We performed a sequence of tests on a partially water-saturated sand sample contained in an x-raytransparent aluminum pressure vessel that is conducive to x-ray computed tomography (CT) observation. These tests were performed to gather data for estimation of thermal properties of the sand/water/gas system and the sand/hydrate/water/gas systems, as well as data to evaluate the kinetic nature of hydrate dissociation. The tests included mild thermal perturbations for the estimation of the thermal properties of the sand/water/gas system, hydrate formation, thermal perturbations with hydrate in the stability zone, hydrate dissociation through thermal stimulation, additional hydrate formation, and hydrate dissociation through depressurization with thermal stimulation. Density changes throughout the sample were observed as a result of hydrate formation and dissociation, and these processes induced capillary pressure changes that altered local water saturation.

Molecular hydrogen evolution catalysts (HECs) are synthetically tunable and often exhibit high activity, but they are also hampered by stability concerns and practical limitations associated with their use in the homogeneous phase. Their incorporation as integral linker units in metal–organic frameworks (MOFs) can remedy these shortcomings. Moreover, the extended three-dimensional structure of MOFs gives rise to high catalyst loadings per geometric surface area. Herein, we report a new MOF that exclusively consists of cobaloximes, a widely studied HEC, that act as metallo-linkers between hexanuclear zirconium clusters. When grown on conducting substrates and under applied reductive potential, the cobaloxime linkers promote electron transport through the film as well as function as molecular HECs. The obtained turnover numbers are orders of magnitude higher than those of any other comparable cobaloxime system, and the molecular integrity of the cobaloxime catalysts is maintained for at least 18 h of electrocatalysis. Being one of the very few hydrogen evolving electrocatalytic MOFs based on a redox-active metallo-linker, this work explores uncharted terrain for greater catalyst diversity and charge transport pathways.

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The first halonium‐ion‐based helices were designed and synthesized using oligo‐aryl/pyridylene‐ethynylene backbones that fold around reactive iodonium ions. Halogen bonding interactions stabilize the iodonium ions within the helices. Remarkably, the distance between two iodonium ions within a helix is shorter than the sum of their van der Waals radii. The helical conformations were characterized by X‐ray crystallography in the solid state, by NMR spectroscopy in solution and corroborated by DFT calculations. The helical complexes possess potential synthetic utility, as demonstrated by their ability to induce iodocyclization of 4‐penten‐1‐ol.

The factors determining the symmetry and the fundamental nature of the three-center, four-electron bonds are assessed.

The methane hydrate dissociation mechanism was studied on the molecular scale using 13C magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. Analysis of time-resolved 13C MAS NMR spectra for methane Structure I (sI) hydrate dissociation obtained by raising the temperature above the hydrate equilibrium conditions permitted the cage occupancy and pressure to be determined during this process. The relationship between NMR methane gas chemical shift, pressure, and temperature was developed, which allows estimating the system pressure in the sealed glass tube sample at any temperature. The large to small cage occupancy ratio remained constant during hydrate dissociation suggesting that there is no preferential dissociation of hydrate cavities and the whole unit cell decomposes during dissociation. This decomposition rate is virtually the same for both the large and the small cages in methane hydrate on a per cage basis. The similar decomposition rate of both cage types shows that the sI methane hydrate dissociation mechanism differs from the formation process where preferential formation of specific hydrate cages has been observed.

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Methane hydrate was formed in two moist sands and a sand-silt mixture under a confining stress in an x-ray transparent pressure vessel. Three initial water saturations were used to form three different methane hydrate saturations in each medium. X-ray computed tomography (CT) was used to observe locationspecific density changes caused by hydrate formation and flowing water. Gas permeability measurements in each test for the dry, moist, frozen, and hydrate-bearing states are presented. As expected, the effective permeabilities (intrinsic permeability of the medium multiplied by the relative permeability) of the moist sands decreased with increasing moisture content. In a series of tests on a single sample, the effective permeability typically decreased as the pore space became more filled, in the order of dry, moist, frozen, and hydrate-bearing. In each test, water was flowed through the hydrate-bearing medium, and we observed the location specific changes in water saturation using CT scanning. We compared our data to a number of models, and our relative permeability data compare most favorably with models in which hydrate occupies the pore bodies rather than the pore throats. Inverse modeling (using the data collected from the tests) will be performed to extend the relative permeability measurements.