Multi-stimuli-responsive polymer degradation by polyoxometalate photocatalysis and chloride ions

Abstract

Photocatalytic polymer degradation based on harnessing the abundant light energy present in the environment is one of the promising approaches to address the issue of plastic waste. In this study,...

A density functional study of the photocatalytic degradation of polycaprolactone by the decatungstate anion in acetonitrile solution

“…46 Such selectivity is due to the formation of highly electrophilic oxygen centers with partial radical character of the photoactive state of W10. As shown by the DFT calculations, 32 the a-C-H bond is the weakest, but the transition state is polarity mismatched due to the adjacent electron-withdrawing carbonyl group. Besides, steric repulsion may have some effect on the reactivity of the alpha position.…”

“…47,48 Preliminary calculations suggest that this reaction may play some role in the recently reported photocatalytic multi-stimuli-responsive polymer degradation. 32 The reaction of the HAT product is severely endergonic for the alpha position or marginally exergonic for the others, and the barrier height is relatively large, 14-28 kcal mol À1 (Fig. 3 and Table S3 in the ESI †).…”

“…This work is the first step toward understanding recently reported multi-stimuliresponsive polymer degradation by a POM photocatalyst. 32…”