Identification of the First Elementary Step in the Photocatalytic Reduction of Nitrobenzenethiols on a Metallic Surface

Han Kyu Choi, Kang Sup Lee, Hyun Hang Shin, Zee Hwan Kim

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17 Scopus citations

Abstract

Reduction of nitrobenzene is widely used for the assessment of the catalytic activities of nanoparticles, yet its mechanism is still largely unverified. Here, using the surface-enhanced Raman scattering (SERS), we have identified an intermediate of the first step in the photocatalytic reduction of nitrobenzenethiols (NBTs) on a metallic surface. The formation of the intermediate is identified by a fast red-shift of the NO2 symmetric-stretching peak of the SERS spectra of reacting NBTs, prior to the slow intensity decay. On the basis of the laser power dependences of the rates of spectral changes, electrochemical SERS, and quantum chemical calculations, we conclude that the intermediate is the anion radical of nitrobenzenethiol that is formed by the metal-to-molecule single-electron transfer reaction. The subsequent intensity decay of the peak, which is the rate-determining step of the whole reduction reaction, corresponds to another single-electron reduction of the anion radical into dihydroxyaminobenzenethiol or dianion of NBT.

Original languageEnglish (US)
Pages (from-to)4099-4104
Number of pages6
JournalJournal of Physical Chemistry Letters
Volume7
Issue number20
DOIs
StatePublished - Oct 20 2016

Bibliographical note

Funding Information:
The work is supported by BioNano Health-Guard Research Center funded by the Ministry of Science, ICT & Future Planning (MSIP) of Korea as Global Frontier Project (HGUARD-2013M3A6B2078947), and by the National Research Foundation of Korea (NRF) grant funded by MSIP (grant no. NRF-2016R1A2B2011160).

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