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Photocatalytic Oxidation of Organic Acids on Quantum-Sized Semiconductor Colloids

Carraway, Elizabeth R. and Hoffman, Amy J. and Hoffmann, Michael R. (1994) Photocatalytic Oxidation of Organic Acids on Quantum-Sized Semiconductor Colloids. Environmental Science and Technology, 28 (5). pp. 786-793. ISSN 0013-936X. https://resolver.caltech.edu/CaltechAUTHORS:20150811-111819378

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Abstract

A detailed analysis of the reaction products and mechanisms of the photocatalytic oxidation of acetate in the presence of quantum-sized ZnO colloids (Dp ≈ 40 Å) is presented. The principal oxidation products and reaction intermediates are determined to be CO_2, HCO_2^-, CHOCO_2^-, HCHO, CH_3OOH, CH_3COOOH, and H_2O_2. Formate and glyoxylate, which are found as intermediates in the photooxidation of acetate, also serve as effective electron donors on illuminated ZnO surfaces. The proposed relative reactivity of electron donors toward photooxidation is in the following order: CHOCO_2- > HCO_2^- > HCHO > CH_3CO_2^- ≥ H_2O_2 CH_3COOOH > CH_3OOH. Observed product distributions are discussed in terms of pathways involving direct oxidation of surface-bound acetate by valence band holes (or trapped holes) and the indirect oxidation of acetate by surface-bound hydroxyl radicals. The product distribution observed at low photon fluxes is not consistent with oxidation primarily by free hydroxyl radicals. A mechanism involving the reaction of an intermediate carbon-centered radical with > ZnOH surface sites is proposed. When electron donors are strongly adsorbed to semiconductor surfaces, surface-mediated reactions appear to play a dominant role in the determination of the time-dependent product distributions.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/es00054a007DOIArticle
http://pubs.acs.org/doi/abs/10.1021/es00054a007PublisherArticle
ORCID:
AuthorORCID
Hoffmann, Michael R.0000-0001-6495-1946
Additional Information:© 1994 American Chemical Society. Received for review May 11,1993. Revised manuscript received November 29,1993. Accepted January 5, 1994. We are grateful to the U.S. Environmental Protection Agency (815041-01-0; 815170-01-0) and DARPA (ONRN0014-92-J-1901) for financial support, and we appreciate the assistance of Drs. Detlef Bahnemann, Claudius Kormann, and Peter Green in various aspects of this research.
Funders:
Funding AgencyGrant Number
Environmental Protection Agency (EPA)815041-01-0
Environmental Protection Agency (EPA)815170-01-0
Office of Naval Research (ONR)N0014-92-J-1901
Defense Advanced Research Projects Agency (DARPA)UNSPECIFIED
Issue or Number:5
Record Number:CaltechAUTHORS:20150811-111819378
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150811-111819378
Official Citation:Photocatalytic Oxidation of Organic Acids on Quantum-Sized Semiconductor Colloids Elizabeth R. Carraway, Amy J. Hoffman, and Michael R. Hoffmann Environmental Science & Technology 1994 28 (5), 786-793 DOI: 10.1021/es00054a007
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:59400
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:12 Aug 2015 16:52
Last Modified:03 Mar 2020 13:01

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