Journal
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
Volume 201, Issue 2-3, Pages 151-156Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.jphotochem.2008.10.013
Keywords
Photopolymerization; Photo-Kolbe reaction; Photocatalysis; Semiconductor nanoparticle; Carboxylic acid
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Funding
- National Nature Science Foundation of China (NSFC) [20574011]
- Science and Technology Commission of Shanghai Municipality [0752nm006, 055207080]
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Polymerizations of vinyl acetate are photocatalyzed by TiO2 nanoparticles in presence of carboxylic acids including propionic acid, n-butyric acid and pivalic acid. Nuclear magnetic resonance (NMR) analysis using C-13-labeled n-butyric acid as the probing molecule demonstrates that the polymerization of vinyl acetate is initiated by alkyl radicals generated from photocatalytic decarboxylation of the carboxylic acid. A universal mechanism is established with extending the photo-Kolbe reaction from acetic acid to the carboxylic acids with longer chains. Kinetics studies find that n-butyric acid has higher initiation rate than acetic acid, indicating more efficient decarboxylation for butyric acid than acetic acid in their aqueous solutions. It is proved that carboxylates participate in the decarboxylation. Attenuated total reflection Fourier-transform infrared (ATR-FTIR) spectra are obtained with aqueous solutions of the carboxylic acids in contact with a layer of the TiO2 nanoparticles, and the observations are discussed with respect to the interaction between the TiO2 and carboxylic acids. (c) 2008 Elsevier B.V. All rights reserved.
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