Journal
JOURNAL OF MATERIALS CHEMISTRY A
Volume 2, Issue 36, Pages 15022-15028Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c4ta02349h
Keywords
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Funding
- Toyota Central RD Labs., Inc.
- Thomas Swan Co. Ltd.
- EPSRC [EP/G007314/1]
- Engineering and Physical Sciences Research Council [1138467, EP/K01658X/1, EP/G007314/1, EP/L001896/1] Funding Source: researchfish
- EPSRC [EP/K01658X/1, EP/G007314/1, EP/L001896/1] Funding Source: UKRI
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In bulk applications, it is essential that graphene sheets disperse individually in solvents or matrices, and therefore, suitable functionalisation regimes are crucially important. Here, isolated, highly soluble, alkyl-grafted graphenes were synthesised by reacting exfoliated Na-reduced graphite intercalation compounds (GIC) with alkyl halides. In this reaction, efficient exfoliation of the Na-reduced GICs into individually-dispersed negatively-charged graphenes provides accessible surface area for grafting. Increasing the alkyl chain length leads to large decrease of the grafting ratio (GR), demonstrating that steric factors also play an important role. However, optimising the Na concentration (C/Na ratio) in the reaction was very effective for improved exfoliation and increased GR. The X-ray diffraction measurements suggest that particular C/Na ratios (C/Na = similar to 12) led to full exfoliation, by balancing total charge and charge condensation effects and that the GR can be significantly increased even in the case of long alkyl chains (eicosyl chains), corresponding to a high solubility of 37 mu g ml(-1) and high yield in o-dichlorobenzene. Moreover, the absolute Na concentration is the critical parameter, with the same optimum (similar to 0.01 M) for exfoliation and grafting of GIC at all graphite concentrations; it was possible to graft even at high graphite concentration (0.3 M (3.6 mg ml(-1))) successfully.
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