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Graphene Nanoreactors: Photoreduction of Prussian Blue in Aqueous Solution

Nappini, S and Matruglio, A and Naumenko, D and Dal Zilio, S and Lazzarino, M and De Groot, FMF and Kocabas, C and Balci, O and Magnano, E (2017) Graphene Nanoreactors: Photoreduction of Prussian Blue in Aqueous Solution. Journal of Physical Chemistry C, 121. pp. 22225-22233. ISSN 1932-7447

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Prussian dyes are characterized by interesting photomagnetic properties due to the photoinduced electron transfer involved in the Fe oxidation and spin state changes. Ferromagnetic Prussian blue (PB) in contact with titanium dioxide (TiO ) can be reduced to paramagnetic Prussian white (PW) upon UV band gap excitation of TiO . This process is promoted by the presence of a hole scavenger, such as water, fundamental to ensure the overall charge balance and the continuity of the process. In order to clarify the photoinduced reduction mechanism and the role of water, an innovative system of graphene nanobubbles (GNBs) filled with a PB aqueous solution was developed, enabling the application of electron spectroscopies to the liquid phase, up to now limited by the vacuum required to overcome the short electron inelastic mean free path in dense medium. In this work GNBs formed on the photocatalytic substrate are able to act as "nanoreactors", and they can control and take part in the reaction. The evolution of Fe L edge X-ray absorption spectra measured in total electron yield through the graphene membrane revealed the electron reduction from PB (Fe -CN-Fe ) to PW (Fe -CN-Fe ) upon UV irradiation, shedding light on the photoinduced electron transfer mechanism in liquid phase. The results, confirmed also by Raman spectroscopy, unequivocally demonstrate that the reaction occurs preferentially in aqueous solution, where water acts as hole scavenger. 2 2 2,3 III II II II

Item Type: Article
Divisions: Div B > Solid State Electronics and Nanoscale Science
Depositing User: Cron Job
Date Deposited: 22 Mar 2018 01:27
Last Modified: 13 Apr 2021 07:22
DOI: 10.1021/acs.jpcc.7b07898