible-light illumination exceeds yields observed for bare TiO2 as well as ZnII-L-TiO2 anodes. The turn-on fluorescent behavior of H2DCF upon oxidation makes it an excellent substrate for the study of new photoanodes. The high fluorescence quantum yield of DCF allows for nanomolar sensitivity and real-time monitoring of substrate oxidation.

AB - A manganese complex covalently attached to a TiO2 electrode via a light-absorbing organic linker (L) was used in the photooxidation of 20,70-dihydrodichlorofluorescein (H2DCF). Significant and sustained photocurrent was observed upon visible-light illumination of the fully assembled anode in the presence of the substrate. The two-electron, two-proton oxidation of H2DCF yields the fluorescent compound, 20,70- dichlorofluorescein (DCF). Our studies suggest that the MnII-L-TiO2 architecture is an effective photoanode for multielectron chemistry, as production of DCF under visible-light illumination exceeds yields observed for bare TiO2 as well as ZnII-L-TiO2 anodes. The turn-on fluorescent behavior of H2DCF upon oxidation makes it an excellent substrate for the study of new photoanodes. The high fluorescence quantum yield of DCF allows for nanomolar sensitivity and real-time monitoring of substrate oxidation.

KW - Dye-sensitized photoelectrochemical cell

KW - Photoanode

KW - Turn-on fluorescence

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