Mesoporous Carbon Production by Nanocasting Technique Using Boehmite as a Template

A series of mesoporous carbonaceous materials were synthesized by the nanocasting technique using boehmite as a template and glucose as a carbon precursor. After pyrolysis and template removal, the resulting material is a mesoporous carbon that can be additionally doped with N, B and K during prepyrolysis impregnation. In addition, the influence of doping on the morphology, crystallinity and stability of the synthesized carbons was studied using X-ray diffraction, nitrogen physisorption, thermogravimetry, Raman and IR spectroscopy and transmission electron microscopy. While the nanocasting process is effective for the formation of mesopores, KOH and urea do not modify the textural properties of carbon. The use of H3PO4 as a dopant, however, led to the formation of an AlPO4 compound and resulted in a solid with a lower specific surface area and higher microporosity. All doped solids present higher thermal stability as a positive effect of the introduction of heteroatoms to the carbon skeleton. The phosphorus-doped sample has better oxidation resistance, with a combustion temperature 120–150 °C higher than those observed for the other materials.

Rippite, K2(Nb,Ti)2(Si4O12)O(O,F), a New K-Nb-Cyclosilicate from Chuktukon Carbonatite Massif, Chadobets Upland, Krasnoyarsk Territory, Russia

Rippite K2(Nb,Ti)2(Si4O12)(O,F)2, a new K-Nb-cyclosilicate, has been discovered in calciocarbonatites from the Chuktukon massif (Chadobets upland, SW Siberian Platform, Krasnoyarsk Territory, Russia). It was found in a primary mineral assemblage, which also includes calcite, fluorcalciopyrochlore, tainiolite, fluorapatite, fluorite, Nb-rich rutile, olekminskite, K-feldspar, Fe-Mn–dolomite and quartz. Goethite, francolite (Sr-rich carbonate–fluorapatite) and psilomelane (romanèchite ± hollandite) aggregates as well as barite, monazite-(Ce), parisite-(Ce), synchysite-(Ce) and Sr-Ba-Pb-rich keno-/hydropyrochlore are related to a stage of metasomatic (hydrothermal) alteration of carbonatites. The calcite–dolomite coexistence assumes crystallization temperature near 837 °C for the primary carbonatite paragenesis. Rippite is tetragonal: P4bm, a = 8.73885(16), c = 8.1277(2) Å, V = 620.69(2) Å3, Z = 2. It is closely identical in the structure and cell parameters to synthetic K2Nb2(Si4O12)O2 (or KNbSi2O7). Similar to synthetic phase, the mineral has nonlinear properties. Some optical and physical properties for rippite are: colorless; Mohs’ hardness—4–5; cleavage—(001) very perfect, (100) perfect to distinct; density (meas.)—3.17(2) g/cm3; density (calc.)—3.198 g/cm3; optically uniaxial (+); ω = 1.737-1.739; ε = 1.747 (589 nm). The empirical formula of the holotype rippite (mean of 120 analyses) is K2(Nb1.90Ti0.09Zr0.01)[Si4O12](O1.78OH0.12F0.10). Majority of rippite prismatic crystals are weakly zoned and show Ti-poor composition K2(Nb1.93Ti0.05Zr0.02)[Si4O12](O1.93F0.07). Raman and IR spectroscopy, and SIMS data indicate very low H2O content (0.09–0.23 wt %). Some grains may contain an outermost zone, which is enriched in Ti (+Zr) and F, up to K2(Nb1.67Ti0.32Zr0.01)[Si4O12](O1.67F0.33). It strongly suggests the incorporation of (Ti,Zr) and F in the structure of rippite via the isomorphism Nb5+ + O2− → (Ti,Zr)4+ + F1−. The content of a hypothetical end-member K2Ti2[Si4O12]F2 may be up to 17 mol. %. Rippite represents a new structural type among [Si4O12]-cyclosilicates because of specific type of connection of the octahedral chains and [Si4O12]8− rings. In structural and chemical aspects it seems to be in close with the labuntsovite-supergroup minerals, namely with vuoriyarvite-(K), K2(Nb,Ti)2(Si4O12)(O,OH)2∙4H2O.

NMR Study of Intercalates and Grafted Organic Derivatives of H2La2Ti3O10

The protonated perovskite-like titanate H2La2Ti3O10 has been used to produce organic-inorganic hybrids with simple organic molecules: methylamine, methanol, monoethanolamine, and n-butylamine. The optimal pathways for the preparation of such hybrids are summarized. Solid-state NMR, combined with thermal analysis, Raman, and IR spectroscopy, has been applied to determine the bonding type in the obtained organic-inorganic hybrids. It has been found that, in the methanolic hybrid, the organic residues are covalently bound to the inorganic matrix. In contrast, in the methylamine and n-butylamine hybrids, the organic molecules are intercalated into the inorganic matrix in cationic forms. The structure of the monoethanolamine hybrid is composite and includes both the covalently bound and intercalated organic species.