Guest-induced symmetry lowering of an ionic clathrate material for carbon capture.

We report a new lattice structure of the ionic clathrate hydrate of tetra-n-butylammonium bromide induced by guest CO2 molecules, which is found to provide high CO2 storage capacity. The structure was characterized by a set of methods, including single crystal X-ray diffraction, NMR, and MD simulations.

Synthesis and characterization of a new structure of gas hydrate.

Atoms and molecules <0.9 nm in diameter can be incorporated in the cages formed by hydrogen-bonded water molecules making up the crystalline solid clathrate hydrates. For these materials crystallographic structures generally fall into 3 categories, which are 2 cubic forms and a hexagonal form. A unique clathrate hydrate structure, previously known only hypothetically, has been synthesized at high pressure and recovered at 77 K and ambient pressure in these experiments. These samples contain Xe as a guest atom and the details of this previously unobserved structure are described here, most notably the host-guest ratio is similar to the cubic Xe clathrate starting material. After pressure quench recovery to 1 atmosphere the structure shows considerable metastability with increasing temperature (T <160 K) before reverting back to the cubic form. This evidence of structural complexity in compositionally similar clathrate compounds indicates that the reaction path may be an important determinant of the structure, and impacts upon the structures that might be encountered in nature.

What we have learned from the study of solid p-tert-butylcalix[4]arene compounds.

The study of solid p-tert-butylcalix[4]arene and its compounds with a variety of techniques has provided a good understanding of the versatility of this host molecule, how to induce a number of distinct host-guest motifs, its molecular recognition properties, the complex phase relationships and unique properties such as gas adsorption without having obvious channels.

Probing the geometry and interconnectivity of pores in organic aerogels using hyperpolarized 129XE NMR spectroscopy.

Hyperpolarized (HP) 129Xe NMR was used for the first time to probe the geometry and interconnectivity of pores in RF aerogels and to correlate them with the [resorcinol]/[catalyst] (R/C) ratio. We have demonstrated that HP 129Xe NMR is an ideal method for accurately measuring the volume-to-surface-area (Vg/S) ratios for soft mesoporous materials without using any geometric models. The Vg/S parameter, which is related both to the geometry and the interconnectivity of the porous space, has been found to correlate strongly with the R/C ratio and exhibits an unusually large span: an increase in the R/C ratio from 50 to 500 results in about 5-fold rise in Vg/S. Unlike conventional techniques, HP 129Xe NMR spectroscopy probes the geometry and interconnectivity of the nano- or mesopores in soft materials, providing new insights into the pore structure.

Chemical shift imaging with continuously flowing hyperpolarized xenon for the characterization of materials.

In this contribution we report new approaches to the MRI of materials using continuously produced laser-polarized (129)Xe gas. This leads to vastly improved sensitivity and makes new kinds of information available. The hyperpolarized xenon is produced in a continuous flow system that conveniently delivers the xenon at low partial pressure to probes for NMR and MRI experiments. We illustrate applications to the study of micropore and other kinds of void space and show for the first time that with flowing hyperpolarized xenon it is possible to obtain chemical-shift-resolved images in a relatively short time.

Titanium carbide, nitride and carbonitrides: a 13C, 14N, 15N and 47,49Ti solid-state nuclear magnetic resonance study.

The first 47,49Ti, 13C, 14N and 15N solid-state nuclear magnetic resonance (NMR) spectra of titanium carbide, nitride and a series of cubic carbonitrides have been obtained under both static and magic-angle spinning (MAS) conditions. The 15N samples were isotopically enriched by gas-solid exchange at 1000 degrees C in a closed system. The Ti spectra of the carbide and nitride are sharp, reflecting the well defined cubic symmetry of these compounds, but become considerably broadened in the carbonitride series, with the spectra being approximately the sum of TiC and TiN together with some small electric field gradient (EFG) effects. The resonance positions and widths of all the NMR spectra change as carbon is progressively replaced by nitrogen. A relationship is observed between the 13C chemical shift and the nitrogen content of the carbonitrides, suggesting a possible NMR method for estimating the composition of these compounds. Although electron paramagnetic resonance (EPR) spectra of all these compounds show typically metallic behaviour, the NMR spectra show few effects attributable to conduction electrons, probably due to the lack of s-orbital contributions to the conduction band.