Identification of Ultraviolet Photoinduced Presolvated Electrons in Water as the Reducing Agent in the Photoreduction of Graphene Oxide

Abstract

Light-induced reduction of graphene oxide (GO) is a promising and an ingenious way of producing reduced GO (rGO) because it avoids the use of harsh chemicals. However, to date, the physicochemical mechanisms underlying photoreduction remain controversial. For example, there is no consensus on whether GO is reduced in water via direct excitation using ultraviolet (UV) laser light or via radiologically produced solvated electrons. Because of the photoinduced solvated electrons, the excited state of GO exhibits similar electronic absorption responses in the visible and near-infrared (NIR) wavelength range; therefore, distinguishing GO photoreduction dynamics from solvated electron dynamics via transient electronic absorption techniques is challenging. In this work, we used femtosecond-stimulated Raman spectroscopy (FSRS) to understand the ultrafast photoreduction dynamics of GO dispersion in water. Raman pump wavelength was selected to prevent the resonance of the excited-state Raman signal of water while obtaining the fingerprint Raman signals of GO. In contrast to the results of previous studies, our FSRS results indicate that upon UV excitation, the reduction of GO is triggered by the precursor of the solvated electron (presolvated electron) in 300 fs.