RESUMEN

Oxygen and hydrogen mobility are among the important characteristics for the operation of solid oxide fuel cells, permselective membranes and many other electrochemical devices. This, along with other characteristics, enables a high-power density in solid oxide fuel cells due to reducing the electrolyte resistance and enabling the electrode processes to not be limited by the electrode-electrolyte-gas phase triple-phase boundary, as well as providing high oxygen or hydrogen permeation fluxes for membranes due to a high ambipolar conductivity. This work focuses on the oxygen and hydrogen diffusion of mixed ionic (oxide ionic or/and protonic)-electronic conducting materials for these devices, and its role in their performance. The main laws of bulk diffusion and surface exchange are highlighted. Isotope exchange techniques allow us to study these processes in detail. Ionic transport properties of conventional and state-of-the-art materials including perovskites, Ruddlesden-Popper phases, fluorites, pyrochlores, composites, etc., are reviewed.

RESUMEN

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.

RESUMEN

Synthesis and study of materials based on bismuth cerates and titanates were carried out. Complex oxides Bi1.6Y0.4Ti2O7 were synthesized by the citrate route; Bi2Ce2O7 and Bi1.6Y0.4Ce2O7-by the Pechini method. The structural characteristics of materials after conventional sintering at 500-1300 °C were studied. It is demonstrated that the formation of a pure pyrochlore phase, Bi1.6Y0.4Ti2O7, occurs after high-temperature calcination. Complex oxides Bi2Ce2O7 and Bi1.6Y0.4Ce2O7 have a pyrochlore structure formed at low temperatures. Yttrium doping of bismuth cerate lowers the formation temperature of the pyrochlore phase. As a result of calcination at high temperatures, the pyrochlore phase transforms into the CeO2-like fluorite phase enriched by bismuth oxide. The influence of radiation-thermal sintering (RTS) conditions using e-beams was studied as well. In this case, dense ceramics are formed even at sufficiently low temperatures and short processing times. The transport characteristics of the obtained materials were studied. It has been shown that bismuth cerates have high oxygen conductivity. Conclusions are drawn about the oxygen diffusion mechanism for these systems. The materials studied are promising for use as oxygen-conducting layers in composite membranes.

RESUMEN

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.

Asunto(s)

2-Propanol , Níquel , Níquel/química , Metano/química , Titanio/química , Óxidos/química , Oxígeno

RESUMEN

MeOx/CeO2 (Me = Fe, Co, Ni) samples were tested in an 18O2 temperature-programmed isotope exchange and N2O decomposition (deN2O). A decrease in the rate of deN2O in the presence of oxygen evidences the competitive adsorption of N2O and O2 on the same sites. A study of isotope oxygen exchange revealed dissociative oxygen adsorption with the subsequent formation of surface oxygen species. The same species, more probably, result from N2O adsorption and the following N2 evolution to the gas phase. We supposed the same mechanism of O2 formation from surface oxygen species in both reactions, including the stages responsible for its mobility. A detailed analysis of the kinetics of isotope exchange has been performed, and the rates of one-atom (RI) and two-atom (RII) types of exchange were evaluated. The rate of the stage characterizing the mobility of surface oxygen was calculated, supposing the same two-step mechanism was relevant for both types of exchange. The effect of oxygen mobility on the kinetics of deN2O was estimated. An analysis of the possible pathways of isotope transfer from MeOx to CeOx showed that direct oxygen exchange on the Me-Ce interface makes a valuable contribution to the rate of this reaction. The principal role of the Me-Ce interface in deN2O was confirmed with independent experiments on FeOx/CeO2 samples with a different iron content.

RESUMEN

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.

RESUMEN

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.

RESUMEN

Nd tungstates and molybdates are promising materials for hydrogen separation membranes due to their high protonic conductivity. This work aims at elucidating the structural, textural and oxygen transport features of Nd5.5WO11.25-δ, Nd5.5W0.5Mo0.5O11.25-δ and (Nd5/6La1/6)5.5WO11.25-δ and their composites with Ni0.5Cu0.5O synthesized by mechanical activation. The oxide materials obtained were distorted double fluorites but their composites with Ni0.5Cu0.5O possess a complex phase composition. Extended defects such as grain boundaries, stacking faults and surface steps/terraces were observed in TEM images, which allow fast diffusion transport along grain boundaries (D* ∼ 10-6 cm2 s-1 at 700 °C) and slower diffusion within grains' bulk (D* ∼ 10-11, 10-12 and 10-13 cm2 s-1 at 700 °C for the rather fast, "middle" and slow channels of bulk diffusion) (2D diffusion). The model gives the best description of experimental data obtained by the isotope exchange of oxygen with C18O2 in a flow reactor. For composites with Ni0.5Cu0.5O, a significant decrease in oxygen diffusivity was shown. The reduction and subsequent reoxidation of composites resulted in an increase in oxygen mobility probably due to the partial unblocking of oxygen diffusion corresponding to the Ln tungstates/molybdates. Fine oxygen transport features allow us to increase the hydrogen yield of hydrogen separation membranes due to the proton transport mechanisms involving oxide anions and the water splitting reaction. Hence, the features of Nd tungstates and their composites with nickel(II)-copper(II) oxide studied demonstrated their high potential for use in catalytic reactors based on hydrogen separation membranes.

