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Harnessing Excess Photon Energy in Photoinduced Surface Electron Transfer between Salicylate and Illuminated Titanium Dioxide Nanoparticles

Grela, María A. and Brusa, Marta A. and Colussi, Agustín J. (1997) Harnessing Excess Photon Energy in Photoinduced Surface Electron Transfer between Salicylate and Illuminated Titanium Dioxide Nanoparticles. Journal of Physical Chemistry B, 101 (51). pp. 10986-10989. ISSN 1520-6106. https://resolver.caltech.edu/CaltechAUTHORS:20150623-154802284

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Abstract

Photons absorbed by nanocrystalline TiO_2 particles at 254 nm are found to be 7.7 times more efficient than those at 366 nm for driving the photocatalytic oxidation of salicylate S in aerated aqueous sols. The occurrence of this phenomenon is ascribed to the conjunction of (1) short diffusion times of photogenerated carriers to the surface of nanoparticles, a fact that allows chemical reaction to compete with energy relaxation, and (2) favorable donor Eo(S^-/S^•) redox potential and interfacial reorganization energy λ_R values, which make electron-transfer rates peak at energies inside the valence band of TiO_2. Master equation kinetic modeling shows that electron transfer from S into hyperthermal valence band holes takes place at rates consistent with k_(sc) ∼ 10^4 cm s^(-1) at optimal exoergicity, if the excess energy is dissipated into the crystal lattice within a few picoseconds. Hydroxyl ions as donors would require much slower thermalization rates.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/jp972172xDOIArticle
http://pubs.acs.org/doi/abs/10.1021/jp972172xPublisherArticle
ORCID:
AuthorORCID
Colussi, Agustín J.0000-0002-3400-4101
Additional Information:© 1997 American Chemical Society. Received: July 3, 1997; In Final Form: NoVember 3, 1997. This project was financially supported by the National Research Council of Argentina (CONICET) under Grant PID1131/91.
Funders:
Funding AgencyGrant Number
Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET)PID1131/91
Issue or Number:51
Record Number:CaltechAUTHORS:20150623-154802284
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150623-154802284
Official Citation:Harnessing Excess Photon Energy in Photoinduced Surface Electron Transfer between Salicylate and Illuminated Titanium Dioxide Nanoparticles María A. Grela, Marta A. Brusa, and Agustín J. Colussi The Journal of Physical Chemistry B 1997 101 (51), 10986-10989 DOI: 10.1021/jp972172x
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:58500
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:24 Jul 2015 20:27
Last Modified:03 Oct 2019 08:36

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