Modulating the Plasmon-Mediated Oxidation of p-Aminothiophenol with Asymmetrically Grafted Thiol Molecules.

A surface plasmon can drive many photochemical reactions, in which effective charge separation and migration is a key. In analogy to the plasmon-semiconductor interface, the plasmon-molecule interface may also be used to improve the separation and migration of hot carriers. In this work, by using in situ Raman spectroscopy, molecular grafting on silver nanostructures is found essential for modulating the charge separation and p-aminothiophenol (PATP) oxidation reaction. When the LUMO of the grafted molecules match well the energy distribution of the plasmon-generated hot electrons, the PATP oxidation process accelerates significantly. Moreover, compared with symmetrical grafting, asymmetrical grafting is more effective in regulating the charge separation and plasmon-mediated chemical reaction. This work provides an effective strategy for deep understanding and fine modulation of plasmon-mediated photochemistry.