Preparation and spectroscopic properties of chlorofullerenes C60Cl24, C60Cl28, and C60Cl30

We report easy preparation of recently discovered highly chlorinated fullerenes T_h-C₆₀Cl₂₄, C₁-C₆₀Cl₂₈, and D_3d-C₆₀Cl₃₀ in high-temperature reactions of C₆₀ with PCl₅ and ICl. Formation and interconversion of chlorofullerenes was investigated in details for C₆₀-ICl system. C₆₀Cl₂₈ is the least stable chlorofullerene that undergoes rearrangement (accompanied by partial chlorine elimination) into more stable T_h-C₆₀Cl₂₄ under more drastic reaction conditions (increased temperature and time of chlorination). T_h-C₆₀Cl₂₄ yields D_3d-C₆₀Cl₃₀ at temperatures above 220 °C via a sequence of rearrangements and further addition of chlorine. In contrast to the fullerene reaction with ICl, interaction of C₆₀ with PCl₅ is very selective with respect to formation of C₆₀Cl₂₄ in a wide temperature range. Solid-state electronic (UV-Vis) and vibrational (IR) spectra of chlorinated fullerenes C₆₀Cl₂₄, C₆₀Cl₂₈, C₆₀Cl₃₀ and fluorinated fullerenes C₆₀F₁₈ and C₆₀F₃₆ were recorded in the spectral range between 30 and 45,000 cm⁻¹. Raman spectra were also acquired for all investigated compounds. Moreover, molecular geometry of the C₆₀Cl₂₄ and its theoretical IR-absorption spectrum were calculated using B3LYP/STO-3G chemistry model.     

Soot-free synthesis of C60

A new synthetic medium for the production of C₆₀ has been found that does not produce soot. C₆₀ was produced in the liquid phase of an aerosol of precursor soot at 700 °C. The precursor soot aerosol, a high temperature stable form of hydrocarbon, was produced by pyrolysis of acetylene at atmospheric pressure in a flow tube reactor. At 700 °C, the effluent particles were found to contain PAHs, small hydrocarbons and fullerenes but no observable black material. However, when the reactor temperature was changed to 800 °C, soot was also produced in the effluent particles along with PAHs and other small hydrocarbons, and the fullerene product disappeared. These results show a clear competition between the production of fullerenes and other forms of carbon. The filter-collected effluent was shown to be completely soluble in conventional solvents suggesting the possibility of an efficient cyclic synthetic process. Fullerenes were only found in the particle phase implying the first observed liquid phase synthesis of C₆₀.     

Electrochemical behavior of C60 films and C60/lipid films in ionic liquids

Cyclic voltammograms (CVs) of C₆₀ films and C₆₀ embedded in cast films of triple-tailed cationic surfactant solutions and salt-free zero-charged cationic/anionic (catanionic) surfactant vesicles on glassy carbon electrode in a typical room-temperature ionic liquid (RT-IL), 1-n-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF₆]), were examined. CVs show typically electrochemical oxidation and reduction. The salt-free zero-charged catanionic surfactant bilayer vesicles were determined by freeze-fracture transmission electron microscopy (FF-TEM) images and small-angle X-ray scattering (SAXS) measurements. The cast films of the salt-free zero-charged catanionic surfactant vesicles incorporated C₆₀ molecules were employed to study the electrochemical properties in RT-ILs, which would open new fields for the bulk electronic properties of fullerenes or their derivatives in ionic liquids.     

Soot-free synthesis of C60

A new synthetic medium for the production of C₆₀ has been found that does not produce soot. C₆₀ was produced in the liquid phase of an aerosol of precursor soot at 700 °C. The precursor soot aerosol, a high temperature stable form of hydrocarbon, was produced by pyrolysis of acetylene at atmospheric pressure in a flow tube reactor. At 700 °C, the effluent particles were found to contain PAHs, small hydrocarbons and fullerenes but no observable black material. However, when the reactor temperature was changed to 800 °C, soot was also produced in the effluent particles along with PAHs and other small hydrocarbons, and the fullerene product disappeared. These results show a clear competition between the production of fullerenes and other forms of carbon. The filter-collected effluent was shown to be completely soluble in conventional solvents suggesting the possibility of an efficient cyclic synthetic process. Fullerenes were only found in the particle phase implying the first observed liquid phase synthesis of C₆₀.     

