Authors
Yu Chen, Zhong-Chen Ding, Xiao-Hui Peng, Yan-Ping Zhao, Xin Yuan, Shu-Xian Lv, Xiao-Shun Zhou, Chen-Chen Jiang, Xuliang Fan, Ya-Hao Wang
Published in
Langmuir : the ACS journal of surfaces and colloids. Oct 10, 2025. Epub Oct 10, 2025.
Abstract
Surface plasmon (SP)-driven catalytic decarboxylation reactions have garnered considerable attention in recent years. However, the mechanism of SP-induced decarboxylation within an electrochemical environment remains systematically unexplored. Herein, we investigate the electrochemical behavior of 4-mercaptobenzoic acid (4-MBA) within a Au nanoparticles/4-MBA molecular self-assembly layer/Au(111) configuration under varying pH conditions by using surface-enhanced Raman spectroscopy. It is found that 4-MBA efficiently converts to thiophenol (TP) in neutral/alkaline solutions. The TP conversion rate increased with applied potential from 10% to 40% at pH = 7, and from 20 to 50% at pH = 9. However, no TP formed at pH 1. In situ shell-isolated nanoparticle-enhanced Raman spectroscopy confirms that the decarboxylation is induced by SP-generated charge carriers. These reveal that increasing potential in neutral/alkaline solutions elevates OH- concentration within the electrical double layer, and significantly lowers the energy barrier for hot holes (h+) to combine with OH-. This promotes the formation of •OH radicals, triggering decarboxylation. Conversely, at pH = 1, extremely low OH- concentration results in a prohibitively high barrier for H2O oxidation to •OH by h+, inhibiting the reaction. This work provides molecular-level insights into the electrochemically promoted oxidation mechanisms governing plasmonic catalytic decarboxylation.
PMID:
41070527
Bibliographic data and abstract were imported from PubMed on 10 Oct 2025.
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