ZSM-5 decrystallization and dealumination in hot liquid water.

Zeolites have recently attracted attention for upgrading renewable resources in the presence of liquid water phases; however, the stability of zeolites in the presence of liquid-phase water is not completely understood. Accordingly, the stability of the ZSM-5 framework and its acid sites was studied in the presence of water at temperatures ranging from 250 to 450 °C and at pressures sufficient to maintain a liquid or liquid-like state (25 MPa). Treated samples were analyzed for framework degradation and Al content and coordination using a variety of complementary techniques, including X-ray diffraction, electron microscopy, N2 sorption, 27Al and 29Si NMR spectroscopy, and several different types of infrared spectroscopy. These analyses indicate that the ZSM-5 framework retains >80% crystallinity at all conditions, and that 300-400 °C are the most aggressive. Decrystallization appears to initiate primarily at crystal surfaces and share many characteristics in common with alkali promoted desilication. Liquid water treatment promotes ZSM-5 dealumination, following a mechanism analogous to that observed under steaming conditions: initiation by Al-O hydrolysis, Al migration to the surface, and finally deposition as extra framework Al or possibly complete dissolution under some conditions. As with the framework, dealumination is most aggressive at 300-400 °C. Several models were evaluated to capture the non-Arrhenius effect of temperature on decrystallization and dealumination, the most successful of which included temperature dependent values of the water auto-ionization constant. These results can help interpretation of previous studies on ZSM-5 catalysis in hot liquid water and suggest future approaches to extend catalyst lifetime.

Rapid Microwave-Assisted Grafting of Layered Perovskites with n-Alcohols.

Dion-Jacobson layered niobates have been extensively researched in recent years because of a variety of useful properties such as dielectric behavior, proton conduction, and solid acid catalysis. The behavior of these materials is strongly dependent on the elemental composition and, more specifically, the interlayer surface environment. A novel method of partial grafting of n-alcohols into the interlayer of HSr2Nb3O10 with approximately 40% conversion has been developed using microwave irradiation to generate high temperatures. This method has reduced the grafting reaction time by more than 97% while maintaining conversion rates consistent with previous methods.

Structural properties of optically clear bacterial cellulose produced by Komagataeibacter hansenii using arabitol.

Bacterial cellulose (BC) exhibits beneficial properties for use in biomedical applications but is limited by its lack of tunable transparency capabilities. To overcome this deficiency, a novel method to synthesize transparent BC materials using an alternative carbon source, namely arabitol, was developed. Characterization of the BC pellicles was performed for yield, transparency, surface morphology, and molecular assembly. Transparent BC was produced using mixtures of glucose and arabitol. Zero percent arabitol pellicles exhibited 25% light transmittance, which increased with increasing arabitol concentration through to 75% light transmittance. While transparency increased, overall BC yield was maintained indicating that the altered transparency may be induced on a micro-scale rather than a macro-scale. Significant differences in fiber diameter and the presence of aromatic signatures were observed. Overall, this research outlines methods for producing BC with tunable optical transparency, while also bringing new insight to insoluble components of exopolymers produced by Komagataeibacter hansenii.

Incomplete double frequency sweeps to select small quadrupolar coupling static powder patterns.

Difference spectra based on the magnitude of the quadrupolar coupling of a site has been observed under static conditions utilizing a double frequency sweep pulse sequence to enhance the central transition of a small electric field gradient (EFG) environment. Through the use of convergent sweeps that only cover the inner satellite transitions of the smaller EFG site, an echo spectrum results that favors the smaller site, which can then be used in conjunction with normal echo spectra to create a difference spectrum that consists primarily of the smaller site. The simplification of the static lineshape data permits simulation for the extraction of chemical shift anisotropy (CSA) information for the site. The method is demonstrated using (93)Nb NMR for samples with multiple niobium environments due to mixtures of compounds, MgNb(2)O(6)/LiNbO(3), or due to crystallographic structure, KCa(2)Nb(3)O(10).

Site-selective QPASS for the isolation of large quadrupolar coupling environments.

Spectral editing of high spinning rate quadrupolar powder patterns observed using the QPASS experiment was achieved through the coupling of QPASS with the selective pi/2-RAPT enhancement sequence. The resulting pi/2-RAPT-QPASS sequence yields spectra that are dominated by the powder patterns form sites with large quadrupolar couplings thus reducing the overlap of patterns from multiple sites of different symmetry in a material. The 93Nb isotropic chemical shifts and quadrupolar coupling parameters were determined for the two niobium crystallographic sites in the layered KCa2Nb3O10. The asymmetric surface site in the structure was selectively enhanced and easily fit to second-order quadrupolar powder pattern with this method.

Substrate and field dependence of the SPINOE transfer to surface 13C from hyperpolarized 129Xe.

The substrate and field dependencies of surface SPINOE enhancements using optical pumping and magic angle spinning NMR were monitored. Relaxation rates and enhancements were examined to gain an understanding of the parameters that determine the SPINOE enhancement. (13)C-labeled deuterated methanol was adsorbed on three different substrates (SnO(2), TiO(2), Ti/SiO(2)) with heats of adsorption for xenon ranging from 14.2 to 22.6 kJ/mol. The different heats of adsorption led to a range of xenon coverages and xenon relaxation rates. Using a simple model along with experimental values for the xenon surface polarization and cross- and self-relaxation rates, the (13)C signal enhancement could be predicted and compared with experimental enhancement values. Magnetic field dependence studies were also made by monitoring the (13)C enhancements via SPINOE from hyperpolarized xenon at fields of 0.075, 4.7, and 9.4 T. The pertinent parameters necessary to achieve maximum SPINOE enhancement are discussed.

Analysis of porosity in porous silicon using hyperpolarized 129Xe two-dimensional exchange experiments.

The porosity in porous silicon was characterized using hyperpolarized (HP) xenon as a probe. HP xenon under conditions of continuous flow allows for the rapid acquisition of xenon NMR spectra that can be used to characterize a variety of materials. Two-dimensional exchange spectroscopy (EXSY) (129)Xe NMR experiments using HP xenon were performed to obtain exchange pathways and rates of xenon mobility between pores of different dimensions within the structure of porous silicon and to the gas phase above the sample. Pore sizes are estimated from chemical shift information and a model for pore geometry is presented.

Molecular dynamics of glucose in solution: a quasielastic neutron scattering study.

The molecular dynamics of glucose dissolved in heavy water have been investigated at 280 K by the technique of quasielastic neutron scattering. The scattering was described by a dynamic structure factor that accounts for decoupled diffusive jumps and free rotational motions of the glucose molecules. With increasing glucose concentration, the diffusion constant decreases by a factor five and the time between jumps increases considerably. Our observations validate theoretical predictions concerning the impact of concentration on the environment of a glucose molecule and the formation of cages made by neighboring glucose molecules at higher concentrations.

Frozen-solution conformational analysis by REDOR spectroscopy.

Frozen-solution conformational analysis (FrSCA) can be performed on organic compounds using REDOR spectroscopy. REDOR measurements on frozen aqueous solutions of 13C-methyl beta-15N-aminoglucoside indicate a bimodal distribution of conformations in a 68:32 ratio, with 13C-15N distances of 4.31 and 3.55 A, respectively. The high resolution and straightforward sample preparation make FrSCA an attractive alternative to solution-based NMR methods of conformational analysis.