First-Principles Study of Graphene and Carbon Nanotubes Functionalized with Benzyne

Abstract

We applied ab initio computational methods based on density functional theory to study the properties of graphene and single-walled carbon nanotubes functionalized with benzyne. The calculations were carried out using the SIESTA electronic structure code combined with the generalized gradient approximation for the exchange correlation functional. Our study showed that the reaction of cycloaddition of benzyne to pristine graphene was exothermic with the possibility of formation of both [2 + 2] and [4 + 2] reaction products. The binding energies of benzyne molecules attached to semiconducting zigzag and metallic armchair nanotubes were found to be inversely proportional to the nanotube diameter. The linear fits of the binding energies between benzyne and carbon nanotubes extrapolated to the zero curvature limit were in good agreement with the binding energies of benzyne attached to graphene. Our calculations demonstrated that the cycloaddition of benzyne could open up a nonzero gap between the valence and conduction bands of graphene and metallic carbon nanotubes. The value of the band gap was significantly affected by the geometry of benzyne attachment and by the choice of the supercell.

Role of Stone-Wales defects on the interfacial interactions among graphene, carbon nanotubes, and Nylon 6: A first-principles study

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First-Principles Study of the Interactions between Graphene Oxide and Amine-Functionalized Carbon Nanotube

“…The computed geometries of the complexes indicate that the covalent functionalizations of graphene and CNTs induce a significant deformation in their structures due to the local sp 2 → sp 3 transition of carbon atoms directly bonded to functional groups, which is consistent with previous observations. 18,25,27 The computed interaction energies (per unit length of CNT) between the first three models of GO and CNTs are summarized in Table 1. All computed interaction energies are negative, indicating that all the complexes are thermodynamically stable and their formations are energetically favorable.…”

A C60-aryne building block: synthesis of a hybrid all-carbon nanostructure

“…Theoretical calculations demonstrate the [4+2] cycloadducts to be the more stable configuration to be formed, although the formation of the [2+2] products cannot be ruled out based on the small difference in energy, which is in accordance with previous theoretical investigations. 23 Based on the remarkable higher reactivity of the fullerene units compared with the graphene layer, work is currently in progress to determine the chemical reactivity and selectivity of the new carbon-based nanoconjugates and their properties as new materials for practical purposes. Financial support from the European Research Council (ERC-320441-Chiralcarbon), the European Commission (EC) FP7 ITN "MOLESCO" Project No.…”