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The real/atomic structure of single phase homogeneous nanocrystalline Ce0.5Zr0.5O2±δ oxides prepared by a modified Pechini route and Ni-loaded catalysts of methane dry reforming on their bases was studied by a combination of neutron diffraction, synchrotron X-ray diffraction, total X-ray scattering and X-ray absorption spectroscopy. The effects of sintering temperature and pretreatment in H2 were elucidated. The structure of the mixed oxides corresponds to a tetragonal space group indicating a homogeneous distribution of Ce and Zr cations in the lattice. A pronounced disordering of the oxygen sublattice was revealed by neutron diffraction, supposedly due to incorporation of water into the structure when in contact with air promoted by the generation of anion vacancies in the lattice after reduction or calcination at high temperatures. However, such disordering has not resulted in any occupation of the oxygen interstitial positions in the bulk of the nanodomains.

Ce0.5Zr0.5O2 mixed oxides were prepared in a flow reactor in supercritical isopropanol with acetylacetone as a complexing agent. Variation of the nature of the Zr salt and the temperature of synthesis affected the phase composition, morphology and specific surface area of oxides. X-ray diffraction and Raman spectroscopy studies revealed formation of metastable t” and t’ phases. Oxides are comprised of agglomerates with sizes depending on the synthesis parameters. Loading NiO decreases the specific surface area without affecting X-ray particle sizes of supports. Such sintering was the most pronounced for a support with the highest specific surface area, which resulted in the lowest surface content of Ni as estimated by X-ray photoelectron spectroscopy and in the formation of flattened NiO particles partially embedded into the support. The catalytic activity and stability of these samples in the dry reforming of methane were determined by the surface concentration of Ni and the morphology of its particle controlled by the metal-support interaction, which also depends on the type of catalyst pretreatment. Samples based on ceria-zirconia oxides prepared under these conditions provide a higher specific catalytic activity as compared with the traditional Pechini route, which makes them promising for the practical application.

Mixed nanocrystalline Ce-Zr-O oxides (Ce/Zr = 1 or 7/3) were prepared by modified Pechini route using ethylene glycol solutions of metal salts. Detailed characterization of their real structure and surface properties by X-ray diffraction on synchrotron radiation with the full-profile Rietveld analysis, high resolution electron microscopy with elemental analysis, Raman spectroscopy, UV-Vis and X-ray photoelectron spectroscopy revealed a high homogeneity of cations distribution in nanodomains resulting in stabilization of disordered cubic phase. This provides a high dispersion of NiO loaded on these mixed oxides by wet impregnation, a high reactivity and mobility of oxygen in these catalysts and strong interaction of Ni with support in the reduced state. This helps to achieve a high activity and coking stability of developed catalysts in CH4 dry reforming in feeds with CH4 concentration up to 15% and CH4/CO2 ratio =1.

Positive environmental and technological contexts make dry methane reforming (DMR) an extensively studied reaction. During this process two main greenhouse gases CH4 and CO2 can be simultaneously converted into syngas – a mixture of CO and H2. Supported-nickel is one of the most frequently applied DMR catalysts. Their activity depends mainly on Ni concentration, kind of its precursor and a deposition method. As DMR is a demanding high-temperature reaction, it requires not only an active but first a very stable catalyst. Structural, textural and functional properties of such support remain thus of crucial efficiency. Main aim of this work was to elucidate how the synthesis of CeO2-ZrO2 support obtained by supercritical fluid method (i.e. at temperature of 400°C under a pressure of 25 MPa), can influence the properties of Ni-based DMR catalysts. The supports of various compositions (CeO2 content from 100 to 0 %), subsequently calcined at 800°C for 6h in air have been analyzed. Nickel was deposited from nitrate(V) precursor via classical wet impregnation. The final catalysts have been characterized structurally (XRD, RS), texturally (BET, SEM) and functionally (UV/Vis-DR, XPS). Catalytic tests in dry methane reforming reaction have been performed to determine activity and stability of the synthesized samples.

