A study of the zeotypic giant pores chromium(III) tricarboxylate Cr(III)3OF(x)(OH)(1-x)(H2O)2 x {C6H3-(CO2)3}2 x nH2O (MIL-100) has been performed. First, its thermal behavior, studied by X-ray thermodiffractometry and infrared spectroscopy, indicates that the departure of water occurs without any pore contraction and no loss in crystallinity, which confirms the robustness of the framework. In a second step, IR spectroscopy has shown the presence of three distinct types of hydroxy groups depending on the outgassing conditions; first, at high temperatures (573 K), only Cr-OH groups with a medium Brønsted acidity are present; at lower temperatures, two types of Cr-H2O terminal groups are observed; and at room temperature, their relatively high Brønsted acidity allows them to combine with H-bonded water molecules. Finally, a CO sorption study has revealed that at least three Lewis acid sites are present in MIL-100 and that fluorine atoms are located on a terminal position on the trimers of octahedra. A first result of grafting of methanol molecules acting as basic organic molecules on the chromium sites has also been shown, opening the way for a postsynthesis functionalization of MIL-100.

Nanosized faujasite (FAU) crystals have great potential as catalysts or adsorbents to more efficiently process present and forthcoming synthetic and renewable feedstocks in oil refining, petrochemistry and fine chemistry. Here, we report the rational design of template-free nanosized FAU zeolites with exceptional properties, including extremely small crystallites (10-15 nm) with a narrow particle size distribution, high crystalline yields (above 80%), micropore volumes (0.30 cm(3) g(-1)) comparable to their conventional counterparts (micrometre-sized crystals), Si/Al ratios adjustable between 1.1 and 2.1 (zeolites X or Y) and excellent thermal stability leading to superior catalytic performance in the dealkylation of a bulky molecule, 1,3,5-triisopropylbenzene, probing sites mostly located on the external surface of the nanosized crystals. Another important feature is their excellent colloidal stability, which facilitates a uniform dispersion on supports for applications in catalysis, sorption and thin-to-thick coatings.

Five silica samples (four precipitated silicas provided by commercial suppliers and one with the MCM-41 structure) have been studied by infrared spectroscopy and by a homemade thermogravimetry-infrared spectrum (TG-IR) setup. The silanol amount, accessibility to water, and different alcohols, and the affinity to water of these various silicas were compared and quantified. TG-IR measurements allowed the precise determination of the integrated molar absorption coefficient of the (nu+delta)OH band, epsilon(nu+delta)OH=(0.16+/-0.01) cm micromol(-1). It is independent of the sample origin and the concentration of silanol groups on silicas. For the precipitated dried samples evacuated at room temperature, the silanol concentration COH varies between 3.6 and 7.0 mmol g(-1). It is 5.3 mmol g(-1) in the case of the MCM-41 sample. Exchange experiments with D2O, followed by back-exchanges with different alcohols (methanol, propan-2-ol, 2-methyl-propan-2-ol, and 3-ethyl-pentan-3-ol) have been followed by infrared spectroscopy. All of the silanols of the MCM-41 sample are accessible to water and alcohol molecules. By contrast, about 20% of the silanols in precipitated samples are not exchanged by D2O (internal silanols). Accessibility decreases with alcohol size; the main effect is relative to methanol. Taking into account the sample specific surface areas and the silanol accessibility to D2O, the surface silanol density of precipitated silicas is close to 8 OH per nm2, at maximum coverage. At variance, the silanol surface density of the MCM silica is much lower, 4 OH per nm2. The TG-IR setup has also been used to determine the amount of water adsorbed on silicas through the intensity of the deltaH2O band. It varies linearly with the concentration of adsorbed water, whatever the silica sample. The integrated molar absorption coefficient of two bands, epsilondeltaH2O=(1.53+/-0.03) cm micromol(-1) and epsilon(nu+delta)H2O=(0.22+/-0.01) cm micromol(-1), have been determined. The number of H2O molecules adsorbed per nm2 has been compared on the five samples under an equilibrium pressure of 13 hPa at room temperature. Taking into account the number of silanols accessible to D2O for each sample, the silica-water affinity has been defined by the H2O/(SiOHsurf) ratio. It is close to 0.8-0.9 for the precipitated samples but lower (0.7) in the case of the MCM one. This result is explained by the more important amount of isolated silanol groups presented by this sample.

