In Situ Study of Reduction of MnxCo3-xO4 Mixed Oxides: The Role of Manganese Content.

A series of Mn-Co mixed oxides with a gradual variation of the Mn/Co molar ratio were prepared by coprecipitation of cobalt and manganese nitrates. The structure, chemistry, and reducibility of the oxides were studied by X-ray diffraction (XRD), X-ray absorption spectroscopy, X-ray photoelectron spectroscopy (XPS), and temperature-programmed reduction (TPR). It was found that at concentrations of Mn below 37 atom %, a solid solution with a cubic spinel structure is formed. At concentrations above 63 atom %, a solid solution is formed on the basis of a tetragonal spinel, while at concentrations in a range of 37-63 atom %, a two-phase system, which contains tetragonal and cubic oxides, is formed. To elucidate the reduction route of mixed oxides, two approaches were used. The first was based on a gradual change in the chemical composition of Mn-Co oxides, illustrating slow changes in the TPR profiles. The second approach consisted in a combination of in situ XRD and pseudo-in situ XPS techniques, which made it possible to directly determine the structure and chemistry of the oxides under reductive conditions. It was shown that the reduction of Mn-Co mixed oxides proceeds via two stages. During the first stage, (Mn, Co)3O4 is reduced to (Mn, Co)O. During the second stage, the solid solution (Mn, Co)O is transformed into metallic cobalt and MnO. The introduction of manganese cations into the structure of cobalt oxide leads to a decrease in the rate of both reduction stages. However, the influence of additional cations on the second reduction stage is more noticeable. This is due to crystallographic peculiarities of the compounds: the conversion from the initial oxide (Mn, Co)3O4 into the intermediate oxide (Mn, Co)O requires only a small displacement of cations, whereas the formation of metallic cobalt from (Mn, Co)O requires a rearrangement of the entire structure.

The Influence of Cu and Al Additives on Reduction of Iron(III) Oxide: In Situ XRD and XANES Study.

The reduction of Fe-based nanocomposite catalysts doped with Al and Cu has been studied using in situ X-ray diffraction (XRD), in situ X-ray absorption near-edge structure (XANES), and temperature-programmed reduction (TPR) techniques. The catalysts have been synthesized by melting of iron, aluminum, and copper salts. According to XRD, the catalysts consist mainly of Fe2O3 and Al2O3 phases. Alumina is in an amorphous state, whereas iron oxide forms nanoparticles with the protohematite structure. The Al3+ cations are partially dissolved in the Fe2O3 lattice. Due to strong alumina-iron oxide interaction, the specific surface area of the catalysts increases significantly. TPR and XANES data indicate that copper forms highly dispersed surface CuO nanoparticles and partially dissolves in iron oxide. It has been shown that the reduction of iron(III) oxide by CO proceeds via two routes: a direct two-stage reduction of iron(III) oxide to metal (Fe2O3 → Fe3O4 → Fe) or an indirect three-stage reduction with the formation of FeO intermediate phases (Fe2O3 → Fe3O4 → FeO → Fe). The introduction of Al into Fe2O3 leads to a decrease in the rate for all reduction steps. In addition, the introduction of Al stabilizes small Fe3O4 particles and prevents further sintering of the iron oxide. The mechanism of stabilization is associated with the formation of Fe3- xAl xO4 solid solution. The addition of copper to the Fe-Al catalyst leads to the formation of highly dispersed CuO particles on the catalyst surface and a mixed oxide with a spinel-type crystalline structure similar to that of CuFe2O4. The low-temperature reduction of Cu2+ to Cu0 accelerates the Fe2O3 → Fe3O4 and FeO → Fe transformations but does not affect the Fe3O4 → FeO/Fe stages. These changes in the reduction properties significantly affect the catalytic performance of the Fe-based nanocomposite catalysts in the low-temperature oxidation of CO.

Synthesis and Concentration of Organosols of Silver Nanoparticles Stabilized by AOT: Emulsion Versus Microemulsion.

In this work, we tried to combine the advantages of microemulsion and emulsion synthesis to obtain stable concentrated organosols of Ag nanoparticles, promising liquid-phase materials. Starting reagents were successively introduced into a micellar solution of sodium bis-(2-ethylhexyl)sulfosuccinate (AOT) in n-decane in the dynamic reverse emulsion mode. During the contact of the phases, Ag+ passes into micelles and Na+ passes into emulsion microdroplets through the cation exchange AOTNaOrg + AgNO3Aq = AOTAgOrg + NaNO3Aq. High concentrations of NaNO3 and hydrazine in the microdroplets favor an osmotic outflow of water from the micelles, which reduces their polar cavities to ∼2 nm. As a result, silver ions are contained in the micelles, and the reducing agent is present mostly in emulsion microdroplets. The reagents interact in the polar cavities of micelles to form ∼7 nm Ag nanoparticles. The produced nanoparticles are positively charged, which permitted their electrophoretic concentration to obtain liquid concentrates (up to 30% Ag) and a solid Ag-AOT composite (up to 75% Ag). Their treatment at 250 °C leads to the formation of conductive films (180 mOhm per square). The developed technique makes it possible to increase the productivity of the process by ∼30 times and opens up new avenues of practical application for the well-studied microemulsion synthesis.

