Surface and porosity of nanocrystalline boehmite xerogels

Boehmite xerogels are prepared by hydrolysis of Al(OC4H9)3 followed by peptization with HNO3 (H+/Al = 0, 0.07, 0.2). XRD and TEM show that these gels are made of nanosized crystals (5–9 nm in width and 3 nm thick). According to the amount of acid, no significant differences are found in size and shape, but only in the spatial arrangement of the crystallites. Nitrogen adsorption–desorption isotherms of nonpeptized gels are of type IV, whereas isotherms of peptized gels are of type I. These isotherms are analyzed by the t-plot method. The majority of pore volume results from intercrystalline mesopores, but the peptized gels also contain intercrystalline micropores. The particle packing is very dense for the gel peptized with H+/Al = 0.2 (porosity = 0.26), but it is less dense in non-peptized gel (porosity = 0.44). Heating these gels under vacuum creates, from 250 °C onwards, an intracrystalline microporosity resulting from the conversion of boehmite into transition alumina. But heating also causes intercrystalline micropores collapsing. The specific surface area increases up to a limit temperature (300 °C for nonpeptized gels and 400 °C for peptized) beyond which sintering of the particles begins and the surface decreases. The PSD are calculated assuming a cylindrical pore geometry and using the corrected Kelvin equation proposed by Kruk et al. Peptized xerogels give a monomodal distribution with a maximum near 2 nm and no pores are larger than 6 nm. Nonpeptized gels have a bimodal distribution with a narrow peak near to 2 nm and a broad unsymmetrical peak with a maximum at 4 nm. Heating in air above 400 °C has a strong effect on the porosity. As the temperature increases, there is a broadening of the distribution and a marked decrease of small pores (below 3 nm). However, even after treatment at 800 °C, micropores are still present

Catalytic coatings on steel for low-temperature propane prereforming to solid oxide fuel cell (SOFC) application

Catalyst layers (4–20 lm) of rhodium (1 wt%) supported on alumina, titania, and ceria–zirconia (Ce0.5Zr0.5O2) were coated on stainless-steel corrugated sheets by dip-coating in very stable colloidal dispersions of nanoparticles in water. Catalytic performances were studied for low-temperature (6500 C) steam reforming of propane at a steam to carbon ratio equal to 3 and low contact time (0.01 s). The best catalytic activity for propane steam reforming was observed for titania and ceria–zirconia supports for which propane conversion started at 250 C and was more than three times better at 350 C than conversion measured on alumina catalyst. For all catalysts a first-order kinetics was found with respect to propane at 500 C. Addition of PEG 2000 in titania and ceria–zirconia sols eliminated the film cracking observed without additive with these supports. Besides, the PEG addition strongly expanded the porosity of the layers, so that full catalytic efficiency was maintained when the thickness of the ceria–zirconia and titania films was increased

Effect of PEG on rheology and stability of nanocrystalline titania hydrosols

Very stable titania hydrosols were prepared by fast hydrolysis of titanium isopropoxide in a large excess of water. XRD patterns show that these sols contain nanocrystals (5–6 nm) of anatase (70%) and brookite (30%). TEM images indicate that these primary particles form aggregates whose mean hydrodynamic diameter, determined by photon correlation spectroscopy, is in the range of 80–90 nm. The flow curves of these colloids, recorded for several volume fractions of nanoparticles, can be perfectly fitted, in the range 0–100 s1, with a power-law model. In this range the behavior is Newtonian but for larger shear rates a shear thinning is observed. The viscosity dependence on particle concentration can be predicted by a Batchelor-type model were the volume fraction of particles is replaced by an effective volume fraction of aggregates, taking into account their fractal dimension. Addition of polyethylene glycol (PEG 2000) induced a marked decrease (more than 50%) of the sol viscosity down to a minimum. This is explained by assuming that PEG adsorbs on the surface of TiO2 particles producing stabilization by steric effects and leading to formation of more compact aggregates. Without PEG the sol viscosity strongly decreases on aging. This effect is not caused by the growth of primary particles. It is rather interpreted as a progressive reorganization of the aggregates toward a more compact packing

Stable hydrosols for TiO2 coatings

The optimum processing parameters required to synthesize, by hydrolysis of titanium isopropoxide (TIP), highly stable hydrosols composed of nanoparticles of the smallest possible size, are deduced both from data available in literature and from our own experiments. The colloids prepared in these conditions are composed of aggregates of anatase (*90%) and brookite crystallites (5–6 nm). They are suitable for coatings and have longterm stability (more than one year) in terms of polymorphic composition, crystallite and agglomerate size. Stable sols composed solely of anatase crystallites (4 nm) can be prepared by partially complexing the TIP by acetylacetone before hydrolysis. It is not possible to produce porous films with these colloids because they are stabilized by electrostatic repulsion which causes the particles to organize themselves, during the drying step, to form materials with a close packed structure. However, coatings with controlled porosity can be prepared from these stable sols through the post addition of polymers, like PEG or block copolymers

