Modulating the Plasmon-Mediated Decarboxylation Reaction on Silver Nanoparticles by Changing the Surface Adsorption of Molecular Cocatalysts of p-Hydroxythiophenol

The decarboxylation reaction can be accelerated with the assistance of localized surface plasmon resonance under mild conditions, benefiting from the enhanced light utilization and excitation of high-energy hot carriers. However, the reaction rate remains far below the theoretical limit since plasmon-excited hot carriers easily recombine due to their ultrashort lifetime. Herein, we effectively accelerate the decarboxylation reaction of p-mercaptobenzoic acid (PMBA) on the surface of silver nanoparticles (AgNPs) by coadsorbing p-hydroxythiophenol (PHTP) molecules as molecular cocatalysts. More importantly, the period of this coadsorption is crucial to the obtained reaction rate acceleration. Compared with short-period coadsorption, long-period coadsorption could lead to a larger acceleration in reaction rate, due to the further promoted separation of plasmon-generated hot carriers. This work provides a simple, convenient, and effective strategy to boost the decarboxylation reactions on silver surfaces. This strategy holds potential for developing a variety of highly efficient plasmon-based catalysts in the near future.