Approaches to the design of efficient and stable catalysts for biofuel reforming into syngas: doping the mesoporous MgAl2O4 support with transition metal cations.

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.

Structural and transport properties of Nd tungstates and their composites with Ni0.5Cu0.5O obtained by mechanical activation.

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.

Comparative Study of Electrical Conduction and Oxygen Diffusion in the Rhombohedral and Bixbyite Ln6MoO12 (Ln = Er, Tm, Yb) Polymorphs.

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.