Technological Institute for Superhard and Novel Carbon Materials

Structured Fischer–Tropsch synthesis catalysts were tested in tubular reactors of industry-standard diameters of 0.5 or 0.75 inches. The structured catalyst bed was manufactured by the obturation of a straight bunch of graphite-based extrudates (D = 1.5 mm, L = 30 mm). A conventional loose bed of granulated catalyst (D = 1.5 mm, L = 3 mm) was tested as a reference. In a 1000–3000 h−1 syngas space velocity range, structured and loose catalyst bed testing showed no significant differences in their main catalytic parameters. Nevertheless, their C5+ hydrocarbon group composition was quite different, i.e., the alkene fraction rose from 9 to 23%, while n-alkanes dropped from 81 to 64%. This could be a result of secondary reaction intensification in the conventional loose bed due to its zeolite acid site’s higher availability. Further FTS testing of the structured catalysts in 4000–6000 h−1 manifested distinctive limits in C5+ productivity for 0.5 and 0.75 inches of 512 kg C5+/(m3 reactor·h) and 362 kg C5+/(m3 reactor·h), respectively. This may be explained by limitations in structured bed thermal conductivity. It suggests that the arrangement of extrudates in the structured catalyst can significantly affect the reaction heat and mass transfer conditions and affords new opportunities for group composition control by means of catalyst bed organization.

It is shown that acid activation of ultralong carbon nanotubes synthesis products increases their reactivity during subsequent thermochemical treatment in air at 480 °C. Such an integrated approach of CNTs processing provides high purity and maximum yield of the target product. For example, the non-CNT fraction decreases by 3.2 times, while the residual iron content decreases by 17–24 times in comparison with thermochemical treatment without acid. Raman spectroscopy and low-temperature nitrogen adsorption showed that acid activation does not lead to extra surface defects, which could initiate further oxidation of carbon matrix in air. It is suggested that the increased reactivity of CNT synthesis products after acid activation during thermo-oxidative degradation may be due to the formation of an “adduct” of carboxyl groups on the surface of nanotube carbon matrix with hydrogen chloride. It was shown by thermogravimetric studies coupled with mass-spectra investigation of gas evolved, that under the constant heating, at the temperatures of the beginning of intensive oxidation (500–600 °C), the decomposition of the “adduct” occurs, bypassing the stage of formation of more temperature-resistant phenolic groups, which can inhibit further oxidation. Water released during the decomposition of the “adduct” can also accelerate the process of thermal oxidation.

The spectra of the optically detected magnetic resonance for single NV– centers have been experimentally studied in two solid-state samples in the range of hyperfine interactions between the electron spin and the nitrogen nucleus spin in the same NV– center. This study has been aimed at reaching a maximal microwave frequency resolution in the experimental setup used. For measurements, two low-nitrogen (no higher than 50 ppb) diamond single-crystal samples have been grown. Measured time T*2 of the spin decoherence in NV– centers was about 2 μs in one sample and 20 μs in the other. For both samples, the spectrum of the optically detected magnetic resonance for the hyperfine splitting of a single NV– center and 14N atom has been taken and investigated. The resolution in these samples has been estimated at a level of 3.5 and 0.18 MHz, respectively. It has been noted that the resolution of the spectrum improves with increasing time T*2 of the spin decoherence of the single NV– center.

The review is dedicated to the topical field of research aimed at creating catalysts combining several types of active sites. At the same time, the composition of Fischer–Tropsch synthesis (FTS) products can be controlled by changing the strength and concentration of the active sites and inter-site distances. A comparative analysis of the literature data allows to formulate the main principles of catalytic particles formation active in FTS and acid-catalyzed transformations of hydrocarbons: (1) the presence of weak Bronsted acid sites to control the cracking depth, (2) an availability of Bronsted acid sites for re-adsorption hydrocarbons and (3) weak Co-zeolite interaction to reduce methane formation.

