10.57647/jnsc.2025.1502.08

Amphiphilic Graphene Quantum Dots and Their Application in the Dispersion of Graphite

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  • Zahra Azimi1,
  • Beheshteh Sohrabi*1,
  • Yasaman Javanmard1,
  • Armin Hajipour Keyvani1,
  1. Department of Physical Chemistry, Faculty of Chemistry, Surface Chemistry Research Laboratory, Iran University of Science and Technology, Tehran, 16846-13114, Iran
Amphiphilic Graphene Quantum Dots and Their Application in the Dispersion of Graphite

Received: 09-03-2025

Revised: 29-03-2025

Accepted: 25-05-2025

Published in Issue 30-04-2025

Copyright (c) 2025 Zahra Azimi, Beheshteh Sohrabi, Yasaman Javanmard, Armin Hajipour Keyvani (Author)

Creative Commons License

This work is licensed under a Creative Commons Attribution 4.0 International License.

How to Cite

Azimi, Z., Sohrabi, B., Javanmard, Y., & Hajipour Keyvani, A. (2025). Amphiphilic Graphene Quantum Dots and Their Application in the Dispersion of Graphite. Journal of Nanostructure in Chemistry, 15(2 (April 2025). https://doi.org/10.57647/jnsc.2025.1502.08
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Abstract

One of the most auspicious and economically sound techniques for generating graphene is recognized as liquid-phase exfoliation (LPE). This empirical investigation has astutely showcased that by functionalizing hydrophilic graphene quantum dots (OH-GQDs) with hydrophobic tridecylamine, an effortlessly devised synthesis approach can be formulated, thereby producing alluringly versatile amphiphilic GQDs. This research aimed to generate a series of graphene quantum dots (GQDs) with varying amine values and employ these nanomaterials to disintegrate and distribute pure graphite in water. Adjacent graphene sheets and the GQDs on the graphene surface exhibit attractive van der Waals forces, generating a steric repulsion between them. Based on our research results, it has been found that tridecyl amine functionalized graphene quantum dots (t-GQDs) exhibit the highest ability to stabilize graphene at a greater extent compared to other functional groups. Notably, the graphene concentration peaked when t-GQDs were functionalized at a molar ratio of Amine / Citric acid = 1. Furthermore, we also explored the impact of varying concentrations of amphiphilic GQDs on the yield and dimensions of graphene nanosheets.

This study compared the stabilization effects of t-GQDs with those of several other functional groups, including amine, carboxyl, and hydroxyl groups. The comparison was based on the degree of graphene dispersion achieved, evaluated through UV-visible spectroscopy, and the stability of the dispersions indicated by zeta potential measurements. Our results showed that t-GQDs provided superior stabilization due to the optimal balance of hydrophobic and hydrophilic functionalities, which enhanced both steric and electrostatic stabilization mechanisms.

Keywords

  • Liquid phase exfoliation,
  • Graphene quantum dot,
  • Aqueous dispersion,
  • High-power sonication,
  • Amphiphilicity
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References

