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.

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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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KEYWORDS

Oxidation

Molecules

Nitrogen

Oxygen

Plasmons

Scattering

Temperature metrology

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