Thick films of YSZ electrolytes by dip-coating process

Yttria stabilized zirconia (YSZ, 8% Y2O3) thick films were coated on porous Ni-YSZ substrates using the dip-coating process and a suspension with a new formulation. The suspension was obtained by addition of a polymeric matrix in a stable suspension of a commercial YSZ (Tosoh) powders dispersed in an azeotropic MEK-EtOH mixture. The green layers were densified after an optimization of the suspension composition. YSZ Tosoh particles encapsulated by a zirconium alkoxide sol and added with colloidal alkoxide precursor are used to load the suspension. The in situ growth of these colloids increases significantly the layers density after an appropriated heat treatment. The obtained films are continuous, homogeneous and 20 μm thick. Different microstructures are obtained depending on the synthesis parameters of the suspension

CO oxidation over nonstoichiometric nickel manganite spinels

Nonstoichiometric nickel–manganese spinel oxides, NixMn3−x ▭3δ/4O4+δ (1≥x≥0), have been synthesized by calcination in air of mixed oxalates at 623 K. These materials are shown to be highly reactive for CO oxidation, some conversion being observed at room temperature for the most active solid (x=1.0). The interaction of CO and O2 with these oxides has been studied by in situ IR spectroscopy under steady-state and transient reaction conditions. A detailed mechanism is proposed wherein CO reacts with coordinatively unsaturated cations to give carbonyl complexes which in turn react with surface oxygen activated on anionic vacancies. Adsorbed and gaseous CO2 also undergo much slower side reactions with lattice oxygen or surface hydroxide groups to give more stable hydrogen carbonate and carbonates species, which lead to catalyst deactivation. Marked effects of pretreatment are explained on the basis of the observed kinetics and the proposed mechanis

“Chimie douce”: A land of opportunities for the designed construction of functional inorganic and hybrid organic-inorganic nanomaterials

Abstract“Chimie douce” based strategies allow, through the deep knowledge of materials chemistry and processing, the birth of the molecular engineering of nanomaterials. This feature article will highlight some of the main research accomplishments we have performed during the last years. We describe successively the design and properties of: sol–gel derived hybrids, Nano Building Blocks (NBBs) based hybrid materials, nanostructured porous materials proceeds as thin films and ultra-thin films, aerosol processed mesoporous powders and finally hierarchically structured materials. The importance of the control of the hybrid interfaces via the use of modern tools as DOSY NMR, SAXS, WAXS, Ellipsometry that are very useful to evaluate in situ the hybrid interfaces and the self-assembly processes is emphasized. Some examples of the optical, photocatalytic, electrochemical and mechanical properties of the resulting inorganic or hybrid nanomaterials are also presented

Composition and porosity graded La2−xNiO4+δ (x≥0) interlayers for SOFC: Control of the microstructure via a sol–gel process

We have developed composition and porosity graded La2−xNiO4+δ (x≥0) cathode interlayers for low-temperature solid oxide fuel cell that exhibit good adhesion with the electrolyte, controlled porosity and grain size and good electrochemical behaviour. La2−xNiO4+δ (x≥0) monolayers are elaborated from a derived sol–gel method using nitrate salts, acetylacetone and hexamethylenetetramine in acetic acid. As a function of the organic concentration and the molar ratio of lanthanum to nickel, these layers present platelets or spherical shape grains with a size distribution ranging from 50 to 200 nm, as verified by SEM-FEG. On the basis of this processing protocol, we prepared porosity and composition graded lanthanum nickelates interlayers with effective control of the pore distribution, the nanocrystalline phase, the thickness and the subsequent electrochemical properties

Synthesis by sol-gel route of oxyapatite powders for dense ceramics. Applications as electrolytes for solid oxide fuel cells

