Abstract
The plasmon-driven oxidation of amine (−NH2) groups and the reduction of nitro (−NO2) groups on a nanostructured metal surface in an aqueous environment have been reported experimentally and theoretically. The question of which process occurs first in the aqueous environment is an interesting question in the field of plasmon-related photochemistry. Para-nitroaniline (PNA), with both nitro (−NO2) and amine (−NH2) groups, is the best candidate for studying the priority of the plasmon-driven oxidation and the reduction reactions in an aqueous environment. Using surface-enhanced Raman scattering (SERS) spectroscopy, our experimental results and theoretical simulations reveal that PNA is selectively catalyzed to 4,4′-diaminoazobenzene (DAAB) through the plasmon-assisted dimerization of the nitro (−NO2) group into an azo group in an aqueous environment. This indicates that the plasmon-driven reduction of the nitro (−NO2) group clearly occurs before the oxidation of the amine (−NH2) group in an aqueous environment. The plasmon-driven reduction of PNA to DAAB is a selective surface catalytic reduced reaction in aqueous environment.
Highlights
It is not clear what role surface plasmons play in the priority of these catalytic reactions
The third possibility is the occurrence of simultaneous oxidation and reduction reactions that produce 4-nitro4′ -aminoazobenzene (NAAB)
Our results revealed that PNA was selectively reduced to DAAB with the help of surface plasmon in the aqueous environment
Summary
Since the first report of the plasmon-driven oxidation reaction in which para-aminothiophenol (PATP, see Fig. 1a) is catalyzed to p,p′ -dimercaptoazobenzene (DMAB, see Fig. 1b) in 20101,2, the realization of plasmon-driven chemical reactions has been one of most important advances in the field of nanoplasmonics[3,4,5,6,7,8,9,10,11,12,13,14,15,16], which is called plasmon chemistry[8]. The plasmon-driven chemical reaction of PNA in an aqueous environment was investigated experimentally using electrochemical surface-enhanced Raman scattering (SERS) spectroscopy, and
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