Dynamics of gap mode induced photocatalytic oxidation of p-alkyl thiophenol and relating molecules

Masayuki Futamata; Kanae Tabei; Keitaro Akai

doi:10.1117/12.2569777

21 September 2020 Dynamics of gap mode induced photocatalytic oxidation of p-alkyl thiophenol and relating molecules

Masayuki Futamata, Kanae Tabei, Keitaro Akai

Proceedings Volume 11468, Enhanced Spectroscopies and Nanoimaging 2020; 1146806 (2020) https://doi.org/10.1117/12.2569777
Event: SPIE Nanoscience + Engineering, 2020, Online Only

Abstract

We found a gap mode plasmon induced photocatlaytic oxidation of p-alkyl thiophenol (p-AlTP) to p-mercaptobenzoic acid (p-MBA). In contrast to p-AlTP, o-methyl TP and m-methyl TP were not oxidized, indicating preferential reactivity of the para position in TP molecules. Nonetheless, the site selectivity is not always valid in this type of photocatalytic reactions, as o-, m-, and p-MBAl molecules were oxidized to corresponding MBA. With respect to the reaction mechanism, we confirmed that the oxidation of p-MeTP is not induced by thermal heating of the samples up to 373 K. Subtle temperature increase (<10 K) during the gap mode-induced oxidation was also corroborated by the observed Stokes and anti-Stokes scattering intensity of p-MeTP. Oxygen molecules accelerated the oxidation of p-MeTP at room temperature, whereas nitrogen atmosphere generated an intermediate species attributable to p-mercaptobenzyl radical. We further investigated the reaction process using density functional theory.

Conference Presentation

Citation Download Citation

Masayuki Futamata, Kanae Tabei, and Keitaro Akai "Dynamics of gap mode induced photocatalytic oxidation of p-alkyl thiophenol and relating molecules", Proc. SPIE 11468, Enhanced Spectroscopies and Nanoimaging 2020, 1146806 (21 September 2020); https://doi.org/10.1117/12.2569777

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