Ethanol steam reforming catalyst’s precursors, i.e., nanocomposites of complex oxides with the general formula [Pr0.15Sm0.15Ce0.35Zr0.35O2 + LaMn0.45Ni0.45Ru0.1O3] (1:1 by mass), were synthesized by three different methods. It was shown that two synthesis methods – ultrasonic dispersion and sequential polymeric method, lead to the formation of the nanocomposite perovskite–fluorite system with the specific surface area up to 50 m2/g. Reduction of samples at 400–500°C lead to the formation of Ni–Ru alloy nanoparticles strongly bound with the surface of oxide nanocomposite. Catalytic tests in ethanol steam reforming reaction at 500–600°C showed the highest specific activity of the sample prepared by the sequential polymeric method due to the location of Ni- and Ru-containing perovskite mainly on the surface of the composite providing a high concentration of active metal centers. At higher temperatures for all samples, ethanol conversion approached 100% with hydrogen yield varying in the range of 65–75%. A study of spent catalysts confirmed the absence of carbon deposits after long-term catalytic tests at 650°C.

Composites comprising MoVTeNbO mixed oxide and zirconia-pillared montmorillonite clays (PilCs) were prepared. XRD and TEM with EDX studies confirmed the preservation of M1 MoVTeNbO phase in these composites responsible for high activity and selectivity in ethane oxidative dehydrogenation into ethylene. For composites with PilC content of 10 wt%, the best ethylene yield exceeding that of bulk MoVTeNbO oxide was demonstrated for clays with zirconia pillars doped with Ce and Al possessing the highest specific surface area. This is explained by optimized chemical interaction of these clays with MoVTeNbO mixed oxide improving its bulk oxygen mobility and reactivity by structure disordering while blocking surface sites responsible for combustion due to the stabilization of the reactive terminal oxygen species.

The mesoporous MgAl2O4 support is promising for the design of efficient and stable to coking catalysts for natural gas and biofuel reforming into syngas. This work aims at doping this support with transition metal cations (Fe, Cr, Ti) to prevent the incorporation of Ni and rare-earth cations (Pr, Ce, Zr), loaded by impregnation, into its lattice along with providing additional sites for CO2 activation required to prevent coking. Doped MgAl1.9Me0.1O4 (Me = Fe, Ti, Cr) mesoporous supports prepared by the one-pot evaporation-induced self-assembly method with Pluronic P123 triblock copolymers were single-phase spinels. Their specific surface area varies in the range of 115–200 m2 g−1, decreasing to 90–110 m2 g−1 after successive addition of the supporting nanocomposite active component 10 wt% Pr0.3Ce0.35Zr0.35O2 + (5 wt% Ni + 1% Ru) by impregnation. Mössbauer spectroscopy for iron-doped spinels confirmed the spatially uniform distribution of Fe3+ cations in the lattice without clustering being mainly located at the octahedral positions. Fourier-transform infrared spectroscopy of the adsorbed CO molecules was performed to estimate the surface density of metal sites. In methane dry reforming, the positive effect of MgAl2O4 support doping was observed from both a higher turn-over frequency as compared with the catalyst on the undoped support as well as the highest efficient first-order rate constant for the Cr-doped catalyst as compared with published data for a variety of Ni-containing catalysts based on the alumina support. In the reaction of ethanol steam reforming, the efficiency of catalysts on the doped supports is comparable, while exceeding that of Ni-containing supported catalysts reported in the literature. Coking stability was provided by a high oxygen mobility in the surface layers estimated by the oxygen isotope heteroexchange with C18O2. A high efficiency and coking stability were demonstrated in the reactions of methane dry reforming and ethanol dry and steam reforming in concentrated feeds for the honeycomb catalyst with a nanocomposite active component on the Fe-doped MgAl2O4 support loaded on the FeCrAl-alloy foil substrate. [ABSTRACT FROM AUTHOR]

