Optical Absorption and Raman Spectroscopy Study of the Fluorinated Double-Wall Carbon Nanotubes

Double-wall carbon nanotube (DWNT) samples have been fluorinated at room temperature with varied concentration of a fluorinating agent BrF3. Content of the products estimated from X-ray photoelectron data was equal to CF0.20 and CF0.29 in the case of deficit and excess of BrF3. Raman spectroscopy showed considerable decrease of carbon nanotube amount in the fluorinated samples. Analysis of optical absorption spectra measured for pristine and fluorinated DWNT samples revealed a selectivity of carbon nanotube fluorination. Nanotubes with large chiral angle are more inert to the fluorinating agent used

Thermal Behavior of Fluorinated Double-Walled Carbon Nanotubes

Double-walled carbon nanotubes (DWNTs), produced by a catalytic chemical vapor deposition method, have been fluorinated using a volatile mixture of BrF3 and Br2. Optical absorption spectroscopic study on the product detected nonfluorinated nanotubes, which could correspond to the inner walls of DWNTs. The fluorinated DWNTs have been annealed in vacuum at fixed temperatures, and X-ray photoelectron spectroscopy showed almost no fluorine in the sample heated to 300 °C. Comparison between X-ray fluorescent C KR spectra of the pristine DWNT sample and the annealed fluorinated sample revealed change of the atomic structure of graphitic shells in the process of thermal defluorination

Effect of ultrasound pretreatment on bromination of double-walled carbon nanotubes

Bromination of double-walled carbon nanotubes (DWCNTs) was carried out using a saturated vapor of Br2 at room temperature with or without a pretreatment in bromine water. X-ray photoelectron spectroscopy revealed that ultrasound pretreatment modified the chemical state of bromine in the product. The binding energies of the Br 3d electrons in the pre-sonicated DWCNT sample were between those characteristic of the covalent C–Br bonds and the negatively charged Br2 molecules, observed when the pretreatment was not performed. Raman spectroscopy, however, clearly evidenced Br–Br vibrations in both brominated samples. Calculations of CNT–Br2 models within density functional theory were used to propose that the electronic state of a Br2 molecule depends on the adsorption site. The bromine molecules prefer to be located near edge hydroxyl groups, which acept the electron density from Br2. This increases the binding energy of Br 3d levels as compared to that for Br2 molecules in other adsorption sites

Study of cytotoxicity performance of carbon nanohorns by method of spin probes

The effects of as-produced and treated by HNO3(3M) carbon nanohorns on the microviscosity of rat erythrocyte membranes and the viscosity of the water-containing plasma protein matrix were investigated by the method of spin probes. Addition of nanohorns at the concentration of 100 μg/ml to a suspension of erythrocytes led to an increase in membrane microviscosity during 4 h (about 60% effect). In addition, it was shown that nanohorns also induced an increased polarity of the microenvironment for lipophilic probes in the outer layer of membrane phospholipids, as well as disorders in erythrocytes membranes. Addition of nanohorns to plasma led to a little decrease in the viscosity of water and protein matrix, apparently, due to its partial destruction, impacting especially albumin. Pristine and treated by HNO3(3M) acid nanohorns was found more cytotoxic than nanoparticles of oxidized graphene, and significantly less than carbon nanotubes, which are known to dramatically increase the microviscosity of the membranes of erythrocytes and disrupt their integrity

Bromine polycondensation in pristine and fluorinated graphitic carbons

Despite decades of study the precise behavior of bromine in graphitic carbons remains unclear. In this report, using Raman spectroscopy, we reveal two types of bromine structure in graphitic carbon materials. Between fluorinated graphene layers with a composition close to C2F, Br2 molecules are intercalated in a form similar to liquid bromine. Bromination of pristine and low-fluorinated graphitic carbons behaves very differently with distinct Br-related Raman spectra. With the guidance of density functional theory (DFT) calculations, all Raman features are assigned to normal vibration modes of specific bromine species over graphene and fluorinated graphene. When intercalated between extended non-fluorinated sp2-hybridized carbon regions, physisorbed Br2 molecules move freely across the non-functionalized region toward the CF border. Multiple Br2 molecules then combine spontaneously into Br3-based chains, whose coupling activates otherwise Raman inactive modes. Significant charge transfer to bromine species occurs in this case. DFT calculated frequencies match precisely the experimental Br-related Raman bands observed in the intercalation carbon compounds. The fluorine-catalyzed bromine chain-formation process shown here is general and should also operate with edges and other defect species

Effect of Hydrogen Fluoride Addition and Synthesis Temperature on the Structure of Double-Walled Carbon Nanotubes Fluorinated by Molecular Fluorine

Double‐walled carbon nanotubes (DWCNTs) have been fluorinated by pure molecular fluorine (F2) at room temperature or 200 °C and a mixture of F2 with hydrogen fluoride (HF) at 200 °C that resulted in products with compositions of CF0.12, CF0.39, and CF0.53 as determined by X‐ray photoelectron spectroscopy. The differences in the structures of three kinds of fluorinated DWCNTs were revealed using transmission electron microscopy, Raman scattering, and near‐edge X‐ray absorption fine structure (NEXAFS) spectroscopy. Quantum‐chemical modeling of the NEXAFS F K‐edge spectra detected a change in the fluorine pattern with the increase of the F2 treatment temperature. The presence of HF in fluorine gas was found to accelerate the fluorination process and cause a partial destruction of outer shells of the DWCNT

Shielding effects in thin films of carbon nanotubes within microwave range

The electromagnetic shielding properties of thin films comprising different types of carbon nanotubes (CNTs) were analysed in the microwave frequency range (26–36 GHz). A comparative analysis of the shielding properties was achieved for films based on long and short single-, double- and multi-walled CNTs. The experimental results proved that long-length single-walled CNTs demonstrate the highest interaction with the electromagnetic (EM) field, thereby providing the best shielding efficiency. At the same time, double-walled CNTs demonstrate a higher level of absorption ability (50%) along with the overall high EM shielding efficiency (88%), which makes them attractive for using in nanoelectronics screens as they produce the smallest secondary EM pollution