  1. Zhao, L., Liu, W., Yi, W., Hu, T., Khodagholian, D., Gu, F., Lin, H., Zurek, E., Zheng, Y., Miao, M.: Nano-makisu: highly anisotropic two-dimensional carbon allotropes made by weaving together nanotubes. Nanoscale. 12, 347–355 (2020). https://doi.org/10.1039/c9nr08069d
  2. Novoselov, K.S., Geim, A.K., Morozov, S. V., Jiang, D., Zhang, Y., Dubonos, S. V., Grigorieva, I. V., Firsov, A.A.: Electric field in atomically thin carbon films. Science. 306, 666–669 (2004). https://doi.org/10.1126/science.1102896
  3. Yang, H., Bao, F., Chen, S., Liu, S., Huang, H., Wang, L., Liu, H., Yu, J., Zhu, C., Xu, J.: Construction of a Borophene-Based Hybrid Aerogel for Multifunctional Applications. ACS Appl. Mater. Interfaces. 16, 41, 56063–56072 (2024). https://doi.org/10.1021/acsami.4c10663
  4. Wei, T., Hauke, F., Hirsch, A.: Evolution of Graphene Patterning: From Dimension Regulation to Molecular Engineering. Adv. Mater. 33, e2104060 (2021). https://doi.org/10.1002/adma.202104060
  5. Narayan, R., Kim, S.O.: Surfactant mediated liquid phase exfoliation of graphene. Nano Converg. 2, 20 (2015). https://doi.org/10.1186/s40580-015-0050-x
  6. Fernandes, J., Nemala, S.S., De Bellis, G., Capasso, A.: Green Solvents for the Liquid Phase Exfoliation Production of Graphene: The Promising Case of Cyrene. Front. Chem. 10, 878799 (2022). https://doi.org/10.3389/fchem.2022.878799
  7. Calistri, S., Ubaldini, A., Telloli, C., Gennerini, F., Marghella, G., Gessi, A., Bruni, S., Rizzo, A.: Exfoliation of Molecular Solids by the Synergy of Ultrasound and Use of Surfactants: A Novel Method Applied to Boric Acid. Molecules. 29, (2024). https://doi.org/10.3390/molecules29143324
  8. Zhao, W., Sugunan, A., Gillgren, T., Larsson, J.A., Zhang, Z.-B., Zhang, S.-L., Nordgren, N., Sommertune, J., Ahniyaz, A.: Surfactant-Free Stabilization of Aqueous Graphene Dispersions Using Starch as a Dispersing Agent. ACS omega. 6, 12050–12062 (2021). https://doi.org/10.1021/acsomega.1c00699
  9. Cho, H.-H., Yang, H., Kang, D.J., Kim, B.J.: Surface engineering of graphene quantum dots and their applications as efficient surfactants. ACS Appl. Mater. Interfaces. 7, 8615–8621 (2015). https://doi.org/10.1021/acsami.5b00729
  10. Kuehl, B., Raman, S., Becker, A., Garg, V., Roberts-Dobie, J., McCaslin, A., Brensdal, J., Attinger, J., Burton, L., Forrester, M., Hohmann, A., Cochran, E.W.: Fully Atom-Efficient Solvent-Mediated Biopolymer Manufacturing: A Base Case Illustrated with Macromolecular Surfactants Tailored to Stable Polymer-Water Interfaces. ACS Appl. Mater. Interfaces. 16, 59280–59290 (2024). https://doi.org/10.1021/acsami.4c12730
  11. Griffin, A., Nisi, K., Pepper, J., Harvey, A., Szydłowska, B.M., Coleman, J.N., Backes, C.: Effect of Surfactant Choice and Concentration on the Dimensions and Yield of Liquid-Phase-Exfoliated Nanosheets. Chem. Mater. 32, 2852–2862 (2020). https://doi.org/10.1021/acs.chemmater.9b04684
  12. Gotzias, A., Lazarou, Y.G.: Graphene Exfoliation in Binary NMP/Water Mixtures by Molecular Dynamics Simulations. Chempluschem. 89, e202300758 (2024). https://doi.org/10.1002/cplu.202300758
  13. Hung, Y.-C., Wu, J.-R., Periasamy, A.P., Aoki, N., Chuang, C.: Advances in spin properties of plant leaf-derived graphene quantum dots from materials to applications. Nanotechnology. 36, (2025). https://doi.org/10.1088/1361-6528/adb851
  14. Zhao, C., Song, X., Liu, Y., Fu, Y., Ye, L., Wang, N., Wang, F., Li, L., Mohammadniaei, M., Zhang, M., Zhang, Q., Liu, J.: Synthesis of graphene quantum dots and their applications in drug delivery. J Nanobiotechnol. 18, 142 (2020). https://doi.org/10.1186/s12951-020-00698-z
  15. Naik, J.P., Sutradhar, P. & Saha, M. Molecular scale rapid synthesis of graphene quantum dots (GQDs). J Nanostruct Chem 7, 85–89 (2017). https://doi.org/10.1007/s40097-017-0222-9
  16. Manjubaashini, N., Thangadurai, T.D., Nataraj, D., Thomas, S. Introduction to Graphene Quantum Dots. Materials Horizons: From Nature to Nanomaterials. Book Chapter Springer, Singapore. p. 27-41 (2024). https://doi.org/10.1007/978-981-97-5722-0_3
  17. Dananjaya, Vimukthi., Marimuthu, Sathish., Yang, Richard (Chunhui)., Grace, Andrews Nirmala., Abeykoon, Chamil.: Synthesis, properties, applications, 3D printing and machine learning of graphene quantum dots in polymer nanocomposites. Progress in Materials Science. 144. 101282, (2024). https://doi.org/10.1016/j.pmatsci.2024.101282
  18. Xie, Z., Lu, R., Zhu, Y., Peng, M., Fan, T., Ren, P., Wang, B., Kang, L., Liu, X., Li, S., Cui, H.: Liquid-phase exfoliation of black sesame to create a nanoplatform for in vitro photoluminescence and photothermal therapy. Nanomedicine (Lond). 15, 2041–2052 (2020). https://doi.org/10.2217/nnm-2020-0151