RESUMEN

Electrical conduction and oxygen diffusion mobility in the bixbyite ( Ia3̅) and rhombohedral ( R3̅) polymorphs of the Ln6MoO12-Δ (Ln = Er, Tm, Yb; Δ = δ, δ1, δ2; δ1 > δ2) heavy lanthanide molybdates, belonging to new, previously unexplored classes of potential mixed (ionic-electronic) conductors, have been studied in the range of 200-900 °C. The oxygen self-diffusion coefficient in bixbyite ( Ia3̅) Yb6MoO12-δ phase estimated by the temperature-programmed heteroexchange with C18O2 was shown to be much higher than that for rhombohedral ( R3̅) RI (with large oxygen deficiency) and ( R3̅) RII (with small oxygen deficiency) Ln6MoO12-Δ (Ln = Tm, Yb; Δ = δ1; δ1 > δ2) oxides. According to the activation energy for total conduction in ambient air, 0.99, 0.93, and 1.01 eV in Er6MoO12-δ, Tm6MoO12-δ, and Yb6MoO12-δ bixbyites, respectively, oxygen ion conductivity prevails in the range ∼200-500 °C. Oxygen mobility data for the rhombohedral Ln6MoO12-Δ (Ln = Er, Tm, Yb; Δ = δ1, δ2) phases RI and RII indicate that the oxygen in these phases exhibits mobility at much higher temperatures, such as those above 600-700 °C. Accordingly, below 600-700 °C they have predominantly electronic conductivity. As shown by total conductivity study of Ln6MoO12-δ (Ln = Er, Tm, Yb) bixbyites ( Ia3̅) and rhombohedral phases Ln6MoO12-Δ (Ln = Er, Tm, Yb; Δ = δ1, δ2) ( R3̅) in dry and wet air, the proton conductivity contribution exists only in Ln6MoO12-δ (Ln = Er, Tm, Yb) bixbyites up to 450-600 °C and decreases with a decreasing of the lanthanide ionic radius. The obtained data on the mobility of oxygen and the presence of proton contribution in bixbyites in the 300-600 °C temperature range make it possible to confirm unequivocally that Ln6MoO12-δ (Ln = Er, Tm, Yb) bixbyites are mixed electron-proton conductors at these temperatures.

RESUMEN

The kinetics of 18O/16O isotopic exchange over CeO2-ZrO2-La2O3 and Pt/CeO2-ZrO2 catalysts have been investigated under the conditions of dynamic adsorption-desorption equilibrium at atmospheric pressure and a temperature range of 650-850 degrees C. The rates of oxygen adsorption-desorption on Pt sites, support surface, oxygen transfer (spillover) from Pt to the support as well as the amount of oxygen accumulated in the oxide bulk, and oxygen diffusion coefficient were estimated. The nanocrystalline structure of lanthana-doped ceria-zirconia prepared via the Pechini route with a developed network of domain boundaries and specific defects guarantees a high oxygen mobility in the oxide bulk (D = (1.5 / 2.0).10-18 m2 s-1 at 650 degrees C) and allows accumulation of over-stoichiometric/excess oxygen. For Pt/CeO2-ZrO2, oxygen transfer from Pt to support (characteristic time < 10-2 s) was shown to be responsible for the fast exchange between the gas-phase oxygen and oxygen adsorbed on the mixed oxide surface. The rate of direct exchange between the gas phase and surface oxygen is increased as well due to the increased concentration (up to 2 monolayers) of surface/near subsurface oxygen species accumulated on the oxygen vacancies (originated from the incorporation of highly dispersed Pt atoms). The characteristic time of diffusion of the oxygen localized in the subsurface layers is about 1 s. The overall quantity of over-stoichiometric oxygen and/or hydroxyl groups accumulated in the bulk can reach the equivalent of 10 monolayers, and characteristic time of oxygen diffusion within the bulk is about 20 s. All these kinetic data are required for the further step of modeling partial oxidation of hydrocarbons under steady- and unsteady-state conditions.