Nanostructuring graphene for controlled and reproducible functionalization

Mali, Kunal S.; Greenwood, John; Adisoejoso, Jinne; Phillipson, Roald; Feyter, Steven De

doi:10.1039/c4nr06470d

Cited by 112 publications

(107 citation statements)

References 133 publications

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“…[90][91][92] However, since the covalent bond formation occurs through sp 2 to sp 3 hybridization, it often leads to undesirable modification or even destruction of the graphene electronic properties. Alternatively, the electronic properties of graphene can be modified by non-covalent functionalization, [93][94][95][96] where the interactions between graphene and adsorbates are dispersive. Following such a strategy the properties that make unique graphene are retained.…”

Section: When Graphene Meets Molecules -The Supramolecular Approachmentioning

confidence: 99%

“…[99,[115][116][117][118] Given that graphite can be seen as a stack of graphene sheets, the Review knowledge gathered on the formation of supramolecular patterns on graphite can be potentially transferred for the non-covalent functionalization of graphene. [119,120] In general, the research on non-covalent functionalization of graphene, i.e., the functionalization of graphene with ordered supramolecular patterns, is targeting two challenges: (i) the understanding and control over the intermolecular and interfacial interactions in order to decorate surfaces with complex multicomponent ordered assemblies, (ii) the modulation of the physico-chemical properties of graphene for technologically relevant purposes such as doping or facilitating atomic layer deposition.…”

Section: Non-covalent Functionalization Of Graphenementioning

confidence: 99%

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Supramolecular Approaches to Graphene: From Self‐Assembly to Molecule‐Assisted Liquid‐Phase Exfoliation

2016

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Graphene, a one-atom thick two-dimensional (2D) material, is at the core of an ever-growing research effort due to its combination of unique mechanical, thermal, optical and electrical properties. Two strategies are being pursued for the graphene production: the bottom-up and the top-down. The former relies on the use of covalent chemistry approaches on properly designed molecular building blocks undergoing chemical reaction to form 2D covalent networks. The latter occurs via exfoliation of bulk graphite into individual graphene sheets. Amongst the various types of exfoliations exploited so far, ultrasound-induced liquid-phase exfoliation (UILPE) is an attractive strategy, being extremely versatile, up-scalable and applicable to a variety of environments. In this review, we highlight the recent developments that have led to successful non-covalent functionalization of graphene and how the latter can be exploited to promote the process of molecule-assisted UILPE of graphite. The functionalization of graphene with non-covalently interacting molecules, both in dispersions as well as in dry films, represents a promising and modular approach to tune various physical and chemical properties of graphene, eventually conferring to such a 2D system a multifunctional nature.

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Section: When Graphene Meets Molecules -The Supramolecular Approachmentioning

confidence: 99%

Section: Non-covalent Functionalization Of Graphenementioning

confidence: 99%

Supramolecular Approaches to Graphene: From Self‐Assembly to Molecule‐Assisted Liquid‐Phase Exfoliation

2016

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“…In this regard, the introduction of a bandgap in graphene through band structure engineering [4][5][6][7] into a semiconductor by opening up the band gap, and thus enhancing its potential practical electronic applications is highly desirable. 8,9 Covalent chemistry provides a powerful pathway to tailor the physical properties of pristine graphene to transform intrinsic zero band gap energy graphene. Based on the well-known covalent chemical reactivity of fullerenes and carbon nanotubes, chemists have already achieved good control of the elemental covalent chemistry of graphene and a broad arsenal of chemical reactions have already been carried out on this flat form of carbon, despite its low chemical reactivity when compared with curved carbon nanostructures such as fullerenes and carbon nanotubes.…”

Section: Introductionmentioning

confidence: 99%

Modulation of the exfoliated graphene work function through cycloaddition of nitrile imines

Barrejón

Gómez‐Escalonilla

Fierro

et al. 2016

Phys. Chem. Chem. Phys.