Cobalt-Imidazole Complexes: Effect of Anion Nature on Thermochemical Properties.

A solvent-free method was proposed for the synthesis of hexaimidazolecobalt(II) nitrate and perchlorate complexes-[Co(C3H4N2)6](NO3)2 and [Co(C3H4N2)6](ClO4)2-by adding cobalt salts to melted imidazole. The composition, charge state of the metal, and the structure of the resulting complexes were confirmed by elemental analysis, XPS, IR spectroscopy, and XRD. The study of the thermochemical properties of the synthesized complexes showed that [Co(C3H4N2)6](NO3)2 and [Co(C3H4N2)6](ClO4)2 are thermally stable up to 150 and 170 °C, respectively. When the critical temperature of thermal decomposition is reached, oxidative two-stage gasification is observed. In this case, the organic component of the [Co(C3H4N2)6](NO3)2 complex undergoes almost complete gasification to form Co3O4 with a slight admixture of CoO, which makes it attractive as a component of gas-generation compositions, like airbags.

Co and Co3O4 in the Hydrolysis of Boron-Containing Hydrides: H2O Activation on the Metal and Oxide Active Centers.

This work focuses on the comparison of H2 evolution in the hydrolysis of boron-containing hydrides (NaBH4, NH3BH3, and (CH2NH2BH3)2) over the Co metal catalyst and the Co3O4-based catalysts. The Co3O4 catalysts were activated in the reaction medium, and a small amount of CuO was added to activate Co3O4 under the action of weaker reducers (NH3BH3, (CH2NH2BH3)2). The high activity of Co3O4 has been previously associated with its reduced states (nanosized CoBn). The performed DFT modeling shows that activating water on the metal-like surface requires overcoming a higher energy barrier compared to hydride activation. The novelty of this study lies in its focus on understanding the impact of the remaining cobalt oxide phase. The XRD, TPR H2, TEM, Raman, and ATR FTIR confirm the formation of oxygen vacancies in the Co3O4 structure in the reaction medium, which increases the amount of adsorbed water. The kinetic isotopic effect measurements in D2O, as well as DFT modeling, reveal differences in water activation between Co and Co3O4-based catalysts. It can be assumed that the oxide phase serves not only as a precursor and support for the reduced nanosized cobalt active component but also as a key catalyst component that improves water activation.

Reducibility of Al3+-Modified Co3O4: Influence of Aluminum Distribution.

The reduction of Co-based oxides doped with Al3+ ions has been studied using in situ XRD and TPR techniques. Al3+-modified Co3O4 oxides with the Al mole fraction Al/(Co + Al) = 1/6; 1/7.5 were prepared via coprecipitation, with further calcination at 500 and 850 °C. Using XRD and HAADF-STEM combined with EDS element mapping, the Al3+ cations were dissolved in the Co3O4 lattice; however, the cation distribution differed and depended on the calcination temperature. Heating at 500 °C led to the formation of an inhomogeneous (Co,Al)3O4 solid solution; further treatment at 850 °C provoked the partial decomposition of mixed Co-Al oxides and the formation of particles with an Al-depleted interior and Al-enriched surface. It has been shown that the reduction of cobalt oxide by hydrogen occurs via the following transformations: (Co,Al)3O4 → (Co,Al)O → Co. Depending on the Al distribution, the course of reduction changes. In the case of the inhomogeneous (Co,Al)3O4 solid solution, Al stabilizes intermediate Co(II)-Al(III) oxides during reduction. When Al3+ ions are predominantly on the surface of the Co3O4 particles, the intermediate compound consists of Al-depleted and Al-enriched Co(II)-Al(III) oxides, which are reduced independently. Different distributions of elemental Co and Al in mixed oxides simulate different types of the interaction phase in Co3O4/γ-Al2O3-supported catalysts. These changes in the reduction properties can significantly affect the state of an active component of the Co-based catalysts.

Insights into the Contribution of Oxidation-Reduction Pretreatment for Mn0.2Zr0.8O2-δ Catalyst of CO Oxidation Reaction.

