Organic Covalent Patterning of Nanostructured Graphene with Selectivity at the Atomic Level

Navarro, José María Martínez; Leret, Sofía; Calleja, F.; Stradi, Daniele; Black, Andrés; Gavito, Ramón Bernardo; Garnica, Manuela; Granados, Daniel; Parga, Amadeo L. Vázquez de; Pérez, Emilio M.; Miranda, Rodolfo

doi:10.1021/acs.nanolett.5b03928

Cited by 39 publications

(40 citation statements)

References 54 publications

(94 reference statements)

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“…Reactivity enhancement at specific topographical features, as patterning induced by moiré superstructures, has been reported for epitaxial graphene on metal1416. We have confirmed that there is not preferential adsorption or nucleation at step edges, buffer layer-induced reconstruction or other morphological defects.…”

Section: Discussionsupporting

confidence: 82%

“…Moreover, only few reactions schemes are available and most of them are promoting direct C–C bond forming reactions with aryl addition89. Other kind of works use ultra high vacuum environments and are usually limited to small molecules, as hydrogen, oxygen or more recently cyanomethyl radicals141516. This kind of works is usually performed for epitaxial graphene grown on metal surfaces and take advantage of the surface patterning obtained by lattice-mismatched graphene on metallic substrates.…”

mentioning

confidence: 99%

“…This kind of works is usually performed for epitaxial graphene grown on metal surfaces and take advantage of the surface patterning obtained by lattice-mismatched graphene on metallic substrates. Nowadays, lack of selectivity is one of the major drawbacks on the covalent modification protocols16.…”

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confidence: 99%

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Highly selective covalent organic functionalization of epitaxial graphene

et al. 2017

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Graphene functionalization with organics is expected to be an important step for the development of graphene-based materials with tailored electronic properties. However, its high chemical inertness makes difficult a controlled and selective covalent functionalization, and most of the works performed up to the date report electrostatic molecular adsorption or unruly functionalization. We show hereafter a mechanism for promoting highly specific covalent bonding of any amino-terminated molecule and a description of the operating processes. We show, by different experimental techniques and theoretical methods, that the excess of charge at carbon dangling-bonds formed on single-atomic vacancies at the graphene surface induces enhanced reactivity towards a selective oxidation of the amino group and subsequent integration of the nitrogen within the graphene network. Remarkably, functionalized surfaces retain the electronic properties of pristine graphene. This study opens the door for development of graphene-based interfaces, as nano-bio-hybrid composites, fabrication of dielectrics, plasmonics or spintronics.

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Section: Discussionsupporting

confidence: 82%

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confidence: 99%

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Highly selective covalent organic functionalization of epitaxial graphene

et al. 2017

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“…For instance, radicals of diazonium salts are able to attach to sp 2 sites but manifests a preference for graphene on hydrophilic substrates [100], due to charge accumulation effects. A similar effect is observed for graphene on metals such as iridium or ruthenium [101,102], where, in addition, a spatially modulated reactivity is created following the nano-metric moiré pattern of corrugation. This open the road to substrate driven functionalization, with the possibility of creating chemical nano-patterns following the symmetry of the moiré superlattice.…”

Section: Multilayers From Epitaxy: a Perspectivesupporting

confidence: 54%

Engineering 3D Graphene-Based Materials: State of the Art and Perspectives

Bellucci

Tozzini

2020

Molecules

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Graphene is the prototype of two-dimensional (2D) materials, whose main feature is the extremely large surface-to-mass ratio. This property is interesting for a series of applications that involve interactions between particles and surfaces, such as, for instance, gas, fluid or charge storage, catalysis, and filtering. However, for most of these, a volumetric extension is needed, while preserving the large exposed surface. This proved to be rather a hard task, especially when specific structural features are also required (e.g., porosity or density given). Here we review the recent experimental realizations and theoretical/simulation studies of 3D materials based on graphene. Two main synthesis routes area available, both of which currently use (reduced) graphene oxide flakes as precursors. The first involves mixing and interlacing the flakes through various treatments (suspension, dehydration, reduction, activation, and others), leading to disordered nanoporous materials whose structure can be characterized a posteriori, but is difficult to control. With the aim of achieving a better control, a second path involves the functionalization of the flakes with pillars molecules, bringing a new class of materials with structure partially controlled by the size, shape, and chemical-physical properties of the pillars. We finally outline the first steps on a possible third road, which involves the construction of pillared multi-layers using epitaxial regularly nano-patterned graphene as precursor. While presenting a number of further difficulties, in principle this strategy would allow a complete control on the structural characteristics of the final 3D architecture.

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“…1A ) because of their bonding to a different adsorption site. This is possible because the experimental manipulation is carried out at 4.6 K, and hence, the −CH 2 CN radicals do not have enough energy to explore the surface and reach the HCP-top adsorption site where the adsorption energy is maximum ( 25 , 26 ). On the basis of the calculated pDOS, we can rationalize the manipulation process in the following way: Because of the high positive bias voltage (>+1.7 V), the tunneling electrons are injected into the tail of the LUMO of the TCNQ-CH 2 CN.…”

Section: Resultsmentioning

confidence: 99%