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Boosting the Plasmon-Mediated Electrochemical Oxidation of p-Aminothiophenol with p-Hydroxythiophenol as Molecular Cocatalyst
ACS Applied Materials & Interfaces ( IF 8.3 ) Pub Date : 2023-12-01 , DOI: 10.1021/acsami.3c12778
Karuppasamy Kohila Rani 1 , Qiong Yang 1 , Yuan-Hui Xiao 2 , Rajkumar Devasenathipathy 1 , Zhihao Lu 1 , Xinya Chen 1 , Lu Jiang 1 , Zemin Li 1 , Qinghua Liu 1 , Haonan Chen 1 , Liuyingzi Yu 1 , Zhuoyao Li 1 , Soukaina Khayour 1 , Junjie Wang 1 , Kaili Wang 1 , Gongqiang Li 1 , De-Yin Wu 2 , Gang Lu 1
Affiliation  

Plasmon-mediated electrochemistry is an emerging area of interest in which the electrochemical reactions are enhanced by employing metal nanostructures possessing localized surface plasmon resonance (LSPR). However, the reaction efficacy is still far below its theoretical limit due to the ultrafast relaxation of LSPR-generated hot carriers. Herein, we introduce p-hydroxythiophenol (PHTP) as a molecular cocatalyst to significantly improve the reaction efficacy in plasmon-mediated electrochemical oxidation of p-aminothiophenol (PATP) on gold nanoparticles. Using electrochemical techniques, in situ Raman spectroscopy, and theoretical calculations, we elucidate that the presence of PHTP improves the hot hole-mediated electrochemical oxidation of PATP by 2-fold through the trapping of plasmon-mediated hot electrons. In addition, the selectivity of PATP oxidation could also be modulated by the introduction of PHTP cocatalyst. This tactic of employing molecular cocatalyst can be drawn out to endorse various plasmonic electrochemical reactions because of its simple protocol, high efficiency, and high selectivity.

中文翻译:

以对羟基苯硫酚作为分子助催化剂促进等离激元介导的对氨基苯硫酚电化学氧化

等离子体介导的电化学是一个新兴的令人感兴趣的领域,其中通过采用具有局域表面等离子体共振(LSPR)的金属纳米结构来增强电化学反应。然而,由于局域表面等离子体共振产生的热载流子的超快弛豫,反应效率仍远低于其理论极限。在此,我们引入对羟基苯硫酚(PHTP)作为分子助催化剂,以显着提高金纳米颗粒上等离激元介导的对氨基苯硫酚(PATP)电化学氧化的反应效率。利用电化学技术、原位拉曼光谱和理论计算,我们阐明了 PHTP 的存在通过捕获等离子体介导的热电子将 PATP 的热空穴介导的电化学氧化提高了 2 倍。此外,PATP氧化的选择性也可以通过引入PHTP助催化剂来调节。这种使用分子助催化剂的策略由于其简单的方案、高效率和高选择性,可以用于支持各种等离子体电化学反应。
更新日期:2023-12-01
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