Interaction of 4-nitrothiophenol with low energy electrons: Implications for plasmon mediated reactions

0533837 - ÚFCH JH 2021 RIV US eng J - Journal Article
Schuermann, R. - Luxford, Thomas Frederick Murray - Vinklárek, Ivo S. - Kočišek, Jaroslav - Zawadzki, Mateusz - Bald, I.
Interaction of 4-nitrothiophenol with low energy electrons: Implications for plasmon mediated reactions.
Journal of Chemical Physics. Roč. 153, č. 10 (2020), č. článku 104303. ISSN 0021-9606. E-ISSN 1089-7690
R&D Projects: GA ČR(CZ) GA19-01159S
Institutional support: RVO:61388955
Keywords : photocatalytic reduction * hot-electrons * attachment * molecules * 4-aminothiophenol * dissociation * desorption * interface * sulfide * anion
OECD category: Physical chemistry
Impact factor: 3.488, year: 2020
Method of publishing: Limited access

The reduction of 4-nitrothiophenol (NTP) to 4-4 'dimercaptoazobenzene (DMAB) on laser illuminated noble metal nanoparticles is one of the most widely studied plasmon mediated reactions. The reaction is most likely triggered by a transfer of low energy electrons from the nanoparticle to the adsorbed molecules. Besides the formation of DMAB, dissociative side reactions of NTP have also been observed. Here, we present a crossed electron-molecular beam study of free electron attachment to isolated NTP in the gas-phase. Negative ion yields are recorded as a function of the electron energy, which helps to assess the accessibility of single electron reduction pathways after photon induced electron transfer from nanoparticles. The dominant process observed with isolated NTP is associative electron attachment leading to the formation of the parent anion of NTP. Dissociative electron attachment pathways could be revealed with much lower intensities, leading mainly to the loss of functional groups. The energy gained by one electron reduction of NTP may also enhance the desorption of NTP from nanoparticles. Our supporting experiments with small clusters, then, show that further reaction steps are necessary after electron attachment to produce DMAB on the surfaces.
Permanent Link: http://hdl.handle.net/11104/0312092