Molecular Coadsorption of <i>p</i>-Hydroxythiophenol on Silver Nanoparticles Boosts the Plasmon-Mediated Decarboxylation Reaction
Yuqin Chen, Yameng Zhu, Huixiang Sheng, Jin Wang, Chengyu Zhang, Yaqi Chen, Wei Huang, Gang Lü
Abstract
Surface plasmons have received much attention in chemical reactions because of their high light-utilizing efficiency, high reaction rate, and mild reaction conditions. However, the potential of plasmonic photochemistry has not been fully exploited, mainly due to the limited lifetime of plasmon-generated hot carriers. Herein, using in situ Raman spectroscopy, we reveal that the coadsorption of p-hydroxythiophenol (PHTP) molecules significantly accelerates the plasmon-mediated decarboxylation reaction of p-mercaptobenzoic acid adsorbed on silver nanoparticles. The observed boosting of the decarboxylation reaction is attributed to the matched energy distribution of the plasmon-generated hot electrons to the lowest unoccupied molecular orbital (LUMO) level of the coadsorbed PHTP molecules. Our findings will help not only to deepen the understanding of the plasmon-mediated chemical reactions but also to fabricate highly efficient plasmonic catalysts conveniently and cost-effectively.