Amorphous carbon (AC) is present in the bulk and on the surface of nanostructured carbon materials (NCMs) and exerts a significant effect on the physical, chemical and mechanical properties of NCMs. Thus, the determination of AC in NCMs is extremely important for controlling the properties of a wide range of materials. In this work, a comparative study of the effect of heat treatment on the structure and content of amorphous carbon in deposited AC film, nanodiamonds, carbon black and multiwalled carbon nanotube samples was carried out by TEM, XPS, XRD and Raman spectroscopy. It has been established that the use of the 7-peak model for fitting the Raman spectra makes it possible not only to isolate the contribution of the modes of amorphous carbon but also to improve the accuracy of fitting the fundamental G and D2 (D) modes and obtain a satisfactory convergence between XPS and Raman spectroscopy. The use of this model for fitting the Raman spectra of deposited AC film, ND, CB and MWCNT films demonstrated its validity and effectiveness for investigating the amorphous carbon in various carbon systems and its applicability in comparative studies of other NCMs.
Apatite is widely used in medicine as a biomaterial for bone tissue restoration. Properties of apatite depend on its composition, including the Ca/P ratio. This paper shows what range of Ca/P ratio can be attained in apatite by the mechanochemical method of synthesis, providing fast formation of a single-phase product. The synthesis was carried out from a reaction mixture of CaHPO4 and CaO at different Ca/P ratios in the range of 1.17–2.10. The products were studied by PXRD, FTIR and NMR spectroscopy, HRTEM, and STA. In mixtures with a low initial Ca/P ratio (1.17–1.48), directly in the mill, the formation of calcium orthophosphate with whitlockite structure containing an HPO42− group and structural water is shown for the first time. This phosphate has structure similar to that of whitlockites of hydrothermal origin and differs from high-temperature β-tricalcium phosphate that has composition Ca3(PO4)3. A series of samples of apatite was obtained with varied composition, which depends on the initial Ca/P ratio. At Ca/P < 1.67, the formation of two types of calcium-deficient apatite was documented. At Ca/P > 1.67, the existence of two types of calcium-rich apatite is confirmed.
The Ni-containing catalysts based on ceria–zirconia doped with Ti and Ti+Nb were prepared by the solvothermal method in supercritical fluids. Ni deposition was carried out by incipient wetness impregnation and the one-pot technique. All materials were investigated by a complex of physicochemical methods (XRD, BET, TEM, H2-TPR). Samples catalytic properties were studied in methane dry reforming in the plug-flow reactor. Conversions of CH4 and CO2, H2/CO ratio, and CO and H2 yields were measured, and detailed kinetics analysis was carried out. The influence of Ni loading method and support modification on the catalytic behavior in the methane dry reforming process was studied. The preparation method of catalysts affects the textural characteristics. For one-pot samples, pore volume and surface area are lower than for impregnated samples. For catalysts on modified supports, strong metal–support interaction was shown to increase catalytic activity. A reduction pretreatment of samples was shown to have significant influence on their catalytic properties. The kinetic parameters such as reaction rate constant at 700 °C, effective activation energy, and TOF were estimated and analyzed.
To achieve a high activity and coking stability of nickel catalysts in dry reforming of methane, materials comprised of ceria–zirconia doped by Ti were investigated as supports. Ceria–zirconia supports doped with titanium were prepared either via the Pechini method or by synthesis in supercritical alcohol media. Ni-containing catalysts were prepared by two techniques: standard incipient wetness impregnation and one-pot synthesis. The catalytic reaction of DRM to synthesis gas was carried out in the 600–750 °C range over 5% wt. Ni/Ce(Ti)ZrO2. Dried and calcined supports and catalysts were characterized by physicochemical methods including N2 adsorption, XRD, Raman, H2-TPR, and HRTEM. Both preparation methods led to formation of solid solution with cubic fluorite-like structure, as well as after addition of Ti. Introduction of Ti should provide improved oxygen storage capacity and mobility of support oxygen. The highest activity was observed with the catalyst of 5% wt. Ni/Ce0.75Ti0.2Zr0.05O2−δ composition due to optimized oxide support structure and support oxygen mobility.
The effect of different regimes of combustion of glycine–nitrate precursors on the formation of perovskite phases (LaMnO3 and LaCrO3) without additional heat treatment was studied. The following three combustion regimes were compared: the traditional solution combustion synthesis (SCS), volume combustion synthesis (VCS) using a powdered precursor, and self-propagating high-temperature synthesis (SHS) using a precursor pellet. The products of combustion were studied using a series of physicochemical methods (attenuated total reflection infrared spectroscopy (ATR FTIR), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), and thermal analysis). SHS was found to be the most productive regime for the formation of perovskite because of its ability to develop high temperatures in the reaction zone, which led to a reduced content of the thermally stable lanthanum carbonate impurities and to an increased yield and crystallite size of the perovskite phase. The reasons for the better crystallinity and purity of LaCrO3 as compared with LaMnO3 is also discussed, namely the low temperatures of the onset of the thermolysis, the fast rate of combustion, and the favorable thermodynamics for the achievement of high temperatures in the reaction zone.
The development of solvent-free methods for the synthesis of catalysts is one of the main tasks of green chemistry. A nickel–alumina catalyst for CO2 methanation was synthesized by solid-state combustion method using hexakis-(imidazole) nickel (II) nitrate complex. Using X-ray Powder Diffraction (XRD), Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and Hydrogen temperature-programmed reduction (H2-TPR), it was shown that the synthesized catalyst is characterized by the localization of easily reduced nickel oxide on alumina surface. This provided low-temperature activation of the catalyst in the reaction mixture containing 4 vol% CO2. In addition, the synthesized catalyst had higher activity in low-temperature CO2 methanation compared to industrial NIAP-07-01 catalyst, which contained almost three times more hard-to-reduce nickel–aluminum spinel. Thus, the proposed approaches to the synthesis and activation of the catalyst make it possible to simplify the catalyst preparation procedure and to abandon the use of solvents, which must be disposed of later on.