Nanostructured cobalt manganese ferrite thin films for gas sensor application

Ferrite compounds are very important because of their optical, electrical or magnetic properties. Moreover, many papers relate to their development as possible gas sensor. In this study, we were interested in using cobalt-manganese-ferrite as sensitive layer for CO2 sensor devices. Such an application required a high surface activity, and consequently a small crystallite size and a large surface area. The physical vapor deposition (RF-sputtering) is widely used for thin film synthesis. In this work, porous thin films were obtained from a Co1Mn0.65Fe1 3504 target sputtered under pure argon plasma, by optimizing the deposition parameters (gas pressure, power). The deposition time was adjusted in order to obtain an average thickness of 300 nm. Structural (G-XRD) and microstructural (SEM-FEG, gas adsorption, electron microprobe) analyses were carried out on these thin films. The chemical composition was found to be homogeneous on the whole surface of the samples. The grain size ranged from 10 to 25 nm. The surface enhancement factor (SEF) was about 100 m2/m2, which is equivalent to a specific surface area of 76 m2/g for the ferrite layer. In conclusion, these nanostructured cobalt-manganese-ferrite films appear to be quite suitable for an application as gas sensors

Synthesis of NiO nanowalls by thermal treatment of Ni film deposited onto a stainless steel substrate

Two-dimensional nanostructures have a variety of applications due to their large surface areas. In this study, the authors present a simple and convenient method to realize two-dimensional NiO nanowalls by thermal treatment of a Ni thin film deposited by sputtering onto a stainless steel substrate. The substrate surface area is supposed to be significantly increased by creating nanowalls. The effects on the nanowall morphology of the thermal treatment temperature and duration are investigated. A mechanism based on the surface diffusion of Ni2+ ions from the Ni base film is then proposed for the growth of the NiO nanowalls. The as-synthesized NiO nanowalls are characterized by scanning electron microscopy, energy-dispersive x-ray analysis, x-ray diffraction, transmission electron microscopy and high resolution transmission electron microscopy

Catalytic coatings on stainless steel prepared by sol–gel route

Stainless steel (flat and microstructured) substrates have been coated with sol–gel catalysts made up of metal nanoparticles (Rh, Ni, Pt) dispersed on alumina and alumina–ceria supports. The aluminum monohydroxyde (boehmite) sols were synthesized by hot hydrolysis/peptization of an aluminum alkoxide (Yoldas method). It is shown that the rheological properties of the sol, especially the thixotropy, play a key role on the homogeneity and the quality of the film deposited on the metal substrate. The catalyst layers have a very good adhesion, a thickness which can be easily controlled (in the range 0.1 to 10 μm), a large specific surface area and a good mechanical and thermal stability

Co–Mn-oxide spinel catalysts for CO and propane oxidation at mild temperature

CoxMn3−xO4 oxides (0≤x≤3) were prepared by controlled decomposition of mixed oxalates near 200 ◦C, followed by a calcination at 300 ◦C. These oxides are amorphous for x < 0.9. For higher cobalt fraction they have a cubic spinel structure and their crystallite size grows with the cobalt fraction. These materials have a large surface area; the highest values, exceeding 250 m2/g, were obtained for x≈2. The spinel oxides exhibit an outstanding catalytic activity for propane oxidation at mild temperature (20–200 ◦C). They are also active for CO oxidation at ambient temperature. This high activity was correlated both with the surface area and the cobalt concentration. The most efficient material is Co2,3Mn0,7O4, which has a better activity than cobalt oxide catalysts reported in the literature

Synthesis of highly porous alumina-based materials

γ-Alumina-based materials with high porous volume, tunable pore size, were synthesized by the addition of both PEO/PPO/PEO triblock copolymers (Pluronics® F127 and P123) and metal nitrates (Al3+, Mn2+, Cu2+) in a boehmite (AlOOH) nanoparticle hydrosol. During the subsequent thermal treatment, the surfactant was removed leaving a highly porous framework. The pore size distribution was strongly dependent on the metal nitrate added and its concentration. By this simple process it was possible to modify the porous volume in the range 0.3–2.6 cm3 g−1 and the median pore diameter in the range 5–40 nm. All these materials presented high surface areas in the range 300–500 m2 g−1. During the drying AlOOH particles aggregate to form linear objects (flat rods, laths) in order to minimize electrostatic repulsion. We think that the improvement of the textural characteristics of γ-alumina could be explained by the adsorption of copolymer on to these fiber-like objects, preventing the compact rearrangement of the boehmite nanoparticles in a compact “card-pack” microstructure during the drying. The addition of electrolytes induces a reduction of electrostatic repulsions, leading to the formation of both fiber-like objects at lower AlOOH concentration, and a 3D network by bridging these 1D objects. This bridging is reversible since the gel returns to a sol state under shearing, but polymer adsorption can prevent the full collapsing of this network during the drying step and a huge porosity can be maintained after calcination

Realization of aligned three-dimensional single-crystal chromium nanostructures by thermal evaporation

Aligned three-dimensional single-crystal chromium nanostructures are fabricated onto a silicon substrate by thermal evaporation in a conventional thermal evaporator, where the incident angle of Cr vapor flux with respect to the substrate surface normal is fixed at 88°. The effects of the deposition time and incident angle on the morphology of the resulting nanostructures are investigated. The achieved Cr nanostructures are characterized by scanning electron microscopy, energy dispersive X-ray analysis, X-ray diffraction, transmission electron microscopy, high-resolution transmission electron microscopy, and surface area measurement. This study provides a convenient way to fabricate three-dimensional single-crystal Cr nanostructures, which is suitable for batch fabrication and mass production. Finally, the same technique is employed to fabricate the nanostructures of other metals such as Ag, Au, Pd, and Ni