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

Platinum/ceria/alumina catalysts on microstructures for carbon monoxide conversion

Platinum/ceria/alumina catalysts have been prepared by a sol–gel method and coated in the microchannels of stainless steel platelets. These catalysts are very active for the water-gas shift reaction between 300 and 400°C. Moreover, they are non-pyrophoric and thus well suited for the purification of hydrogen for PEM fuel cells. The obtained coatings show good adherence and catalytic activity. The influence of the amount of platinum and ceria as well as the effect of a binder on the catalytic performance has been investigated. The samples have been characterized before reaction by XRD, SEM and by N2 adsorption measurements. The kinetics, free from internal diffusion limitations, over these thin films have been described by a power law rate equation. An activation energy of 86 kJ/mol has been found and at 260 °C the TOF corresponds to 0.6 ± 0.1 s−1 for all investigated samples. The superior activity of the platelets compared to the powder samples is attributed to the diffusion limitations inside the powder pellets. Thus catalysts deposited on microstructured platelets lead to a better platinum utilization

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

Structure and thermal behavior of nanocrystalline boehmite

First, the structural features of nanocrystalline boehmite synthesized by hydrolysis of aluminum sec-butoxide according to the Yoldas method are reported. The nanosized boehmite consists of rectangular platelets averaging 8 by 9 nm and 2–3 nm in thickness which contain a large excess of water. Dehydration by heating under vacuum induced an increase in the specific surface area, down to a minimum water content ( 0.2 H2O per Al2O3); values up to 470 m2/g can be reached. However this enlargement of specific surface area only results from water loss, the surface area remaining constant. The particle morphology, the excess of water, as well as the specific surface area, depend on the amount of acid used for the peptization during the synthesis. Second, a comprehensive investigation of the dehydration kinetics is presented. The simulations of the non-isothermal experiments at constant heating rates show that thermally stimulated transformation of nanocrystalline boehmite into alumina can be accurately modeled by a 4-reaction mechanism involving: (I) the loss of physisorbed water, (II) the loss of chemisorbed water, (III) the conversion of boehmite into transition alumina, (IV) the dehydration of transition alumina (loss of residual hydroxyl groups). The activation energy of each step is found to be very similar for experiments done in various conditions (heating rate, atmosphere, kind of sample,…)

Sliced-Wasserstein on Symmetric Positive Definite Matrices for M/EEG Signals

When dealing with electro or magnetoencephalography records, many supervised prediction tasks are solved by working with covariance matrices to summarize the signals. Learning with these matrices requires using Riemanian geometry to account for their structure. In this paper, we propose a new method to deal with distributions of covariance matrices and demonstrate its computational efficiency on M/EEG multivariate time series. More specifically, we define a Sliced-Wasserstein distance between measures of symmetric positive definite matrices that comes with strong theoretical guarantees. Then, we take advantage of its properties and kernel methods to apply this distance to brain-age prediction from MEG data and compare it to state-of-the-art algorithms based on Riemannian geometry. Finally, we show that it is an efficient surrogate to the Wasserstein distance in domain adaptation for Brain Computer Interface applications

Mechanochemical synthesis and ion transport properties of Na₃OX (X = Cl, Br, I and BH₄) antiperovskite solid electrolytes

The push towards the development of next-generation solid-state batteries has motivated the search for novel solid electrolyte materials. Sodium antiperovskites represent a structural family of ion conductors that has emerged as a result, with expected advantages in terms of composition tuning, electrochemical stability, mechanical softness and high ionic conductivity. Here, we report the mechanochemical synthesis of several materials in this structural family, including novel mixed-halide compositions such as Na3OCl0.5(BH4)0.5, Na3OBr0.5(BH4)0.5 Na3OI0.5(BH4)0.5 and Na3OCl0.33Br0.33(BH4)0.33. We rationalize the effect of halide substitution on the structure and ion transport properties of these materials through diffraction, impedance spectroscopy and molecular dynamics. We conclude with a discussion on Na3OBH4, which has recently been reported to be a fast ion conductor, owing to the rotational disorder of the complex superhalide anion BH4−. We are unable to reproduce the reported high ionic conductivity of Na3OBH4 neither by experiment nor ab initio simulation.</p

