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Graphite and graphene fairy circles: a bottom-up approach for the formation of nanocorrals
Phan, T.H.; Van Gorp, H.; Li, Z.; Huynh, T.M.T.; Fujita, Y.; Verstraete, L.; Eyley, S.; Thielemans, W.; Uji-i, H.; Hirsch, B.E.; Mertens, S.F.L.; Greenwood, J.; Ivasenko, O.; De Feyter, S. (2019). Graphite and graphene fairy circles: a bottom-up approach for the formation of nanocorrals. ACS Nano 13(5): 5559-5571. https://dx.doi.org/10.1021/acsnano.9b00439
In: ACS Nano. AMER CHEMICAL SOC: Washington. ISSN 1936-0851; e-ISSN 1936-086X, more
Peer reviewed article  

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Author keywords
    covalent functionalization; electrochemical grafting cyclic voltammetry; chronoamperometry; nanoconfined self-assembly; on-surface polymerization

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Abstract
    A convenient covalent functionalization approach and nanopatterning method of graphite and graphene is developed. In contrast to expectations, electrochemically activated dediazotization of a mixture of two aryl diazonium compounds in aqueous media leads to a spatially inhomogeneous functionalization of graphitic surfaces, creating covalently modified surfaces with quasi-uniform spaced islands of pristine graphite or graphene, coined nanocorrals. Cyclic voltammetry and chronoamperometry approaches are compared. The average diameter (45–130 nm) and surface density (20–125 corrals/μm2) of these nanocorrals are tunable. These chemically modified nanostructured graphitic (CMNG) surfaces are characterized by atomic force microscopy, scanning tunneling microscopy, Raman spectroscopy and microscopy, and X-ray photoelectron spectroscopy. Mechanisms leading to the formation of these CMNG surfaces are discussed. The potential of these surfaces to investigate supramolecular self-assembly and on-surface reactions under nanoconfinement conditions is demonstrated.

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