  19. Azimi, Z., Alimohammadian, M., Sohrabi, B.: Graphene Quantum Dots Based on Mechanical Exfoliation Methods: A Simple and Eco-Friendly Technique. ACS Omega. 9, 29, 31427–31437 (2024). https://doi.org/10.1021/acsomega.4c00453
  20. Ma, R., Zeng, M., Huang, D., Wang, J., Cheng, Z., Wang, Q.: Amphiphilicity-adaptable graphene quantum dots to stabilize pH-responsive pickering emulsions at a very low concentration. J. Colloid Interface Sci. 601, 106–113 (2021). https://doi.org/10.1016/j.jcis.2021.05.104
  21. Zhou, Q., Xia, G., Du, M., Lu, Y., Xu, H.: Scotch-tape-like exfoliation effect of graphene quantum dots for efficient preparation of graphene nanosheets in water. Appl. Surf. Sci. 483, (2019). https://doi.org/10.1016/j.apsusc.2019.03.290
  22. Hadi, A., Zahirifar, J., Karimi-Sabet, J., Dastbaz, A.: Graphene nanosheets preparation using magnetic nanoparticle assisted liquid phase exfoliation of graphite: The coupled effect of ultrasound and wedging nanoparticles. Ultrason. Sonochem. 44, 204–214 (2018). https://doi.org/10.1016/j.ultsonch.2018.02.028
  23. Ke, Z., Azam, M., Ali, S., Zubair, M., Cao, Y., Khan, A.A., Hassan, A., Xue, W.: Role of Functional Groups in Tuning Luminescence Signature of Solution-Processed Graphene Quantum Dots: Experimental and Theoretical Insights. Molecules. 29, (2024). https://doi.org/10.3390/molecules29122790
  24. Pan, D., Zhang, J., Li, Z., & Wu, M.:Hydrothermal Route for Cutting Graphene Sheets into Blue‐Luminescent Graphene Quantum Dots. Advanced Materials, 22(6), 734–738, (2010). https://doi.org/10.1002/adma.200902825
  25. Maoxin Cai, Lu Lai, Mingwei Zhao.: Synthesis, properties, and applications of amphiphilic carbon dots: A review,Carbon, 233,119921,(2025). https://doi.org/10.1016/j.carbon.2024.119921.
  26. Fengna Xi , Jingwen Zhao , Chao Shen , Jingbo He , Jie Chen , Yibo Yan , Kaixin Li , Jiyang Liu , Peng Chen: Amphiphilic graphene quantum dots as a new class of surfactants. Carbon, 153, 127–135 (2019). https://doi.org/10.1016/j.carbon.2019.07.014.
  27. Dong, Y., Shao, J., Chen, C., Li, H., Wang, R., Chi, Y., Lin, X., Chen, G.: Blue luminescent graphene quantum dots and graphene oxide prepared by tuning the carbonization degree of citric acid. Carbon N. Y. 50, 4738–4743 (2012). https://doi.org/10.1016/J.CARBON.2012.06.002
  28. Saito, N., Itoyama, S., Takahashi, R., Takahashi, Y., Kondo, Y.: Synthesis and surface activity of photoresponsive hybrid surfactants containing both fluorocarbon and hydrocarbon chains. J. Colloid Interface Sci. 582, 638–646 (2021). https://doi.org/10.1016/j.jcis.2020.08.054
  29. Kapoor, S., Jha, A., Ahmad, H., Islam, S.S.: Avenue to Large-Scale Production of Graphene Quantum Dots from High-Purity Graphene Sheets Using Laboratory-Grade Graphite Electrodes. ACS omega. 5, 18831–18841 (2020). https://doi.org/10.1021/acsomega.0c01993
  30. Singh, P., Vithalani, H., Adhyapak, A., Semwa, T., Singh, N., Dhanka, M., Bhatia, D., Saha, J.: Microwave-Assisted Green Synthesis of Fluorescent Graphene Quantum Dots: Metal Sensing, Antioxidant Properties, and Biocompatibility Insights. J. Fluoresc. 35 (2025). https://doi.org/10.1007/s10895-025-04140-1
  31. Zhang, W., Liu, Y., Meng, X., Ding, T., Xu, Y., Xu, H., Ren, Y., Liu, B., Huang, J., Yang, J., Fang, X.: Graphenol defects induced blue emission enhancement in chemically reduced graphene quantum dots. Phys. Chem. Chem. Phys. 17, 22361–22366 (2015). https://doi.org/10.1039/c5cp03434e
  32. Bhosle, A.A., Banerjee, M., Hiremath, S.D., Sisodiya, D.S., Naik, V.G., Barooah, N., Bhasikuttan, A.C., Chattopadhyay, A., Chatterjee, A.: A combination of a graphene quantum dots-cationic red dye donor-acceptor pair and cucurbituril as a supramolecular sensor for ultrasensitive detection of cancer biomarkers spermine and spermidine. J. Mater. Chem. B. 10, 8258–8273 (2022). https://doi.org/10.1039/d2tb01269c
  33. Golubewa, L., Kulahava, T., Klimovich, A., Rutkauskas, D., Matulaitiene, I., Karpicz, R., Belko, N., Mogilevtsev, D., Kavalenka, A., Fetisova, M., Karvinen, P., Svirko, Y., Kuzhir, P.: Visualizing hypochlorous acid production by human neutrophils with fluorescent graphene quantum dots. Nanotechnology. 33, (2021). https://doi.org/10.1088/1361-6528/ac3ce4
  34. Wang, J., Manga, K.K., Bao, Q., Loh, K.P.: High-Yield Synthesis of Few-Layer Graphene Flakes through Electrochemical Expansion of Graphite in Propylene Carbonate Electrolyte. J. Am. Chem. Soc. 133, 8888–8891 (2011). https://doi.org/10.1021/ja203725d
  35. Kang, M.S., Kim, K.T., Lee, J.U., Jo, W.H.: Direct exfoliation of graphite using a non-ionic polymer surfactant for fabrication of transparent and conductive graphene films. J. Mater. Chem. C. 1, 1870–1875 (2013). https://doi.org/10.1039/C2TC00586G