Ultralong carbon nanotubes (UCNTs) are in high demand for nanocomposites applications due to their magnificent physical and chemical properties. UCNTs are synthesized by the catalytic chemical vapor deposition (CCVD) method and, before use as fillers in nanocomposites, should be purified of residual catalyst and non-CNT particles without significant destruction or scissoring of the UCNT. This study investigates the role of water vapor for purification of UCNTs from iron catalyst particles and the importance of water assistance in this process is confirmed. It was shown that wet air treatment of products of UCNTs CCVD synthesis under mild conditions can be used to sufficiently decrease residual iron catalyst content without significant carbon losses in comparison to the results obtained with dry air, while the residual iron content was shown to significantly influence the subsequent oxidation of different forms of carbons, including UCNTs. The increasing of D/G ratio of Raman spectra after wet air treatment of products of UCNTs CCVD synthesis makes it possible to conclude that iron catalyst particles transform into iron oxides and hydroxides that caused inner structural strains and destruction of carbon shells, improving removal of the catalyst particles by subsequent acid treatment. UCNTs purification with water assistance can be used to develop economically and ecologically friendly methods for obtaining fillers for nanocomposites of different applications.

In the present study we investigated the nanostructuring processes in locally suspended few-layer graphene (FLG) films by irradiation with high energy ions (Xe, 26–167 MeV). For such an energy range, the main channel of energy transfer to FLG is local, short-term excitation of the electronic subsystem. The irradiation doses used in this study are 1 × 1011–5 × 1012 ion/cm2. The structural transformations in the films were identified by Raman spectroscopy and transmission electron microscopy. Two types of nanostructures formed in the FLG films as a result of irradiation were revealed. At low irradiation doses the nanostructures were formed preferably at a certain distance from the ion track and had the form of 15–35 nm “bunches”. We assumed that the internal mechanical stress that arises due to the excited atoms ejection from the central track part creates conditions for the nanodiamond formation near the track periphery. Depending on the energy of the irradiating ions, the local restructuring of films at the periphery of the ion tracks can lead either to the formation of nanodiamonds (ND) or to the formation of AA’ (or ABC) stacking. The compressive strain value and pressure at the periphery of the ion track were estimated as ~0.15–0.22% and ~0.8–1.2 GPa, respectively. The main novel results are the first visualization of ion tracks in graphene in the form of diamond or diamond-like rings, the determination of the main condition for the diamond formation (the absence of a substrate in combination with high ion energy), and estimates of the local strain at the track periphery. Generally, we have developed a novel material and have found how to control the film properties by introducing regions similar to quantum dots with the diamond interface in FLG films.

Abstract A method for leaching Co2Al9 alloy was developed and optimized to produce nonpyrophoric Raney cobalt, which is used as a component of a highly efficient granular Fischer–Tropsch synthesis catalyst. A comparative study of the laboratory‐produced Raney cobalt with commercially available analog was done using the methods of low‐temperature nitrogen sorption, thermoprogrammed reduction (TPR), thermoprogrammed ammonia desorption, thermal analysis, thermal conductivity, and scanning and transmission electron microscopy. Partial dissolution of cobalt with the formation of Co2+ and Co3+ ions was detected during aluminum leaching. It was found that incomplete purification of commercial Raney cobalt from aluminum hydroxide impurity may lead to overestimation of specific surface area. It was also found that the acidity of the molded catalyst is mainly determined not by Raney cobalt, but by elements of the composite catalyst carrier. For the first time, a linear dependence between the content of structures in a Fischer–Tropsch synthesis catalyst with TPR‐AR maxima of 500–800°C and the amount of synthesized liquid hydrocarbons has been established. It is concluded that metal nanoparticles with partial charge transfer (Coδ+) are active centers of selective formation of C5+ hydrocarbons. Obtaining the maximum number of these centers and reaching a high thermal conductivity of the composite with a developed system of transport pores is a criterion for creating an effective cobalt catalyst for low‐temperature synthesis of hydrocarbons.