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

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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.

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Acknowledgements

This research is supported by the Deutsche Forschungsgemeinschaft project No. 392444269 (DFG, German Research Foundation), the China Scholarship Council (CSC); We would also like to acknowledge the assistance of the Core Facility BioSupraMol supported by the DFG. C. N. and A. T. acknowledge DFG financial support via the research infrastructure grant INST 275/257-1 FUGG (project No. 313713174), funding through ESF Research Groups 2019 FGR 0080 “EST” and 2020 FGR 0051 “GraphSens” as well as BMWi project ZF4817401VS9 “TDraCon”. Z. H. from Soochow University is acknowledged for conducting TEM measurements. U. R. G and L. S. gratefully acknowledge financial support by the European Metrology Programme for Innovation and Research (EMPIR) as part of the projects 18HLT02 “AeroTox”. The EMPIR initiative is co-funded by the European Union’s Horizon 2020 research and innovation programme and by the EMPIR participating states.

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Authors and Affiliations

  1. Institute of Chemistry and Biochemistry, Freie Universität Berlin, Takustraße 3, 14195, Berlin, Germany

    Yalei Hu, Lena Scholtz & Siegfried Eigler

  2. Institute of Physical Chemistry and Abbe Center of Photonics, Friedrich Schiller University Jena, Lessingstraße 10, 07743, Jena, Germany

    Christof Neumann & Andrey Turchanin

  3. Division Biophotonics, Federal Institute for Materials Research and Testing (BAM), Richard Willstätter Straße 11, 12489, Berlin, Germany

    Lena Scholtz & Ute Resch-Genger

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  1. Yalei Hu
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  2. Christof Neumann
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  3. Lena Scholtz
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  5. Ute Resch-Genger
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  6. Siegfried Eigler
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Correspondence to Ute Resch-Genger or Siegfried Eigler.

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12274_2022_4752_MOESM1_ESM.pdf

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

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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 Res. 16, 45–52 (2023). https://doi.org/10.1007/s12274-022-4752-1

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