Chemical and Physical Viewpoints About the Bonding in Fullerene–Graphene Hybrid Materials: Interaction on Pristine and Fe-Doped Graphene

Abstract

A DFT scheme was adopted to study the noncovalent/covalent attachment of fullerenes (C60, Si24C36, and B24N36) to graphene and Fe-doped graphene nanosheets (FeG). Geometrical, energetic, and electronic properties related to the physical and chemical nature of the bonding were characterized. The results show that fullerenes are physisorbed on graphene with adsorption energies of 0.7–1.2 eV, while the chemisorption is reached on FeG by cycloadditions with adsorption energies of 1.6–4.4 eV and is depending on the topology of FeG. The origin of the stability was analyzed from chemical and physical viewpoints, applying methods such as atom-in-molecules (AIM), natural bond orbital (NBO), and energy decomposition analysis based on absolutely localized molecular orbitals (ALMO-EDA). It is shown that noncovalent graphene–fullerene hybrids are assembled by van der Waals interactions but are also governed by permanent electrostatic Coulombic interactions that contribute at least 31% to the binding stability and depending on the bond polarity of fullerenes. Otherwise, the cycloaddition of fullerenes with FeG is reached by the formation of highly polarized chemical bonds, which were described in a detailed orbital picture. The structural stability of the covalent complexes is dominated by the contribution of charge transfer and permanent electrostatic physical effects. Additionally, the polarizability is an intrinsic property of fullerenes that also determines its binding strength on graphene (up to 35%); in this way, the larger polarizability of fullerenes increases the interaction stability. Therefore, this work gives insights into the bonding properties governing the stability of hybrid materials formed by self-assembly of fullerenes onto emerging low-dimensional nanostructures.

Phosphorene–Fullerene Nanostructures: A First-Principles Study

“…6c-d system shows EELEC and EDISP contributions of 45 and 39%, respectively (major contribution of electrostatics, Fig. 5a); while the Graphene−C60 system is reported with EELEC and EDISP contributions of 33 and 67%, respectively (major contribution of dispersion) 40 .…”

“…As can be seen, Eads=0.9 eV for Phos−C60 complexes agrees with the experimental favorable non-covalent adsorption of fullerenes on phosphorene-based materials. Furthermore, the C60 adsorption stability increases at least 30% compared to related 2D materials such as graphene, where Eads0.7 eV is reported for Graphene−C60 non-covalent complexes [40][41][42][43][44] . Therefore, phosphorene serves as excellent support for fullerenes to form new hybrid nanostructures, ensuring a stable interaction.…”

“…Consequently, carbon fullerenes act as mild p-dopants for phosphorene, introducing up to 0.3 holes/molecule on the substrate. Moreover, carbon, boron, boron nitride, and silicon carbide fullerenes have also behaved as p-dopants upon adsorption on related 2D materials such as pristine graphene and metal-doped graphene 40,42,[49][50] .…”

“…In this regard, the minimization of dispersion and electrostatic interactions also plays a key role in forming organic molecular crystals, phthalocyanine self-assemblies, and DNA nucleobase patterns onto phosphorene-based substrates, standing for 85% of the stability 19,[59][60][61] . It can be pointed out although phosphorene is not a -electron system, it behaves with a similar attractive ability than graphene or carbon nanotubes to bind aromatic molecules, where fullerenes adsorb by - stacking [39][40][41][42][43][44][45] . In this regard, the 3D g inter isosurface representation of weak intermolecular interactions is visually displayed for Phos−C60 complex as a representative case and compared against Graphene−C60 (Fig.…”

Sensing of toxic Lewisite (L1, L2, and L3) molecules by graphdiyne nanoflake using density functional theory calculations and quantum theory of atoms in molecule analysis

“…[ 9–12 ] Literature reveals that 2‐D carbon materials emerge as ideal candidates for the adsorption of metal atoms, [ 13,14 ] gases, [ 15 ] neutral and charged clusters. [ 16,17 ] Recently, graphdiyne nanosheets are reported for the adsorption of different compounds. [ 18–22 ] For example, Srimathi et al [ 18 ] theoretically reported the affective use of graphdiyne as a biosensor material by adsorbing regorafenib drugs.…”