Template-free nanosized faujasite-type zeolites.

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.

High energy ion irradiation-induced ordered macropores in zeolite crystals.

The present study demonstrated the possibility to form a secondary system of parallel macropores in zeolite crystals. The secondary pore formation was predetermined by the creation of defect zones in ZSM-5 crystals. A high energy (238)U ion beam was employed to form latent tracks in zeolite crystals, which were further subjected to attack with diluted HF solution and thus developed to uniformally sized macropores. The selective extraction of material from latent tracks was due to the higher etching velocity of highly agitated zones created by heavy ion bombardment. The combination of complementary methods unambiguously demonstrated the formation of hierarchical zeolite material comprising parallel macropores that extended through the entire crystal. The catalytic tests revealed improved activity at retained selectivity in the reaction of m-xylene conversion. The possibility to control the number of macropores per unit of crystal surface and thus the catalytic performance of the material was demonstrated. This model material is expected to bring better understanding to the effect of a secondary pore system in the catalytic performance of hierarchical zeolites obtained by the top-down or bottom-up approach.

Quantification of water and silanol species on various silicas by coupling IR spectroscopy and in-situ thermogravimetry.

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.

Coupling sol-gel synthesis and microwave-assisted techniques: a new route from amorphous to crystalline high-surface-area aluminium fluoride.

A non-aqueous sol-gel Al-based fluoride has been subjected to the microwave solvothermal process. The final material depends on the temperature heat treatment used. Three types of material have been prepared: 1) for low temperature heat treatment (90 degrees C) X-ray amorphous alkoxy fluoride was obtained; 2) for the highest temperature used (200 degrees C) the metastable form beta-AlF3 was obtained with a very large surface area of 125 m2 g(-1). The mechanism of the amorphous=crystalline transformation has been rationalised by the occurrence of a decomposition reaction of the gel fluoride induced by the microwave irradiation. 3) Finally, at intermediate temperature (180 degrees C) a multi-component material mixture exhibiting a huge surface area of 525 m2 g(-1) has been obtained and further investigated after mild post-treatment fluorination using F2 gas. The resulting aluminium-based fluoride still possesses a high-surface-area of 330 m2 g(-1). HRTEM revealed that the solid is built from large particles (50 nm) identified as alpha-AlF3, and small ones (10 nm), relative to an unidentified phase. This new high-surface-area material exhibits strong Lewis acidity as revealed by pyridine adsorption and catalytic tests. By comparison with other materials, it has been shown that whatever the composition/structure of the Al-based fluoride materials, the number of strong Lewis acid sites is related to the surface area, highlighting the role of surface reconstruction occurring on a nanoscopic scale on the formation of the strongest Lewis acid sites.

Investigation of acid sites in a zeotypic giant pores chromium(III) carboxylate.

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.