CO2 Methanation: Solvent-Free Synthesis of Nickel-Containing Catalysts from Complexes with Ethylenediamine.

CO2 methanation was studied in the presence of nickel catalysts obtained by the solid-state combustion method. Complexes with a varying number of ethylenediamine molecules in the coordination sphere of nickel were chosen as the precursors of the active component of the catalysts. Their synthesis was carried out without the use of solvents, which made it possible to avoid the stages of their separation from the solution and the utilization of waste liquids. The composition and structure of the synthesized complexes were confirmed by elemental analysis, IR spectroscopy, powder XRD and XPS methods. It was determined that their thermal decomposition in the combustion wave proceeds in multiple stages with the formation of NiO and Ni(OH)2, which are reduced to Ni0. Higher ethylenediamine content in the complex leads to a higher content of metal in the solid products of combustion. However, different ratios of oxidized and reduced forms of nickel do not affect the initial activation temperature of nickel catalysts in the presence of CO2. It was noted that, after activation, the sample obtained from [Ni(C2H8N2)2](NO3)2 exhibited the highest activity in CO2 methanation. Thus, this complex is a promising precursor for CO2 methanation catalysts, and its synthesis requires only a small amount of ethylenediamine.

The Use of Hybrid Genetic Algorithm in the Kinetic Analysis of Thermal Decomposition of [Ni(C2H8N2)3](ClO4)2 with Overlapping Stages.

This work describes the mathematical modeling of the thermal decomposition of the complex compound [Ni(En)3](ClO4)2 (En = C2H8N2 = ethylenediamine) in an inert atmosphere under non-isothermal conditions. This process is characterized by several simultaneous and intense stages: elimination of ethylenediamine from the nickel coordination sphere, decomposition of perchlorate anions, and explosive-like oxidation of free or bound ethylenediamine. These stages overlap and merge into a one step on the differential thermogravimetric curve. Typically, this curve is modeled as a one-stage process during kinetic analysis. In this paper, for the first time, the data from the dynamic mass-spectral thermal analysis and thermogravimetric analysis were modeled using the hybrid genetic algorithm, and the results were compared. A two-stage scheme of [Ni(En)3](ClO4)2 thermolysis was proposed and the kinetic parameters for each stage were obtained. It was shown that the decomposition of [Ni(En)3](ClO4)2 begins with the elimination of one molecule of ethylenediamine (stage A), then the perchlorate anions quickly decompose with the evolution of oxygen (stage B). We believe that the resulting ClO4-x- (x = 1-3), as stronger oxidizing agents, instantly start an explosive-like exothermic process of ethylenediamine oxidation (stage B).

New Solvent-Free Melting-Assisted Preparation of Energetic Compound of Nickel with Imidazole for Combustion Synthesis of Ni-Based Materials.

In this work two approaches to the synthesis of energetic complex compound Ni(Im)6(NO3)2 from imidazole and nicklel (II) nitrate were applied: a traditional synthesis from solution and a solvent-free melting-assisted method. According to infrared spectroscopy, X-ray diffraction, elemental and thermal analysis data, it was shown that the solvent-free melt synthesis is a faster, simpler and environmentally friendly method of Ni(Im)6(NO3)2 preparation. The results show that this compound is a promising precursor for the production of nanocrystalline Ni-NiO materials by air-assisted combustion method. The combustion of this complex together with inorganic supports makes it possible to synthesize supported nickel catalysts for different catalytic processes.

Catalytic Behavior of Iron-Containing Cubic Spinel in the Hydrolysis and Hydrothermolysis of Ammonia Borane.

The paper presents a comparative study of the activity of magnetite (Fe3O4) and copper and cobalt ferrites with the structure of a cubic spinel synthesized by combustion of glycine-nitrate precursors in the reactions of ammonia borane (NH3BH3) hydrolysis and hydrothermolysis. It was shown that the use of copper ferrite in the studied reactions of NH3BH3 dehydrogenation has the advantages of a high catalytic activity and the absence of an induction period in the H2 generation curve due to the activating action of copper on the reduction of iron. Two methods have been proposed to improve catalytic activity of Fe3O4-based systems: (1) replacement of a portion of Fe2+ cations in the spinel by active cations including Cu2+ and (2) preparation of highly dispersed multiphase oxide systems, involving oxide of copper.

The Formation of Perovskite during the Combustion of an Energy-Rich Glycine-Nitrate Precursor.

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.