Abstract Solid oxide fuel cells have considerable interest in recent years, because of their high efficiency and environmentally friendly nature. Such systems required oxygen-conducting electrolytes and now the most common electrolyte is yttria stabilized zirconia (YSZ). This compound exhibits high oxide ion conductivity at elevated temperatures (850-1000°C). However, this high working temperature causes problems in terms of materials selection and lifetime. One solution is to develop new oxide ions conductors exhibiting high oxide ion conductivity at intermediary temperatures (700-800°C). Recent work has identified Ln 10-x Si 6 O 26±z (Ln = rare earths) as a good fast oxide ion conductor. Undoped and doped Ln 10-x B 6 O 26±z (B = Si or Ge) oxides are currently prepared by solid-state methods. In that work, we propose a sol-gel process to synthesize powders of La 9.33 Si 6 O 26 type-silicated apatites. The main advantage is to decrease the crystallization temperature in comparison to the conventional methods, allowing the synthesis of reactive powders with nanometric particles size. These oxides are synthesized using silicon alkoxide and lanthanum nitride as precursors. In the litterature, no study refers to the synthesis of mixed oxides with silicon alcoxides. However, there are several studies on sol-gel synthesis of glasses with this precursor. In this study, several processing parameters have been investigated (the hydrolysis ratio, the concentration of metallic precursors in the sol and the role of organic compounds) in order to synthesize pure phases after the decomposition of the sols. Pure powders of La 9.33 Si 6 O 26 type-silicated apatites are obtained at 800°C. These powders were used to prepare ceramics. Several processing parameters as morphology of powders (agglomeration, particle sizes) and, heating profiles have been studied on the densification. Dense ceramics (90-95%) have been prepared at temperatures around 1400°C. The used of sol-gel powders allow the decrease of the sintering temperature of about 200°C

Correction Mesoporous thin film WO3 photoanode for photoelectrochemical water splitting a sol gel dip coating approach

Correction for Mesoporous thin film WO3 photoanode for photoelectrochemical water splitting a sol gel dip coating approach by Samantha Hilliard et al., Sustainable Energy Fuels, 2017, 1, 145 15

Hierarchically Porous Gd3+-Doped CeO2 Nanostructures for the Remarkable Enhancement of Optical and Magnetic Properties

Rare earth ion-doped CeO2 has attracted more and more attention because of its special electrical, optical, magnetic, or catalytic properties. In this paper, a facile electrochemical deposition route was reported for the direct growth of the porous Gd-doped CeO2. The formation process of Gd-doped CeO2 composites was investigated. The obtained deposits were characterized by SEM, EDS, XRD, and XPS. The porous Gd3+- doped CeO2 (10 at% Gd) displays a typical type I adsorption isotherm and yields a large specific surface area of 135 m2/g. As Gd3+ ions were doped into CeO2 lattice, the absorption spectrum of Gd3+-doped CeO2 nanocrystals exhibited a red shift compared with porous CeO2 nanocrystals and bulk CeO2, and the luminescence of Gd3+-doped CeO2 deposits was remarkably enhanced due to the presence of more oxygen vacancies. In addition, the strong magnetic properties of Gd-doped CeO2 (10 at% Gd) were observed, which may be caused by Gd3+ ions or more oxygen defects in deposits. In addition, the catalytic activity of porous Gd-doped CeO2 toward CO oxidation was studied

Synthesis of La2NiO4+d oxides by sol–gel process: Structural and microstructural evolution from amorphous to nanocrystallized powders

In this paper, the structural and microstructural transition from amorphous to La2NiO4+d nanocrystallized oxides synthesized by a polymeric route based on Pechini’s work has been studied by several experimental techniques including infrared spectroscopy and wide angle X-ray scattering. The synthesis parameters which govern this transition have been identified in order to synthesize La2NiO4+d oxides with various mean crystallite sizes and non stoichiometry levels. Therefore, it has been demonstrated that the control of the nature and the content of organic compounds in the polymeric sols allows the preparation of La2NiO4+d metastable phases with a mean crystallite size ranging from 100 to 220 nm and a non stoichiometry level ranging from 0.15 to 0.22 at 25 8C. As the cathodic performance strongly depends on the physical characteristics of the oxides, this study shows that our versatile process may be suitable to elaborate electrodes with different electrochemical behaviours

Energetics of nanoparticle oxides: interplay between surface energy and polymorphism†

Many oxides tend to form different structures (polymorphs) for small particles. High temperature oxide melt solution calorimetry has been used to measure the enthalpy as a function of polymorphism and surface area for oxides of Al, Ti, and Zr. The results confirm crossovers in polymorph stability at the nanoscale. The energies of internal and external surfaces of zeolitic silicas with open framework structures are an order of magnitude smaller than those of oxides of normal density