Abstract
Plasmon-assisted reactions have different reaction mechanisms than conventional chemical reactions occurring in solutions, and the hot electrons produced by plasmon decay play an irreplaceable role in plasmon-assisted coupling reactions. Here, we use p-mercaptobenzoic acid (pMBA) to illustrate this point from different aspects. In a typical chemical reaction, a base is added to deprotonate the carboxylic acid group in pMBA. In this system, however, there is no alkali or external charge to remove the hydrogen, but it is obvious that this system is a dynamic process. Here, although a Lewis base (Ag NPs) was used as the base, the generated hot electrons were trapped by hydrogen ions in an acidic environment, which reduced the efficiency of the ionization reaction. We used SERS to study the ionization of pMBA and to propose a method to regulate its ionization by adjusting its substituents. Furthermore, in contrast to previous studies, the direction of electron flow is clearly defined in this reaction system.
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