A Mn0.2Zr0.8O2-δ mixed oxide catalyst was synthesized via the co-precipitation method and studied in a CO oxidation reaction after different redox pretreatments. The surface and structural properties of the catalyst were studied before and after the pretreatment using XRD, XANES, XPS, and TEM techniques. Operando XRD was used to monitor the changes in the crystal structure under pretreatment and reaction conditions. The catalytic properties were found to depend on the activation procedure: reducing the CO atmosphere at 400-600 °C and the reaction mixture (O2 excess) or oxidative O2 atmosphere at 250-400 °C. A maximum catalytic effect characterized by decreasing T50 from 193 to 171 °C was observed after a reduction at 400 °C and further oxidation in the CO/O2 reaction mixture was observed at 250 °C. Operando XRD showed a reversible reduction-oxidation of Mn cations in the volume of Mn0.2Zr0.8O2-δ solid solution. XPS and TEM detected the segregation of manganese cations on the surface of the mixed oxide. TEM showed that Mn-rich regions have a structure of MnO2. The pretreatment caused the partial decomposition of the Mn0.2Zr0.8O2-δ solid solution and the formation of surface Mn-rich areas that are active in catalytic CO oxidation. In this work it was shown that the introduction of oxidation-reduction pretreatment cycles leads to an increase in catalytic activity due to changes in the origin of active states.

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.

Magnetically Recovered Co and Co@Pt Catalysts Prepared by Galvanic Replacement on Aluminum Powder for Hydrolysis of Sodium Borohydride.

Magnetically recovered Co and Co@Pt catalysts for H2 generation during NaBH4 hydrolysis were successfully synthesized by optimizing the conditions of galvanic replacement method. Commercial aluminum particles with an average size of 80 µm were used as a template for the synthesis of hollow shells of metallic cobalt. Prepared Co0 was also subjected to galvanic replacement reaction to deposit a Pt layer. X-ray diffraction analysis, X-ray photoelectron spectroscopy, scanning electron microscopy, and elemental analysis were used to investigate catalysts at each stage of their synthesis and after catalytic tests. It was established that Co0 hollow microshells show a high hydrogen-generation rate of 1560 mL·min-1·gcat-1 at 40 °C, comparable to that of many magnetic cobalt nanocatalysts. The modification of their surface by platinum (up to 19 at% Pt) linearly increases the catalytic activity up to 5.2 times. The catalysts prepared by the galvanic replacement method are highly stable during cycling. Thus, after recycling and washing off the resulting borate layer, the Co@Pt catalyst with a minimum Pt loading (0.2 at%) exhibits an increase in activity of 34% compared to the initial value. The study shows the activation of the catalyst in the reaction medium with the formation of cobalt-boron-containing active phases.

Promoting effect of Zn in high-loading Zn/Ni-SiO2 catalysts for selective hydrogen evolution from methylcyclohexane.

The dehydrogenation of methylcyclohexane to toluene was investigated over high-loading monometallic Ni-SiO2 and bimetallic Zn/Ni-SiO2 catalysts. The catalysts were prepared by the impregnation coupled with the advantageous heterophase sol-gel technique. Their performance was tested in a fixed-bed flow reactor at 250-350 °C, 0.1 MPa pressure, equimolar ratio H2/Ar (24 nL h-1 in total), and a methylcyclohexane feed rate of 12 mL h-1. Information regarding the structure of Ni-Zn catalysts was obtained by N2 and CO adsorption, temperature-programmed reduction, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, in situ X-ray diffraction, and in situ X-ray absorption spectroscopy. The results have shown that the addition of zinc leads to the hindrance of Ni reducibility along with weakening the Ni interaction with the silica matrix. This behavior particularly indicated the formation of solid oxide nickel-zinc solutions. The catalytic properties of Zn-modified catalysts in the dehydrogenation of methylcyclohexane appeared significantly superior to their Ni-Cu counterparts. For example, the selectivity of Zn/Ni-SiO2 catalysts toward toluene formation increased markedly with a decrease in the Ni : Zn mass ratio, achieving 97% at 350 °C over the sample with Ni : Zn = 80 : 20. This is attributed to the promoting geometric and electronic effects arising from the formation of bimetallic Ni-Zn solid solutions. Moreover, a deeper reduction of zinc and a more efficient formation of solid bimetallic solutions are observed after the catalytic tests.

The Formation of Mn-Ce Oxide Catalysts for CO Oxidation by Oxalate Route: The Role of Manganese Content.

