Recently, by performing molecular dynamics simulations in the methane-water system, we have measured the static lifetimes of cagelike water clusters (CLWC) immersed in bulk liquid water, during which the member-water molecules of CLWCs are not allowed to exchange with their surrounding water molecules [J. Phys. Chem. C, 2007, 111, 2595]. In this study, we measure the dynamic lifetimes of CLWCs with permitting such water exchanges. It is found that the dynamic lifetimes of CLWCs are not less than the static lifetimes previously obtained, and their ratio increases with the lifetime values. The results strengthen that CLWCs are metastable structures in liquid water and the occurrence probability of long-lived CLWCs will increase if one uses the dynamic lifetimes instead of the static lifetimes. The implications of this study for hydrate nucleation are discussed.

Methane hydrate nucleation and growth in porous model carbon materials illuminates the way towards the design of an optimized solid-based methane storage technology. High-pressure methane adsorption studies on pre-humidified carbons with well-defined and uniform porosity show that methane hydrate formation in confined nanospace can take place at relatively low pressures, even below 3 MPa CH4, depending on the pore size and the adsorption temperature. The methane hydrate nucleation and growth is highly promoted at temperatures below the water freezing point, due to the lower activation energy in ice vs. liquid water. The methane storage capacity via hydrate formation increases with an increase in the pore size up to an optimum value for the 25 nm pore size model-carbon, with a 173% improvement in the adsorption capacity as compared to the dry sample. Synchrotron X-ray powder diffraction measurements (SXRPD) confirm the formation of methane hydrates with a sI structure, in close agreement with natural hydrates. Furthermore, SXRPD data anticipate a certain contraction of the unit cell parameter for methane hydrates grown in small pores.

Methane hydrate nucleation and growth in porous model carbon materials illuminates the way towards the design of an optimized solid-based methane storage technology. High-pressure methane adsorption studies on pre-humidified carbons with well-defined and uniform porosity show that methane hydrate formation in confined nanospace can take place at relatively low pressures, even below 3 MPa CH4, depending on the pore size and the adsorption temperature. The methane hydrate nucleation and growth is highly promoted at temperatures below the water freezing point, due to the lower activation energy in ice vs. liquid water. The methane storage capacity via hydrate formation increases with an increase in the pore size up to an optimum value for the 25 nm pore size model-carbon, with a 173% improvement in the adsorption capacity as compared to the dry sample. Synchrotron X-ray powder diffraction measurements (SXRPD) confirm the formation of methane hydrates with a sI structure, in close agreement with natural hydrates. Furthermore, SXRPD data anticipate a certain contraction of the unit cell parameter for methane hydrates grown in small pores.

Gas hydrate formation was studied in Gulf of Mexico (GOM) sediments. Sediments studied were from six-meter long cores from Mississippi Canyon Block 118 and a 27-meter core from a cruise in 2002 of the Marion Dufresne. These sediments retained their in situ seawater before testing. Hydrate formation rate and induction times were measured. The hydrate memory effect was studied in GOM sediments with and without in situ seawater. Hydrate induction time was short when in situ seawater was present. Bioproducts adsorbed on particles in the sediments are postulated to shorten the induction times by maintaining seawater structuring around coated particles. Hydrate nucleation was studied by Dynamic Light Scattering and Scanning Electron Microscopy. Particles around 50 to 100 nm nucleated hydrate formation. These small nucleating particles appeared to be clays or surfactant molecules and interactions thereof. Hydrate capillaries were studied and found to be at least 100 nm in diameter because the sediment nucleating particles with bioproducts diffused through the hydrate capillaries. Large complexes of nontronite smectite clay and Emulsan, an anionic biosurfactant, were found to facilitate hydrate formation. It was determined that Emulsan entered the interlayer of nontronite. The clay contents of the GOM sediments were determined. All sediments contained smectite, illite, chlorite, and kaolinite in different proportions. The study gave new insight into the gas hydrate formation mechanism in seafloor sediments.