C60 structural transformation by electrorheological testing

The electrorheological properties of a C₆₀ laden silicon oil suspension was studied. Samples were prepared by dispersing C₆₀ molecules in toluene, the solution was then incorporated into silicon oil, and finally the solvent was allowed to evaporate by heating the suspension below its boiling temperature. As prepared, C₆₀ particles precipitated and formed small crystals. Samples were then homogenized for electrorheological testing. Electrorheological analysis showed an increase in the storage modulus as well the typical alignment of the suspension between electrodes (18/8 steel) though, the increase in storage modulus was not reversible. Fullerenes formed whiskers similar to those produced by liquid-liquid precipitation. Moreover, under a higher electric field thicker fibers were formed. C₆₀ acts as a precursor of fibers under these circumstances. In all the cases, C₆₀ whiskers/fibers remain after switching off the applied electric field making it a non-reversible effect, therefore not an electrorheological system.     

Fluorination of pressure-polymerized C60 phases

The reactivity of O-, T- and R-phases of the high pressure-high temperature (HPHT) polymerized C₆₀ towards gaseous fluorine in the temperature range of 50-250 °C was investigated. The reaction products were characterized by FTIR, powder X-ray diffraction, SEM, EDX, and VTP-EIMS to determine the bulk stoichiometries, bonding patterns, phase compositions, crystalline structures and thermal decomposition behavior of the fluorinated polymers. At 1 h isothermal treatment duration, fluorinated products with various bulk stoichiometries were obtained from different polymer phases with the R-phase showing the highest fluorine uptake. At 250 °C, all C₆₀ polymers showed partial decomposition to unfluorinated C₆₀ monomer under fluorine atmosphere. At 200 °C, the fluorination of R-phase yielded a pure fluoropolymer most likely having a {C₆₀F_x}_n (x = 36-44) composition. The same fluoropolymer was presumably obtained from O- and T-phases in lower yields. The linear chain structure was suggested for this new fluorocarbon polymer in agreement with the molecular mechanics modeling calculations.     

Solvated structure of C60 nanowhiskers

This work characterizes the structure of C₆₀ nanowhiskers prepared by the liquid-liquid interfacial precipitation method in the C₆₀-saturated m-xylene and isopropyl alcohol system. Transmission electron microscopy and X-ray diffraction measurement show that the C₆₀ nanowhiskers had a hexagonal structure with cell dimensions a = 2.407 nm and c = 1.018 nm which is different from pristine C₆₀. The structure of the C₆₀ nanowhiskers in solution is different from that of the solvated structure reported for the C₆₀ nanotubes but similar to that reported for the C₆₀ bulk crystal solvated with m-xylene. X-ray diffraction analysis also showed a shift to fcc structure after solvent evaporation. The C₆₀ nanowhiskers prepared using toluene as solvent also showed a similar solvated structure, and a more rapid structural change into fcc upon drying was again observed.     

Synthesis of alkali-metal-doped C60 nanotubes

C₆₀ nanotubes have been synthesized by a solution-solution method. After degassing in a dynamic vacuum, the C₆₀ nanotubes doped with alkali metals by means of vapor evaporation method. Different temperatures have been studied to evaporate the alkali metals for the doping experiments. Raman spectrum was further employed to analyze the doping concentration of the obtained samples. It was found that all three alkali metals (Li, Na and K) used can be efficiently doped into the C₆₀ nanotubes, forming A_xC₆₀ nanotubes. The doping concentration of Li, Na changed from low to high level, depending on the experiment temperatures, while K doping always gave saturated doping. The melt points, the ionic sizes and vapor pressures of alkali metals were thought to affect the final doping results.     

