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Cited by 70Graphene research and applicationsGraphene and Nanomaterials ApplicationsGraphite, nuclear technology, radiation studies

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Principles governing control of aggregation and dispersion of aqueous graphene oxide

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Suter, James L., Coveney, Peter V.·2021·Scientific Reports
DOI 10.1038/s41598-021-01626-3PMC PMC8599484
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Abstract

Controlling the structure of graphene oxide (GO) phases and their smaller analogues, graphene (oxide) quantum dots (GOQDs), is vitally important for any of their widespread intended applications: highly ordered arrangements of nanoparticles for thin-film or membrane applications of GO, dispersed nanoparticles for composite materials and three-dimensional porous arrangements for hydrogels. In aqueous environments, it is not only the chemical composition of the GO flakes that determines their morphologies; external factors such as pH and the coexisting cations also influence the structures formed. By using accurate models of GO that capture the heterogeneity of surface oxidation and very large-scale coarse-grained molecular dynamics that can simulate the behaviour of GO at realistic sizes of GOQDs, the driving forces that lead to the various morphologies in aqueous solution are resolved. We find the morphologies are determined by a complex interplay between electrostatic, $${\pi }$$ π –$${\pi }$$ π and hydrogen bonding interactions. Assembled morphologies can be controlled by changing the degree of oxidation and the pH. In acidic aqueous solution, the GO flakes vary from fully aggregated over graphitic domains to partial aggregation via hydrogen bonding between hydroxylated domains, leading to the formation of planar extended flakes at high oxidation ratios and stacks at low oxidation ratios. At high pH, where the edge carboxylic acid groups are deprotonated, electrostatic repulsion leads to more dispersion, but a variety of aggregation behaviour is surprisingly still observed: over graphitic regions, via hydrogen bonding and “face-edge” interactions. Calcium ions cause additional aggregation, with a greater number of “face-face” and “edge-edge” aggregation mechanisms, leading to irregular aggregated structures. “Face-face” aggregation mechanisms are enhanced by the GO flakes possessing distinct domains of hydroxylated and graphitic regions, with $${\pi }$$ π –$${\pi }$$ π and hydrogen bonding interactions prevalent between these regions on aggregated flakes respectively. These findings furnish explanations for the aggregation characteristics of GO and GOQDs, and provide computational methods to design directed synthesis routes for self-assembled and associated applications.

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  • GOs tend to aggregate due to negative charge and van der Waals forces.

    “Although GOs tend to aggregate due to negative charge and van der Waals forces49,50, nanosized GOs have a high salt tolerance and weakened van der Waals forces between layers, resulting in a greater dispersion stability and lower aggregation compared to microsized GOs51.”

    From Bioengineered liver crosslinked with nano-graphene oxide enables efficient liver regeneration via MMP suppression and immunomodulation (2023) · cites this paper as [50]

    The Results and discussion identify van der Waals interactions as one cause of some GO aggregation. But they say negative charge creates electrostatic repulsion and reduces aggregation compared with uncharged flakes; it does not cause aggregation. (LLM, conf=0.88)

    Experimental — accuracy not yet measured

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Authors
Suter, J. L., & Coveney, P. V.
Affiliations
University College London (GB)
Corresponding author
Coveney, Peter V.
ORCID
Venue
Scientific Reports
Publisher
Springer Science and Business Media LLC
Published
2021-11-17
Volume
11
Issue
1
Pages
22460-22460
ISSN
2045-2322 (ISSN-L)
DOI
10.1038/s41598-021-01626-3
PMC
PMC8599484
OpenAlex
W3212079518
Cited by
70
References
0
Citations by year
2026: 20 · 2025: 22 · 2024: 14 · 2023: 8 · 2022: 6
FWCI
2.13
Type
journal article
Language
en
Open access
Licence
Locations
  • Scientific Reports (publishedVersion, cc-by)
  • PubMed Central (publishedVersion, cc-by)
  • PubMed (publishedVersion)
  • UvA-DARE (University of Amsterdam) (submittedVersion, cc-by)
  • DOAJ (DOAJ: Directory of Open Access Journals) (submittedVersion, cc-by-sa)
  • UCL Discovery (University College London) (submittedVersion)
Funders
  • European Commission (HORIZON2020, 800925)
  • Engineering and Physical Sciences Research Council (EP/R029598/1, EP/L00030X/1, ARCHER2)
Topics
  • Physical Sciences › Materials Science › Materials Chemistry › Graphene research and applications
  • Physical Sciences › Engineering › Biomedical Engineering › Graphene and Nanomaterials Applications
  • Physical Sciences › Materials Science › Materials Chemistry › Graphite, nuclear technology, radiation studies
Keywords
graphene oxide, graphene oxide quantum dots, aggregation, dispersion, aqueous dispersions, pH effect, oxidation degree, hydrogen bonding, electrostatic interactions, van der Waals interactions, calcium ions, coarse-grained molecular dynamics, self-assembly

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