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Photocatalytic Degradation of Pentachlorophenol on TiO_2 Particles: Identification of Intermediates and Mechanism of Reaction

Mills, German and Hoffmann, Michael R. (1993) Photocatalytic Degradation of Pentachlorophenol on TiO_2 Particles: Identification of Intermediates and Mechanism of Reaction. Environmental Science and Technology, 27 (8). pp. 1681-1689. ISSN 0013-936X. https://resolver.caltech.edu/CaltechAUTHORS:20150811-111820190

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Abstract

The photoassisted oxidation of pentachlorophenol (PCP) in TiO_2 particle suspensions was investigated. Complete dechlorination of 47 µM PCP was achieved after 3 h of illumination at high intensity with apparent quantum efficiencies (ΦPCP, ΦCI, ΦH+, ΦH_2O_2) ranging from 1 to 3%. p-Chloranil, tetrachlorohydroquinone, H_2O_2, and o-chloranil were formed as the principal intermediates. Formate and acetate were formed as products during the latter stages of photooxidation. The mechanism for photooxidation of PCP proceeds via hydroxyl radical attack on the para position of the PCP ring to form a semiquinone radical which in turn disproportionates to yield p-chloranil and tetrachlorohydroquinone. Under high-intensity illumination, the reaction intermediates are attacked further by •OH to yield HCO_2^-, CH_3CO_2^-, CO_2, H^+, and Cl^-.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/es00045a027DOIArticle
http://pubs.acs.org/doi/abs/10.1021/es00045a027PublisherArticle
ORCID:
AuthorORCID
Hoffmann, Michael R.0000-0001-6495-1946
Alternate Title:Photocatalytic degradation of pentachlorophenol on titanium dioxide particles: identification of intermediates and mechanism of reaction
Additional Information:© 1883 American Chemical Society. Received for review July 6, 1992. Revised manuscript received April 13, 1993. Accepted May 13,1993. Publication Date: August 1993. With are grateful to the U.S. Environmental Protection Agency (Grant R813326-01-0) for the financial resources to pursue this project and to the Degussa Corporation for a gift of the titanium dioxide.
Funders:
Funding AgencyGrant Number
Environmental Protection Agency (EPA)R813326-01-0
Issue or Number:8
Record Number:CaltechAUTHORS:20150811-111820190
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150811-111820190
Official Citation:Photocatalytic degradation of pentachlorophenol on titanium dioxide particles: identification of intermediates and mechanism of reaction German Mills and Michael R. Hoffmann Environmental Science & Technology 1993 27 (8), 1681-1689 DOI: 10.1021/es00045a027
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:59403
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:11 Aug 2015 18:58
Last Modified:03 Mar 2020 13:01

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