Synthesis and growth mechanism of differently shaped C60 nano/microcrystals produced by evaporation of various aromatic C60 solutions

We present a detailed study of the synthesis of C₆₀ nano- and microrods as well as crystals with normal shapes by the evaporation of C₆₀ solutions based on different aromatic solvents. C₆₀ nano- and microrods are grown with high yield by vaporizing C₆₀ solutions in meta-isomers of aromatic solvents on different substrates while para-isomers give a different type of growth leading to highly crystalline two- and three-dimensional nano- and microcrystals with fcc structure. The role of solvent properties was investigated by using positional isomers containing different halogen radicals. The as-grown crystal rods form hexagonal structures but transform into fcc structure on annealing in vacuum. IR and EDX analysis indicate that solvents remain in the hexagonal nano- and microrods, while it is hard to detect any trace of solvents in the two- or three-dimensional nano- and microcrystals. Furthermore, we present direct proof of the nucleation-growth mechanism for C₆₀ rods. By the vaporization method, the solubility of C₆₀ in the studied halogen aromatic solvents is found to correlate with the diameter distribution of the C₆₀ rods and we suggest that the chemical affinity of the aromatic solvent molecules to C₆₀ may determine its ability to force C₆₀ to form rod-shaped crystals.     

Molecular dynamics simulation of triaxial compression of C60 and C80 solids

Present work investigates the triaxial compression behavior of face-centered cubic C₆₀ and C₈₀ solids using molecular dynamics simulation. Second-generation empirical bond-order potential governs the atomic interactions within a C₆₀ or C₈₀ molecule, whereas van der Waals potential dominates the interactions between C₆₀ or C₈₀ molecules. The equilibrium lattice spacings for C₆₀ and C₈₀ solids are obtained as 14.26 Å and 15.56 Å, respectively. Investigation focuses on the effects of: (i) van der Waals potential, (ii) temperature and (iii) loading rate, on the bulk moduli and hydrostatic stress vs. volumetric strain curves of C₆₀ and C₈₀ solids. Our results showed that these properties are dependent on loading rate and the choice of van der Waals potential, but insensitive to temperature change.     

Ethylene physisorption on C60 fullerene

Monte Carlo computer simulation results on the adsorption of ethylene on C₆₀ fullerene are employed to locate the adsorption sites observed for the adsorption of other simple gases. The distributions of molecules according to the gas-solid interaction energy obtained from the simulations are in agreement with experimental results reported in the literature. We focused our attention on the isotherm obtained at 150 K. At this temperature, the molecules with a certain gas-solid energy have been identified and their location employed to find out the adsorption sites. This sort of distribution has been averaged over all the equilibrated configurations generated during the simulation. The results obtained confirm the assignment of adsorption sites previously reported for the adsorption of N₂, Ar, and CO₂. The distribution of molecules over the gas-gas interaction energy is also analyzed and the obtained results suggest that the adsorbed molecules prefer a T-shaped stacking. This conclusion is obtained through the analysis of the distributions with the aid of the gas-gas interaction potential. This observation agrees with recently published results by other authors. The information obtained from the microdensity profiles has also been employed to locate the adsorption sites.     

Functionalization of C60 with gold nanoparticles

Gold nanoparticles (GNPs) with attached C₆₀ molecules (C₆₀-GNPs) were prepared through the amination reaction of fullerene C₆₀ with peripheral amino groups located on the surface of gold. Molecules of 4-aminobenzenethiol/1-hexanethiol containing amino groups were introduced onto the surface of gold by the reduction of a gold salt (HAuCl₄) with sodium borohydride (NaBH₄) in a one-pot way, which was accompanied by anchoring of the targeted thiol mixture on the gold cluster by Au-S bonds. This simple system avoids many difficult reactions and purification processes and does not involve a complicated chemical modification of C₆₀ and exchange reactions of GNPs.     

Polymeric fullerene oxide (fullerene ozopolymers) produced by prolonged ozonation of C60 and C70 fullerenes