This paper is devoted to the study of active and stable nickel catalysts for methane dry reforming based on Pr-doped ceria–zirconia obtained via the solvothermal continuous method. Studies on the physicochemical and catalytic properties of the 5%Ni/Ce0.75Zr0.25−xPrxO2 series have showed that Pr introduction leads to an increase in the amount of highly reactive oxygen in the oxide lattice. Praseodymium-based catalysts showed significantly higher reactant conversions. In addition to the nature of support, the method of nickel introduction was also studied; Ni was added both using impregnation and the one-pot procedure with mixed oxide preparation. The method of Ni addition was shown to have significant effect on the morphology of its particles and Ni-support interaction, and, respectively, on catalytic activity and coking stability. The 5%Ni/Ce0.75Zr0.15Pr0.1O2 catalyst prepared by one-pot method showed stable operation in the MDR reaction for 30 h at CO2 and CH4 conversions of ~40% and an H2 yield of ~18% (T = 700 °C, τ = 10 ms). [ABSTRACT FROM AUTHOR]

A series of 5%Ni/Ce1-xTixO2 catalysts was prepared with nickel impregnation of mixed Ce–Ti oxides obtained via synthesis in supercritical isopropanol. All oxides have a cubic fluorite phase structure. Ti is incorporated into the fluorite structure. Small amounts of impurities of TiO2 or mixed Ce–Ti oxides appear with Ti introduction. Supported Ni is presented as the NiO or NiTiO3 perovskite phase. Ti introduction increases total samples reducibility and results in stronger interaction of supported Ni with the oxide support. The fraction of rapidly replaced oxygen and the average tracer diffusion coefficient also increase. The number of metallic nickel sites decreased with increasing Ti content. All catalysts except Ni-CeTi0.45 demonstrate close activity in tests of dry reforming of methane. The lower activity of Ni-CeTi0.45 can be connected to Ni decoration with species of the oxide support. The incorporation of Ti prevents detachment of Ni particles from the surface and their sintering during dry reforming of methane. [ABSTRACT FROM AUTHOR]

Mixed Ce−Zr oxides with a fluorite structure were synthesized by the solvothermal method in a supercritical medium of isopropanol. The prepared mixed oxides Ce0.5Zr0.5O2 and Ce0.75Zr0.25O2 were used as supports for 5 wt%Ni and bimetallic 2.5 wt%Ni+2.5 wt%Co catalysts. The catalysts were fully characterized (specific surface area, morphology, particle size, phase composition, surface atomic composition) and tested in ethanol dry reforming. The dependences of the conversion of C2H5OH and CO2, the yield of CO and H2, and the H2/CO ratio were estimated. The effect of the supported metals interaction and the effect of Ce/Zr ratio in the support on the catalytic activity were shown. The presence of nickel in the composition of the catalyst is necessary for high catalytic activity. It has been shown that the addition of cobalt cannot contribute to increase the catalytic activity and stability, but helps to decrease the deposition of carbon and significantly reduces the rate of carbon formation during ethanol dry reforming comparing to the monometallic nickel material. [ABSTRACT FROM AUTHOR]

As an example of principally different type of catalytic support in the paper by Suboch and Podyacheva [[11]], bamboo-like nitrogen-doped carbon nanotubes (N-CNTs) were used to synthesize supported palladium catalysts (0.2-2 wt.%) for hydrogen production via gas phase formic acid decomposition. Similarly, high activity and stability were demonstrated in the formic acid decomposition by a single-atom Ni catalyst supported on N-doped porous carbon with active Ni-N SB 4 sb sites [[2]]. To solve problems related to global warming, environmental pollution, and green energy fields, a lot of research is now devoted to the catalysis of biofuels and biogas transformation into syngas and hydrogen. [Extracted from the article]

