Photoelectrochemical hole injection revealed in polyoxotitanate nanocrystals functionalized with organic adsorbates

Christian F.A. Negre; Karin J. Young; Ma Belén Oviedo; Laura J. Allen; Cristián G. Sánchez; Katarzyna N. Jarzembska; Jason B. Benedict; Robert H. Crabtree; Philip Coppens; Gary W. Brudvig; Victor S. Batista

doi:10.1021/ja509270f

Photoelectrochemical hole injection revealed in polyoxotitanate nanocrystals functionalized with organic adsorbates

Christian F.A. Negre, Karin J. Young, Ma Belén Oviedo, Laura J. Allen, Cristián G. Sánchez, Katarzyna N. Jarzembska, Jason B. Benedict, Robert H. Crabtree, Philip Coppens, Gary W. Brudvig, Victor S. Batista

Yale University

Research output: Contribution to journal › Article

41 Citations (Scopus)

Abstract

We find that crystallographically resolved Ti₁₇O₂₄(OPrⁱ)₂₀ nanoparticles, functionalized by covalent attachment of 4-nitrophenyl-acetylacetonate or coumarin 343 adsorbates, exhibit hole injection into surface states when photoexcited with visible light (λ = 400-680 nm). Our findings are supported by photoelectrochemical measurements, EPR spectroscopy, and quantum dynamics simulations of interfacial charge transfer. The underlying mechanism is consistent with measurements of photocathodic currents generated with visible light for thin layers of functionalized polyoxotitanate nanocrystals deposited on FTO working electrodes. The reported experimental and theoretical analysis demonstrates for the first time the feasibility of p-type sensitization of TiO₂ solely based on covalent binding of organic adsorbates.

Original language	English
Pages (from-to)	16420-16429
Number of pages	10
Journal	Journal of the American Chemical Society
Volume	136
Issue number	46
DOIs	https://doi.org/10.1021/ja509270f
Publication status	Published - Nov 19 2014

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ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

Cite this

Negre, C. F. A., Young, K. J., Oviedo, M. B., Allen, L. J., Sánchez, C. G., Jarzembska, K. N., Benedict, J. B., Crabtree, R. H., Coppens, P., Brudvig, G. W., & Batista, V. S. (2014). Photoelectrochemical hole injection revealed in polyoxotitanate nanocrystals functionalized with organic adsorbates. Journal of the American Chemical Society, 136(46), 16420-16429. https://doi.org/10.1021/ja509270f

Photoelectrochemical hole injection revealed in polyoxotitanate nanocrystals functionalized with organic adsorbates. / Negre, Christian F.A.; Young, Karin J.; Oviedo, Ma Belén; Allen, Laura J.; Sánchez, Cristián G.; Jarzembska, Katarzyna N.; Benedict, Jason B.; Crabtree, Robert H.; Coppens, Philip; Brudvig, Gary W.; Batista, Victor S.

In: Journal of the American Chemical Society, Vol. 136, No. 46, 19.11.2014, p. 16420-16429.

Research output: Contribution to journal › Article

Negre, CFA, Young, KJ, Oviedo, MB, Allen, LJ, Sánchez, CG, Jarzembska, KN, Benedict, JB, Crabtree, RH, Coppens, P, Brudvig, GW & Batista, VS 2014, 'Photoelectrochemical hole injection revealed in polyoxotitanate nanocrystals functionalized with organic adsorbates', Journal of the American Chemical Society, vol. 136, no. 46, pp. 16420-16429. https://doi.org/10.1021/ja509270f

Negre, Christian F.A. ; Young, Karin J. ; Oviedo, Ma Belén ; Allen, Laura J. ; Sánchez, Cristián G. ; Jarzembska, Katarzyna N. ; Benedict, Jason B. ; Crabtree, Robert H. ; Coppens, Philip ; Brudvig, Gary W. ; Batista, Victor S. / Photoelectrochemical hole injection revealed in polyoxotitanate nanocrystals functionalized with organic adsorbates. In: Journal of the American Chemical Society. 2014 ; Vol. 136, No. 46. pp. 16420-16429.

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title = "Photoelectrochemical hole injection revealed in polyoxotitanate nanocrystals functionalized with organic adsorbates",

abstract = "We find that crystallographically resolved Ti17O24(OPri)20 nanoparticles, functionalized by covalent attachment of 4-nitrophenyl-acetylacetonate or coumarin 343 adsorbates, exhibit hole injection into surface states when photoexcited with visible light (λ = 400-680 nm). Our findings are supported by photoelectrochemical measurements, EPR spectroscopy, and quantum dynamics simulations of interfacial charge transfer. The underlying mechanism is consistent with measurements of photocathodic currents generated with visible light for thin layers of functionalized polyoxotitanate nanocrystals deposited on FTO working electrodes. The reported experimental and theoretical analysis demonstrates for the first time the feasibility of p-type sensitization of TiO2 solely based on covalent binding of organic adsorbates.",

author = "Negre, {Christian F.A.} and Young, {Karin J.} and Oviedo, {Ma Bel{\'e}n} and Allen, {Laura J.} and S{\'a}nchez, {Cristi{\'a}n G.} and Jarzembska, {Katarzyna N.} and Benedict, {Jason B.} and Crabtree, {Robert H.} and Philip Coppens and Brudvig, {Gary W.} and Batista, {Victor S.}",

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AU - Allen, Laura J.

AU - Sánchez, Cristián G.

AU - Jarzembska, Katarzyna N.

AU - Benedict, Jason B.

AU - Crabtree, Robert H.

AU - Coppens, Philip

AU - Brudvig, Gary W.

AU - Batista, Victor S.

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AB - We find that crystallographically resolved Ti17O24(OPri)20 nanoparticles, functionalized by covalent attachment of 4-nitrophenyl-acetylacetonate or coumarin 343 adsorbates, exhibit hole injection into surface states when photoexcited with visible light (λ = 400-680 nm). Our findings are supported by photoelectrochemical measurements, EPR spectroscopy, and quantum dynamics simulations of interfacial charge transfer. The underlying mechanism is consistent with measurements of photocathodic currents generated with visible light for thin layers of functionalized polyoxotitanate nanocrystals deposited on FTO working electrodes. The reported experimental and theoretical analysis demonstrates for the first time the feasibility of p-type sensitization of TiO2 solely based on covalent binding of organic adsorbates.

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10.1021/ja509270f