The interaction of phenol, anisole, and guaiacol, representatives of oxygenate functions present in pyrolysis bio-oils, with oxides such as silica, alumina (pure or doped with K or F), and silica-alumina is investigated by infrared spectroscopy. While phenolic type compounds mainly interact via H-bonding with silica, chemisorption is their main mode of adsorption on alumina. Besides, guaiacol interacts very strongly by forming doubly anchored phenates instead of monoanchored ones with phenol and anisole. At temperatures typical of hydrodeoxygenation (HDO) operating conditions (∼673 K), the phenate type species cover 2/3 of the alumina surface. This study clearly indicates that substantial carbon deposition could take place on aluminasupported HDO catalysts. Hence, this suggests that silica-based supports should be considered as potential candidates to design HDO catalyst with better stability.

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To increase the power density of battery materials, without significantly affecting their main advantage of a high energy density, novel material architectures need to be developed. Using the example of LiFePO 4 , we demonstrate a simple, sol-gel-based route that leads to large (up to 20 µm) primary LiFePO 4 particles, each of which contains hierarchically organized pores in the meso and macro range. As the pores are formed due to vigorous gas evolution (mainly CO and CO 2 ) during degradation of a citrate precursor, they are perfectly interconnected within each particle. Elementary carbon, the other citrate-degradation product, is deposited on the walls of emerging pores. The superposition of a continuous 1-2 nm thick carbon film (electron conductor) on pores (ion conductor when filled with electrolyte) represents a unique architecture in which the electrons and ions are simultaneously supplied to the site of insertion in the particle interior. The material can operate at current rates up to 50 C while preserving a high tap density of ca. 1.9 g cm -3 .

Chemical etching with fluoride ions is a new approach for secondary porosity engineering of aluminosilicate zeolite frameworks. We show that diluted HF solutions extract preferentially aluminum from zeolite frameworks. The Brønsted acidity of ZSM-5 treated in such a way decreases, while its structure is unaffected after an HF treatment. With higher HF concentrations, the number of undissociated HF molecules and the concentration of HF2 – ions, extracting indiscriminately Al and Si, increase. The addition of NH4F shifts the chemical equilibria to produce more HF2 –, avoiding the use of highly concentrated HF solutions; it also suppresses HF dissociation. The etching selectivity of such solutions is concentration-independent and extracts indiscriminately both framework Si and Al. Zeolite dissolution in NH4F-HF solutions starts preferentially at small intergrowth domains and goes deeply in the crystals without a substantial increase of the external surface area. Macropores are produced without altering zeolite acidity. Hierarchical materials obtained by these two approaches are characterized extensively by complementary methods and the catalytic impact illustrated in the m-xylene conversion.

Fe͑III͒ citrate was used as a source for synthesis of microsized porous LiFePO 4 /C particles. All samples, prepared either by solid-state or by sol-gel techniques, are phase-pure triphylite phases, which, however, have different morphology highly influenced by the type of synthesis and synthesis parameters. Their common feature is porosity due to thermal decomposition of citrate anion. The impact of particle porosity on the electrochemical behavior is discussed in terms of qualitative results obtained from scanning electron microscopy ͑SEM͒ micrographs and in terms of quantitative results obtained from N 2 adsorption isotherms. The best electrochemical behavior ͑above 140 mAh/g at C/2 rate during continuous cycling͒ was obtained with composites prepared at a relatively high heating rate ͑above 5 K/min͒. This suggests that interlaced pores were formed inside particles. A strong correlation between the electrochemical results and the heating rate was observed, which could easily be explained based on SEM micrographs and on some trends found in porosity measurements. The latter reveal the main difference between samples prepared by solid-state and by sol-gel techniques.