The prolonged ozonation of C₆₀ and C₇₀ fullerene produces light brown to brown amorphous solids which are insoluble in chlorinated and hydrocarbon solvents but which are readily soluble in water, acetone and ethanol where they give dark-brown solutions. The polymeric and polyelectrolytic nature of these solids has been shown by viscosimetric and cryoscopic measurements. Due to the polymeric nature the solids have been called ‘ozopolymers’. The reactivity and the ozone uptake have been measured quantitatively during the ozonation of C₆₀ and C₇₀ fullerene in CCl₄. Three different C₆₀ ozopolymer samples have been produced at different degrees of ozonation: at O₃/C₆₀ molar ratio of 8, 14 and 26. The C₇₀ ozopolymer has been produced at an O₃/C₇₀ molar ratio of 30. All the samples have been studied by FT-IR spectroscopy and the C₆₀ ozopolymers have been easily reduced by the action of Zn dust and acetic acid or by the action of H₂S and studied by FT-IR. The action of oxidizing agents has been studied as well. C₆₀ ozopolymer is a polyelectrolyte rich in carboxyl groups and for this reason it possesses a high metal binding capacity similar to that of humic acids. The thermal stability of C₆₀ ozopolymer and its reduced derivatives as well as the thermal stability of C₇₀ ozopolymer has been checked by thermogravimetric analysis in nitrogen and air flow. Finally, the electrical conductivity of C₆₀ ozopolymer was found to be σ=2.8×10⁻⁸ S/cm which is three orders of magnitude lower than that of pure C₆₀.     

Stability of hexagonal modification of fullerite C60

Stability of the hcp modification of fullerite C₆₀ under heating, compression, and mechanical grinding was studied. It was established that uniaxial load and mechanical grinding caused transition of the hcp modification into more stable fcc modification, while no transition was observed upon heating or hydrostatic pressure. The results were discussed in terms of the theory of the deformation of solids.     

C60(Cg) and C70(g): A computational study of the pressure and temperature dependence of their populations

Equilibrium mixtures of pure carbon gas-phase aggregates, C_n(g). are treated combining all available observational as well as computational thermodynamical data for n = 1, 2, 3, 4, 5, 60 and 70. A considerable sensitivity to temperature and pressure is pointed out, showing that there are both regions of a higher relative population of C₆₀(g) as well as of C₇₀(g). There can be significant competition between the formation of small and large clusters. Relations between the full-equilibrium situation (i.e., including graphite), gas-phase equilibrium, and the nonequilibrium situation are discussed.     

Synthesis of C60 Fullerene-Silica Hybrid Nano Structures

We have recently demonstrated a procedure for the synthesis of silica nanometer and micrometer particles under modest conditions. Here we report the synthesis of C₆₀ fullerene-silica hybrid nanometer sized materials via sol-gel processing at neutral pH and under ambient conditions. The C₆₀ fullerene, when functionalized, was water-soluble and also able to facilitate the formation of silica structures from an aqueous silica precursor. This C₆₀ fullerene had similar functionality to the cationically charged polymers, which have been reported earlier to act as catalysts/templates for silicification. The resulting organic-inorganic hybrid was studied using SEM, EDS and UV/Vis spectroscopy. These hybrid materials may have applications in areas such as optical devices, semiconductors, chemical sensors, catalysis and in the medical field. The results presented in this study may be useful in developing a process for the synthesis of novel organic-inorganic nanometer sized materials and for the biomimetic synthesis of silica.     

High-pressure solubility of fullerene C60 in toluene

The solubility of fullerene C₆₀ in toluene was measured at temperatures between 278.2 and 308.2 K and pressures up to 340 MPa, and also at temperatures between 258.2 and 298.2 K under atmospheric pressure. The solubility increased with increasing pressure, and then decreased with a sharp maximum, suggesting a transition between solid phases. A thermodynamic analysis of the solubility supported the proposal of Korobov, et al. that the two solids correspond to C₆₀ (fcc) and C₆₀ · 2 (toluene) solvate. The solubility enhancement of C₆₀ by pressure in a low-pressure region is an unusual phenomenon when compared with the decrease in solubility of nonpolar molecular solids generally observed with rises in pressure.     

Self-assembled network structures in Al/C60 composites

A method is explored for the development of nano-network structures in aluminum-based composites containing C₆₀-fullerenes by annealing at 500 °C. During annealing, although carbon atoms are decomposed from fullerenes attempting to form carbides, they cannot readily form carbides because C₆₀-fullerenes are individually dispersed and the driving force for long-range diffusion of carbon atoms is not sufficient at 500 °C. Carbon atoms rather occupy the interstices of aluminum, providing a meta-stable supersaturated aluminum phase with distorted crystal structures. The supersaturated aluminum phases grow with a strong anisotropy derived from lattice mismatch, meet neighboring phases, and then self-assemble into network structures. These nano-scale network structures are extremely stable at 500 °C, and offer significant potential for the development of structural aluminum matrix composites with a GPa-level strength.