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Research Article

Polarity, intramolecular charge transfer, and hydrogen bond co-mediated solvent effects on the optical properties of graphene quantum dots

Yalei Hu1, Christof Neumann2, Lena Scholtz1,3, Andrey Turchanin2, Ute Resch-Genger3( ), Siegfried Eigler1( )
Institute of Chemistry and Biochemistry, Freie Universität Berlin, Takustraße 3, 14195 Berlin, Germany
Institute of Physical Chemistry and Abbe Center of Photonics, Friedrich Schiller University Jena, Lessingstraße 10, 07743 Jena, Germany
Federal Institute for Materials Research and Testing (BAM), Division Biophotonics, Richard Willstätter Straße 11, 12489 Berlin, Germany
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Graphical Abstract

Based on luminescence studies of graphene quantum dots (GQDs) in solvents of varying polarity and proticity, a fluorescence (FL) mechanism is proposed to explain the observed solvent dependence utilizing a molecular picture and a combination of polarity, intramolecular charge transfer (ICT), and hydrogen bonding effects.

Abstract

Graphene quantum dots (GQDs) have attracted increasing attention due to their favorable optical properties and have been widely used, e.g., in the biomedical field. However, the properties related to the chemical structure of GQDs, resulting in solvent-dependent optical properties, still remain unclear. Herein, we present the synthesis of long-wavelength emitting GQDs with a size of about 3.6 nm via a solvothermal method using oxo-functionalized graphene (oxo-G) and p-phenylenediamine as precursors and their structural and surface chemical analysis by transmission electron and atomic force microscopy (TEM; AFM) as well as Fourier-transform infrared, Raman, and X-ray photoelectron spectroscopy (FTIR; Raman; XPS). Subsequently, the influence of solvent polarity and proticity on the optical properties of the as-prepared GQDs bearing –OH, –NH2, –COOH and pyridine surface groups was investigated. Based on the results of the absorption and fluorescence (FL) studies, a possible luminescence mechanism is proposed. The observed solvent-induced changes in the spectral position of the FL maximum, FL quantum yield, and FL decay kinetics in protic and aprotic solvents of low and high polarity are ascribed to a combination of polarity effects, intramolecular charge transfer (ICT) processes, and hydrogen bonding. Moreover, the potential of GQDs for the optical sensing of trace amount of water was assessed. The results of our systematic spectroscopic study will promote the rational design of GQDs and shed more light on the FL mechanism of carbon-based fluorescent nanomaterials.

Keywords

graphene quantum dots (GQDs)polarityintramolecular charge transfer (ICT)hydrogen bondoptical properties

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Nano Research
Volume 16 Issue 1,
January 2023
Pages 45-52
DOI: 10.1007/s12274-022-4752-1
Cite this article:
Hu Y, Neumann C, Scholtz L, et al. Polarity, intramolecular charge transfer, and hydrogen bond co-mediated solvent effects on the optical properties of graphene quantum dots. Nano Research, 2023, 16(1): 45-52. https://doi.org/10.1007/s12274-022-4752-1
Topics:
FluorescenceGraphene quantum dots

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Received: 20 April 2022
Revised: 06 July 2022
Accepted: 08 July 2022
Published: 02 September 2022
© Tsinghua University Press 2022
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