Ni-Assisted Transformation of Graphene Flakes to Fullerenes

Transformation of graphene flakes to fullerenes assisted by Ni clusters is investigated using molecular dynamics simulations. The bond-order potential for Ni–C systems is developed. The potential reproduces the experimental and first-principles data on the physical properties of pure Ni as well as on relative energies of carbon species on Ni surfaces and in Ni bulk. The potential is applied for molecular dynamics simulations of the transformation of graphene flakes consisting of 50–400 atoms with and without Ni clusters attached. Free fullerenes, fullerenes with Ni clusters attached from outside, and fullerenes encapsulating Ni clusters (Ni endofullerenes) are observed to form in the presence of Ni clusters consisting of 5–80 atoms. Moreover, a new type of heterofullerenes with a patch made of a Ni cluster is found to form as an intermediate structure during the transformation. The Ni clusters are shown to reduce the activation energy for the graphene–fullerene transformation from 4.0 eV to 1.5–1.9 eV, providing the decrease of the minimal temperature at which such a transformation can be observed experimentally from about 1400 K for free graphene flakes to about 700–800 K. While the transformation of free graphene flakes is found to occur through formation of chains of two-coordinated carbon atoms at the flake edges, the mechanism of the Ni-assisted graphene–fullerene transformation is revealed to be based on the transfer of carbon atoms from the graphene flake to the Ni cluster and back. The way of controlled synthesis of endofullerenes with a transition metal cluster inside and heterofullerenes with a transition metal patch is also proposed

Ni-Assisted Transformation of Graphene Flakes to Fullerenes

Transformation of graphene flakes to fullerenes assisted by Ni clusters is investigated using molecular dynamics simulations. The bond-order potential for Ni–C systems is developed. The potential reproduces the experimental and first-principles data on the physical properties of pure Ni as well as on relative energies of carbon species on Ni surfaces and in Ni bulk. The potential is applied for molecular dynamics simulations of the transformation of graphene flakes consisting of 50–400 atoms with and without Ni clusters attached. Free fullerenes, fullerenes with Ni clusters attached from outside, and fullerenes encapsulating Ni clusters (Ni endofullerenes) are observed to form in the presence of Ni clusters consisting of 5–80 atoms. Moreover, a new type of heterofullerenes with a patch made of a Ni cluster is found to form as an intermediate structure during the transformation. The Ni clusters are shown to reduce the activation energy for the graphene–fullerene transformation from 4.0 eV to 1.5–1.9 eV, providing the decrease of the minimal temperature at which such a transformation can be observed experimentally from about 1400 K for free graphene flakes to about 700–800 K. While the transformation of free graphene flakes is found to occur through formation of chains of two-coordinated carbon atoms at the flake edges, the mechanism of the Ni-assisted graphene–fullerene transformation is revealed to be based on the transfer of carbon atoms from the graphene flake to the Ni cluster and back. The way of controlled synthesis of endofullerenes with a transition metal cluster inside and heterofullerenes with a transition metal patch is also proposed

Ni-Assisted Transformation of Graphene Flakes to Fullerenes

Transformation of graphene flakes to fullerenes assisted by Ni clusters is investigated using molecular dynamics simulations. The bond-order potential for Ni–C systems is developed. The potential reproduces the experimental and first-principles data on the physical properties of pure Ni as well as on relative energies of carbon species on Ni surfaces and in Ni bulk. The potential is applied for molecular dynamics simulations of the transformation of graphene flakes consisting of 50–400 atoms with and without Ni clusters attached. Free fullerenes, fullerenes with Ni clusters attached from outside, and fullerenes encapsulating Ni clusters (Ni endofullerenes) are observed to form in the presence of Ni clusters consisting of 5–80 atoms. Moreover, a new type of heterofullerenes with a patch made of a Ni cluster is found to form as an intermediate structure during the transformation. The Ni clusters are shown to reduce the activation energy for the graphene–fullerene transformation from 4.0 eV to 1.5–1.9 eV, providing the decrease of the minimal temperature at which such a transformation can be observed experimentally from about 1400 K for free graphene flakes to about 700–800 K. While the transformation of free graphene flakes is found to occur through formation of chains of two-coordinated carbon atoms at the flake edges, the mechanism of the Ni-assisted graphene–fullerene transformation is revealed to be based on the transfer of carbon atoms from the graphene flake to the Ni cluster and back. The way of controlled synthesis of endofullerenes with a transition metal cluster inside and heterofullerenes with a transition metal patch is also proposed

