Probing Plasmon-Induced Chemical Mechanisms by Free-Radical Nanophotopolymerization
Résumé
Localized surface plasmon-induced photopolymerization of free-radical acrylate monomers is an efficient, smart, and versatile method for preparing metal/polymer hybrid nanoparticles (NPs) with accurate control of the thickness and spatial distribution of the polymer on the NP surface. Despite a growing number of practical demonstrations, the mechanism leading to polymerization of the acrylate monomer by localized surface plasmon resonance (LSPR) is still controversial. It could be related to either a photochemical mechanism enhanced by electromagnetic hot spots (enhanced near field) or thermoplasmonic (photothermal heating) or electrochemical (via hot-carrier injection) mechanisms, as proposed in different studies. After developing a high-resolution characterization method based on transmission electron microscopy and by tuning the photopolymer composition and the irradiation conditions, the LSPR-induced physicochemical mechanism is revealed. We demonstrate that the photochemical pathway is the main mechanism under the mild irradiation conditions chosen for this process. In a more general way, photopolymerization proves to be a powerful tool to investigate the coupling between metal nanostructures and organic moieties.
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20210330_Article_revised#2_final for HAL.pdf (2.31 Mo)
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20210330_Article SI_revised#2_final for HAL.pdf (4.47 Mo)
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