Framework and extra-framework aluminium in wet ion exchanged Fe-ZSM5 and the effect of steam during the decomposition of N2O

The role of extra-framework and framework aluminium in wet-ion exchanged Fe-ZSM5 has been studied using ²⁹Si NMR and ²⁷Al triple quantum magic angle spinning (3QMAS) NMR. A series of samples were studied, the parent material, the wet ion exchanged Fe-ZSM5 and Fe-ZSM5 that has been used in the decomposition of N₂O with varying reaction conditions. Various framework and extra-framework aluminium species have been identified. It was found that cationic Fe species prefer to replace the Brønsted acid protons in their charge balancing role at those aluminium sites associated with the largest quadrupolar product. The framework aluminium atoms that pertain to the smaller quadrupolar product, which are either charge balanced by extra-framework aluminium or a proton, are much less prone to exchange. In the catalytic decomposition of N₂O it seemed that water present in small amounts enhances the catalytic activity. However, water also decreases the long term stability and performance by dealuminating the zeolite framework. With a high amount of water present, Fe-ZSM5 was destabilised and catalytically inferior.     

Li17Sb13S28: A New Lithium Ion Conductor and addition to the Phase Diagram Li2S–Sb2S3

Li₁₇Sb₁₃S₂₈ was synthesized by solid‐state reaction of stoichiometric amounts of anhydrous Li₂S and Sb₂S₃. The crystal structure of Li₁₇Sb₁₃S₂₈ was determined from dark‐red single crystals at room temperature. The title compound crystallizes in the monoclinic space group C2/m (no. 12) with a=12.765(2) Å, b=11.6195(8) Å, c=9.2564(9) Å, β=119.665(6)°, V=1193.0(2) ų, and Z=4 (data at 20 °C, lattice constants from powder diffraction). The crystal structure contains one cation site with a mixed occupation by Li and Sb, and one with an antimony split position. Antimony and sulfur form slightly distorted tetragonal bipyramidal [SbS₅E] units (E=free electron pair). Six of these units are arranged around a vacancy in the anion substructure. The lone electron pairs E of the antimony(III) cations are arranged around these vacancies. Thus, a variant of the rock salt structure type with ordered vacancies in the anionic substructure results. Impedance spectroscopic measurements of Li₁₇Sb₁₃S₂₈ show a specific conductivity of 2.9×10^?9 Ω^?1 cm^?1 at 323 K and of 7.9×10^?6 Ω^?1 cm^?1 at 563 K, the corresponding activation energy is E_A=0.4 eV below 403 K and E_A=0.6 eV above. Raman spectra are dominated by the Sb?S stretching modes of the [SbS₅] units at 315 and 341 cm^?1 at room temperature. Differential thermal analysis (DTA) measurements of Li₁₇Sb₁₃S₂₈ indicate peritectic melting at 854 K.     

Mutable Lewis and Brønsted acidity of aluminated SBA-15 as revealed by NMR of adsorbed pyridine-15N

(1)H and variable-temperature (15)N NMR techniques have been used to study the effect of the gradual alumination of SBA-15 on the structure and adsorption properties of this mesoporous material. The interpretation of experimental spectra suggests that aluminum chlorhydrol most effectively reacts with silica surfaces in the confinement of the cavities of rough mesopore walls, instead of forming a homogeneous aluminum film. This first leads to a gradual filling of the cavities and finally results in aluminum islands on the inner surfaces of mesopores. In the sample with a Si/Al atomic ratio of 4.1, up to half of the inner surface area of the mesopores is covered with aluminum. The alumination produces Br?nsted acid sites attributed to silanol groups interacting with aluminum but does not affect the proton-donating ability of isolated silanol groups. At high Si/Al ratios, the surface contains only one type of Lewis site attributed to tetracoordinated aluminum. At lower Si/Al ratios, Lewis acid sites with a lower electron-accepting ability appear, as attributed to pentacoordinated aluminum. The numerical values of the surface densities of all chemically active sites have been estimated after annealing at 420 and 700 K. We were surprised to observe that gaseous nitrogen can occupy Lewis acid sites and hinder the interaction of the aluminum with any other electron donor. As a result, aluminated surfaces saturated with nitrogen do not exhibit any Br?nsted or Lewis acidity. At room temperature, it takes days before pyridine replaces nitrogen at the Lewis acid sites.     

Equilibrium lithium-ion transport between nanocrystalline lithium-inserted anatase TiO2 and the electrolyte

The power density of lithium-ion batteries requires the fast transfer of ions between the electrode and electrolyte. The achievable power density is directly related to the spontaneous equilibrium exchange of charged lithium ions across the electrolyte/electrode interface. Direct and unique characterization of this charge-transfer process is very difficult if not impossible, and consequently little is known about the solid/liquid ion transfer in lithium-ion-battery materials. Herein we report the direct observation by solid-state NMR spectroscopy of continuous lithium-ion exchange between the promising nanosized anatase TiO(2) electrode material and the electrolyte. Our results reveal that the energy barrier to charge transfer across the electrode/electrolyte interface is equal to or greater than the barrier to lithium-ion diffusion through the solid anatase matrix. The composition of the electrolyte and in turn the solid/electrolyte interface (SEI) has a significant effect on the electrolyte/electrode lithium-ion exchange; this suggests potential improvements in the power of batteries by optimizing the electrolyte composition.