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Novel photopolymerizations initiated by alkyl radicals generated from photocatalyzed decarboxylation of carboxylic acids over oxide semiconductor nanoparticles: Extended photo-Kolbe reactions

Paper ID Volume ID Publish Year Pages File Format Full-Text
28958 44109 2009 6 PDF Available
Title
Novel photopolymerizations initiated by alkyl radicals generated from photocatalyzed decarboxylation of carboxylic acids over oxide semiconductor nanoparticles: Extended photo-Kolbe reactions
Abstract

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 13C-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.

Keywords
Photopolymerization; Photo-Kolbe reaction; Photocatalysis; Semiconductor nanoparticle; Carboxylic acid
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Novel photopolymerizations initiated by alkyl radicals generated from photocatalyzed decarboxylation of carboxylic acids over oxide semiconductor nanoparticles: Extended photo-Kolbe reactions
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Publisher
Database: Elsevier - ScienceDirect
Journal: Journal of Photochemistry and Photobiology A: Chemistry - Volume 201, Issues 2–3, 25 January 2009, Pages 151–156
Authors
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Subjects
Physical Sciences and Engineering Chemical Engineering Bioengineering
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Price was $35.95
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Price after discount Only $4.95
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