From the territories to the genes: Developing sustainable multi-purpose sorghum value chains

To face global warming and fossil fuel depletion crisis, plant biomass will provide a renewable source of energy, materials and chemicals. Accordingly, agriculture will have to adapt not only to avoid competition between food-feed and non-food non-feed uses but also to ensure the economical and environmental sustainability of these productions. In this context, we are developing an integrative strategy merging genetics, breeding, material sciences, energy production, animal nutrition and socio economic analyses to accelerate the development of multipurpose sorghum value chains for both Mediterranean and tropical semi-arid conditions (West Africa). As a first step, new products (biocomposites) and uses (biomethane production) are being developed. Then the plant traits impacting the production and quality of the different end-products and uses are being identified taking advantage of the genetic diversity of sorghum. As a third step, the set-up of these key traits in the plant is being analyzed in order to describe their patterns of development / accumulation, their susceptibility to environmental constraints and provide some insights regarding their molecular determinism. Taking advantage of these functional information, the genomic regions impacting the key traits are being deciphered and used to develop new breeding tools and breeding strategies. In parallel, to maximize the probability to convert scientific results in local impacts, the different stakeholders of the value chains are being mobilized and territorial analyses aiming to assess the relevance of the different value chains are performed

Surface and porosity of nanocrystalline boehmite xerogels

International audienceBoehmite 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

Structure and thermal behavior of nanocrystalline boehmite

International audienceFirst, the structural features of nanocrystalline boehmite synthesized by hydrolysis of aluminum sec-butoxide according to the Yoldas method are reported. The nanosized boehmite consists of rectangular platelets averaging 8 by 9 nm and 2–3 nm in thickness which contain a large excess of water. Dehydration by heating under vacuum induced an increase in the specific surface area, down to a minimum water content ( 0.2 H2O per Al2O3); values up to 470 m2/g can be reached. However this enlargement of specific surface area only results from water loss, the surface area remaining constant. The particle morphology, the excess of water, as well as the specific surface area, depend on the amount of acid used for the peptization during the synthesis. Second, a comprehensive investigation of the dehydration kinetics is presented. The simulations of the non-isothermal experiments at constant heating rates show that thermally stimulated transformation of nanocrystalline boehmite into alumina can be accurately modeled by a 4-reaction mechanism involving: (I) the loss of physisorbed water, (II) the loss of chemisorbed water, (III) the conversion of boehmite into transition alumina, (IV) the dehydration of transition alumina (loss of residual hydroxyl groups). The activation energy of each step is found to be very similar for experiments done in various conditions (heating rate, atmosphere, kind of sample,...)

Thermal and Photo‐Degradation Study of α ‐FAPbI 3 ‐Based Perovskite Using In Situ X‐Ray Diffraction

International audienceHybrid halide perovskite has established its credibility as high performance thin film photovoltaic technology. Perovskite based on formamidinium cation is at the core composition to top performances and stability. Herein, a depth study based on temperature‐controlled in situ X‐ray diffraction focusing on the photo‐active formamidinium lead iodide ( α ‐FAPbI 3 ) is reported. In particular, the thermal stability of the latter and the degradation pathways under different experimental conditions are clarified. Based on this in situ technique, the lattice thermal expansion coefficient is reported that provides relevant information on possible mechanical stress created upon temperature cycling or damp heat test. The results support that α ‐FAPbI 3 degradation is substantially accelerated when temperature is combined to illumination and when it is interfaced with the extraction layers. In addition, by contrast to in darkness for which α ‐FAPbI 3 degrades directly into PbI 2 , the existence of a temperature gap under illumination involving an intermediate step with a non‐crystalline phase resulting from the perovskite degradation and contributing to the formation of PbI 2 by‐product is revealed