Molecular Cocatalyst of p-Mercaptophenylboronic Acid Boosts the Plasmon-Mediated Reduction of p-Nitrothiophenol.

Abstract

Localized surface plasmon resonance (LSPR) has been demonstrated to be highly effective in the initialization or acceleration of chemical reactions because of its unique optical properties. However, because of the ultrashort lifetime (fs to ps) of plasmon-generated hot carriers, the potential of LSPR in photochemical reactions has not been fully exploited. Herein, we demonstrate an acceleration of the plasmon-mediated reduction of p-nitrothiophenol (PNTP) molecules on the surface of silver nanoparticles (AgNPs) with in situ Raman spectroscopy. p-Mercaptophenylboronic acid (PMPBA) molecules coadsorbed on AgNP surfaces act as a molecular cocatalyst in the plasmon-mediated reaction, resulting in a boosting of the PNTP reduction. This boosting is attributed to the improved transfer and separation of the plasmon-generated hot carriers at the interface of the AgNPs and coadsorbed PMPBA molecules. Our finding provides a highly simple, cost-effective, and highly effective strategy to promote plasmonic photochemistry by introducing a molecular cocatalyst, and this strategy can be extended to promote various plasmon-mediated reactions.