The Mn-Ce oxide catalysts active in the oxidation of CO were studied by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction (TPR), transition electron microscopy (TEM), energy dispersive X-Ray (EDX), and a differential dissolution technique. The Mn-Ce catalysts were prepared by thermal decomposition of oxalates by varying the Mn:Ce ratio. The nanocrystalline oxides with a fluorite structure and particle sizes of 4-6 nm were formed. The introduction of manganese led to a reduction of the oxide particle size, a decrease in the surface area, and the formation of a MnyCe1-yO2-δ solid solution. An increase in the manganese content resulted in the formation of manganese oxides such as Mn2O3, Mn3O4, and Mn5O8. The catalytic activity as a function of the manganese content had a volcano-like shape. The best catalytic performance was exhibited by the catalyst containing ca. 50 at.% Mn due to the high specific surface area, the formation of the solid solution, and the maximum content of the solid solution.

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.

Coupling Hydrogenation of Guaiacol with In Situ Hydrogen Production by Glycerol Aqueous Reforming over Ni/Al2O3 and Ni-X/Al2O3 (X = Cu, Mo, P) Catalysts.

Biomass-derived liquids, such as bio-oil obtained by fast pyrolysis, can be a valuable source of fuels and chemicals. However, these liquids have high oxygen and water content, needing further upgrading typically involving hydrotreating using H2 at high pressure and temperature. The harsh reaction conditions and use of expensive H2 have hindered the progress of this technology and led to the search for alternative processes. In this work, hydrogenation in aqueous phase is investigated using in-situ produced hydrogen from reforming of glycerol, a low-value by-product from biodiesel production, over Ni-based catalysts. Guaiacol was selected as a bio-oil model compound and high conversion (95%) to phenol and aromatic ring hydrogenation products was obtained over Ni/γ-Al2O3 at 250 °C and 2-h reaction time. Seventy percent selectivity to cyclohexanol and cyclohexanone was achieved at this condition. Hydrogenation capacity of P and Mo modified Ni/γ-Al2O3 was inhibited because more hydrogen undergoes methanation, while Cu showed a good performance in suppressing methane formation. These results demonstrate the feasibility of coupling aqueous phase reforming of glycerol with bio-oil hydrogenation, enabling the reaction to be carried out at lower temperatures and pressures and without the need for molecular H2.

CuFeAl Nanocomposite Catalysts for Coal Combustion in Fluidized Bed.

A method of oil-drop granulation was suggested for the preparation of spherical CuFeAl nanocomposite catalysts. The catalysts were characterized by a set of physicochemical methods (X-ray diffraction, temperature-programmed reduction by H2, low-temperature nitrogen adsorption, crushing strength) and tested in the oxidation of CO and burning of brown coal in a fluidized bed. It was found that the catalysts have high mechanical strength (16.2 MPa), and their catalytic properties in the oxidation of CO are comparable to the characteristics of industrial Cr-containing catalysts. It was shown that the addition of pseudoboehmite at the stage of drop formation contributes to the production of uniform spherical high-strength granules and facilitates the stabilization of the phase state of the active component. The use of CuFeAl nanocomposite catalysts for the burning of brown coal provides a low emission of CO (600 ppm) and NOx (220 ppm) and a high degree of coal burnout (95%), which are close to those of the industrial Cr-containing catalysts (emission of CO is 700 ppm, NOx-230 ppm, and degree of coal burnout is 95%).

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.

Reduction of double manganese-cobalt oxides: in situ XRD and TPR study.

The work reported here was aimed at determining differences in redox properties of simple and double oxides. Comparison between the reduction of double oxides (Mn,Co)3O4 and simple oxides Co3O4 and Mn3O4 was performed using in situ X-ray diffraction (XRD), temperature-programmed reduction (TPR) and transmission electron microscopy (TEM). The double oxides with a ratio of cations Mn : Co = 1 : 1 were prepared by the coprecipitation method and contained a mixture of 50% MnCo2O4 and 50% CoMn2O4. It was shown that the mechanism of reduction of double oxides with hydrogen differs significantly from the processes occurring on simple oxides. For simple cobalt and manganese oxides, transformations Co3O4→ CoO → Co and Mn3O4→ MnO are observed under a hydrogen atmosphere. The reduction of mixed-metal oxides occurs in two steps. In the first step, at 300-450 °C, (Mn,Co)3O4 transforms to (Mn,Co)O solid solutions. In situ XRD under isothermal conditions illustrates that Co-rich Co2MnO4 oxide starts to be reduced to Co0.6Mn0.4O first, and then Mn-rich Mn2CoO4 passes into Mn0.6Co0.4O. In the second step, at 450-700 °C, the reduction of solid solutions (Mn,Co)O to metallic cobalt Co and MnO proceeds. Again, the reduction begins with transformation of Co-rich oxide with the Co0.6Mn0.4O structure. The temperature of appearance of the intermediate phase (Mn,Co)O shifts to the higher values as compared to those observed for CoO, and to lower temperatures as compared to MnO during simple oxide reduction.