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After the feasibility of the 1,3-dipolar cycloaddition reaction between nitrile imines and exfoliated graphene by density functional theory calculations was proved, very few-layer graphene was effectively functionalized using this procedure. Hydrazones with different electronic properties were used as precursors for the 1,3-dipoles, and microwave irradiation as an energy source enabled the reaction to be performed in a few minutes. The anchoring of organic addends on the graphene surface was confirmed by Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis.Ultraviolet photoelectron spectroscopy (UPS) was used to measure the work function and band gap of these new hybrids. Our results demonstrate that it is possible to modulate these important electronic valence band parameters by tailoring the electron richness of the organic addends and/or the degree of functionalization.

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“…Doping of graphene by organic compounds [1][2][3][4][5][6][7]37] may also cause chemical shift changes in their NMR spectra.…”

Section: −1mentioning

confidence: 99%

“…">IntroductionThe non-covalent interactions between polyaromatic carbon and the hydrocarbon-based structure of organic molecules are both of fundamental interest and a promising means of modifying graphene-based electronics [1][2][3][4][5][6][7], spintronics [8][9][10], optoelectronics and sensors [11][12][13][14]. The high relative surface area of graphene is attractive for the sequestration of xenobiotics in environmental [15][16][17] …”

mentioning

confidence: 99%

NMR detects molecular interactions of graphene with aromatic and aliphatic hydrocarbons in water

et al. 2017

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IntroductionThe non-covalent interactions between polyaromatic carbon and the hydrocarbon-based structure of organic molecules are both of fundamental interest and a promising means of modifying graphene-based electronics [1][2][3][4][5][6][7], spintronics [8][9][10], optoelectronics and sensors [11][12][13][14]. The high relative surface area of graphene is attractive for the sequestration of xenobiotics in environmental [15][16][17] AbstractPolyaromatic carbon is widely held to be strongly diamagnetic and hydrophobic, with textbook van der Waals and 'π-stacked' binding of hydrocarbons, which disrupt their self-assembled supramolecular structures. The NMR of organic molecules sequestered by polyaromatic carbon is expected to be dominated by shielding from the orbital diamagnetism of π electrons. We report the first evidence of very different polar and magnetic behavior in water, wherein graphene remained well-dispersed after extensive dialysis and behaved as a 1 H-NMR-silent ghost. Magnetic effects dominated the NMR of organic structures which interacted with graphene, with changes in spinspin coupling, vast increase in relaxation, line broadening and decrease in NMR peak heights when bound to graphene. However, the interactions were weak, reversible and did not disrupt organic self-assemblies reliant on hydrophobic 'π-stacking', even when substantially sequestered on the surface of graphene by the high surface area available. Interacting assemblies of aromatic molecules retained their strongly-shielded NMR signals and remained within self-assembled structures, with slower rates of diffusion from association with graphene, but with no further shielding from graphene. Binding to graphene was selective for positively-charged organic assemblies, weaker for non-aromatic and negligible for strongly-negatively-charged molecules, presumably repelled by a negative zeta potential of graphene in water. Stronger binders, or considerable excess of weaker binders readily reversed physisorption, with no evidence of structural changes from chemisorption. The fundamental nature of these different electronic interactions between organic and polyaromatic carbon is considered with relevance to electronics, charge storage, sensor, medical, pharmaceutical and environmental research.

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Nanostructuring graphene for controlled and reproducible functionalization

Cited by 112 publications

References 133 publications

Supramolecular Approaches to Graphene: From Self‐Assembly to Molecule‐Assisted Liquid‐Phase Exfoliation

Supramolecular Approaches to Graphene: From Self‐Assembly to Molecule‐Assisted Liquid‐Phase Exfoliation

Modulation of the exfoliated graphene work function through cycloaddition of nitrile imines

NMR detects molecular interactions of graphene with aromatic and aliphatic hydrocarbons in water

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