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.
Skip Nav Destination
Article navigation
14 September 2020
Research Article|
September 11 2020
Interaction of 4-nitrothiophenol with low energy electrons: Implications for plasmon mediated reactions
Robin Schürmann
;
Robin Schürmann
a)
1
Physical Chemistry, Institute of Chemistry, University of Potsdam
, Karl-Liebknecht-Str. 24-25, 14476 Potsdam-Golm, Germany
a)Author to whom correspondence should be addressed: robin.schuermann@uni-potsdam.de
Search for other works by this author on:
Thomas F. M. Luxford
;
Thomas F. M. Luxford
2
J. Heyrovský Institute of Physical Chemistry of the Czech Academy of Sciences
, Dolejškova 3, 18223 Prague, Czech Republic
Search for other works by this author on:
Ivo S. Vinklárek;
Ivo S. Vinklárek
2
J. Heyrovský Institute of Physical Chemistry of the Czech Academy of Sciences
, Dolejškova 3, 18223 Prague, Czech Republic
Search for other works by this author on:
Jaroslav Kočišek
;
Jaroslav Kočišek
2
J. Heyrovský Institute of Physical Chemistry of the Czech Academy of Sciences
, Dolejškova 3, 18223 Prague, Czech Republic
Search for other works by this author on:
Mateusz Zawadzki
;
Mateusz Zawadzki
3
Department of Atomic, Molecular and Optical Physics, Faculty of Applied Physics and Mathematics, Gdańsk University of Technology
, ul. G. Narutowicza 11/12, 80-233 Gdańsk, Poland
Search for other works by this author on:
Ilko Bald
Ilko Bald
1
Physical Chemistry, Institute of Chemistry, University of Potsdam
, Karl-Liebknecht-Str. 24-25, 14476 Potsdam-Golm, Germany
Search for other works by this author on:
a)Author to whom correspondence should be addressed: robin.schuermann@uni-potsdam.de
J. Chem. Phys. 153, 104303 (2020)
Article history
Received:
June 17 2020
Accepted:
August 14 2020
Citation
Robin Schürmann, Thomas F. M. Luxford, Ivo S. Vinklárek, Jaroslav Kočišek, Mateusz Zawadzki, Ilko Bald; Interaction of 4-nitrothiophenol with low energy electrons: Implications for plasmon mediated reactions. J. Chem. Phys. 14 September 2020; 153 (10): 104303. https://doi.org/10.1063/5.0018784
Download citation file:
Sign in
Don't already have an account? Register
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Sign in via your Institution
Sign in via your InstitutionPay-Per-View Access
$40.00