Two series of Ni/Ce(Ti/Nb)ZrO2 catalysts were prepared using citrate route and original solvothermal continuous flow synthesis in supercritical isopropanol and studied in dry reforming of methane (DRM). TEM, XPS and FTIRS of adsorbed CO confirm influence of support composition and preparation method on the catalysts' morphology and surface features. The oxygen mobility was studied by isotope heteroexchange with C18O2. After testing in DRM, carbon deposits after catalysts' testing in DRM were investigated by temperature-programmed oxidation with thermo-gravimetric analysis. The lowest amounts of carbon deposits were obtained for unmodified Ni-CeZr and Ni-CeNbZr compositions. Ti addition lead to an increased amount of carbon, which was removed at higher temperatures. The use of supercritical supports also resulted in the formation of a higher amount of coke. Catalysts prepared by the supercritical synthesis were tested in DRM for 25 h. The highest activity drop was observed in the first three hours. For all compositions, close values of carbon deposits were revealed. [ABSTRACT FROM AUTHOR]

Lanthanide tungstates and molybdates are promising materials for hydrogen separation membranes due to their high protonic conductivity. A promising approach to fabricating ceramics based on these materials is radiation thermal sintering. The current work aims at studying the effect of radiation thermal sintering on the structural morphological and transport properties of (Nd,Ln)5.5(W,Mo)O11.25–δ as promising materials for hydrogen separation membranes. The defect fluorite structure was shown to be preserved during radiation thermal sintering at 1100 °C. The presence of protons in hydrated samples was confirmed by TGA. According to four-electrode studies and the isotope exchange of oxygen with C18O2, the samples demonstrate a high proton conductivity and oxygen mobility. Residual porosity (up to 29%) observed for these samples can be dealt with during membrane preparation by adding sintering aids and/or metal alloys nanoparticles. Hence, sintering by e-beams can be applied to the manufacturing of hydrogen separation membranes based on these materials. [ABSTRACT FROM AUTHOR]

Catalysts based on perovskite—fluorite nanocomposites with supported nickel 5%Ni/[Pr0.15Sm0.15Ce0.35Zr0.35O2 + LaMn0.9Ru0.1O3] were synthesized by three different methods. Structural and surface features of as-prepared samples were elucidated by N2 adsorption, XRD, HR TEM with EDX; reducibility and reactivity were estimated by H2-TPR, and catalytic properties were studied in ethanol steam reforming in the 500–700 °C temperature range. The best catalytic activity without coke accumulation was demonstrated for the 5%Ni/[Pr0.15Sm0.15Ce0.35Zr0.35O2+ LaMn0.9Ru0.1O3] catalyst with nanocomposite support obtained by a simple sequential polymeric preparation method. Highly dispersed particles of metallic nickel strongly fixed on the support after the reaction were shown by the HR-TEM and H2 –TPR data. The catalyst provides stable full conversion of ethanol and hydrogen yield above 60% at 600 °C for at least 6 h. [ABSTRACT FROM AUTHOR]

Orthoniobates of rare-earth elements are a promising group of materials attractive for the design of nanocomposite hydrogen separation membranes owing to a perspective type of proton conductivity, good mechanical properties, and high stability in H2O- and CO2-containing atmospheres. In general, the promising method involves the synthesis of nanocomposites with transition metals (Cu, Ni, and Cu-Ni alloys) and their oxides with high electronic conductivity. For the first time, lanthanum orthoniobates and nanocomposites with NiCu and NiCo nanoparticles were synthesized using alcohol solutions of salts of the corresponding metals by the solvothermal method in a flow reactor in a supercritical isopropanol medium. This method made it possible to obtain single-phase La0.99Ca0.01NbO4–δ oxide. The introduction of doping titanium cations did not allow obtaining a single-phase La0.99Ca0.01Nb0.98Ti0.02O4–δ sample, as impurities in lanthanum methaniobate and La2Ti2O7 were found. Calcined powders and gastight pellets of orthoniobates and nanocomposites were characterized by X-ray diffraction analysis as well as scanning and transmission electron microscopy. Transport characteristics were investigated by the Van der Pauw technique, varying measurement temperatures in a wet H2 atmosphere. The oxygen mobility was estimated by the oxygen isotope heteroexchange with C18O2. [ABSTRACT FROM AUTHOR]