Ni-Assisted Transformation of Graphene Flakes to Fullerenes

Transformation of graphene flakes to fullerenes assisted by Ni clusters is investigated using molecular dynamics simulations. The bond-order potential for Ni–C systems is developed. The potential reproduces the experimental and first-principles data on the physical properties of pure Ni as well as on relative energies of carbon species on Ni surfaces and in Ni bulk. The potential is applied for molecular dynamics simulations of the transformation of graphene flakes consisting of 50–400 atoms with and without Ni clusters attached. Free fullerenes, fullerenes with Ni clusters attached from outside, and fullerenes encapsulating Ni clusters (Ni endofullerenes) are observed to form in the presence of Ni clusters consisting of 5–80 atoms. Moreover, a new type of heterofullerenes with a patch made of a Ni cluster is found to form as an intermediate structure during the transformation. The Ni clusters are shown to reduce the activation energy for the graphene–fullerene transformation from 4.0 eV to 1.5–1.9 eV, providing the decrease of the minimal temperature at which such a transformation can be observed experimentally from about 1400 K for free graphene flakes to about 700–800 K. While the transformation of free graphene flakes is found to occur through formation of chains of two-coordinated carbon atoms at the flake edges, the mechanism of the Ni-assisted graphene–fullerene transformation is revealed to be based on the transfer of carbon atoms from the graphene flake to the Ni cluster and back. The way of controlled synthesis of endofullerenes with a transition metal cluster inside and heterofullerenes with a transition metal patch is also proposed

Ni-Assisted Transformation of Graphene Flakes to Fullerenes

Transformation of graphene flakes to fullerenes assisted by Ni clusters is investigated using molecular dynamics simulations. The bond-order potential for Ni–C systems is developed. The potential reproduces the experimental and first-principles data on the physical properties of pure Ni as well as on relative energies of carbon species on Ni surfaces and in Ni bulk. The potential is applied for molecular dynamics simulations of the transformation of graphene flakes consisting of 50–400 atoms with and without Ni clusters attached. Free fullerenes, fullerenes with Ni clusters attached from outside, and fullerenes encapsulating Ni clusters (Ni endofullerenes) are observed to form in the presence of Ni clusters consisting of 5–80 atoms. Moreover, a new type of heterofullerenes with a patch made of a Ni cluster is found to form as an intermediate structure during the transformation. The Ni clusters are shown to reduce the activation energy for the graphene–fullerene transformation from 4.0 eV to 1.5–1.9 eV, providing the decrease of the minimal temperature at which such a transformation can be observed experimentally from about 1400 K for free graphene flakes to about 700–800 K. While the transformation of free graphene flakes is found to occur through formation of chains of two-coordinated carbon atoms at the flake edges, the mechanism of the Ni-assisted graphene–fullerene transformation is revealed to be based on the transfer of carbon atoms from the graphene flake to the Ni cluster and back. The way of controlled synthesis of endofullerenes with a transition metal cluster inside and heterofullerenes with a transition metal patch is also proposed

Formation of Nickel Clusters Wrapped in Carbon Cages: Toward New Endohedral Metallofullerene Synthesis

Despite the high potential of endohedral metallofullerenes (EMFs) for application in biology, medicine and molecular electronics, and recent efforts in EMF synthesis, the variety of EMFs accessible by conventional synthetic methods remains limited and does not include, for example, EMFs of late transition metals. We propose a method in which EMF formation is initiated by electron irradiation in aberration-corrected high-resolution transmission electron spectroscopy (AC-HRTEM) of a metal cluster surrounded by amorphous carbon inside a carbon nanotube serving as a nanoreactor and apply this method for synthesis of nickel EMFs. The use of AC-HRTEM makes it possible not only to synthesize new, previously unattainable nanoobjects but also to study in situ the mechanism of structural transformations. Molecular dynamics simulations using the state-of-the-art approach for modeling the effect of electron irradiation are performed to rationalize the experimental observations and to link the observed processes with conditions of bulk EMF synthesis