Hydrogen hydrates with tetrahydrofuran (THF) as a promoter molecule are investigated to probe critical unresolved observations regarding cage occupancy and storage capacity. We adopted a new preparation method, mixing solid powdered THF with ice and pressurizing with hydrogen at 70 MPa and 255 +/- 2 K (these formation conditions are insufficient to form pure hydrogen hydrates). All results from Raman microprobe spectroscopy, powder X-ray diffraction, and gas volumetric analysis show a strong dependence of hydrogen storage capacity on THF composition. Contrary to numerous recent reports that claim it is impossible to store H(2) in large cages with promoters, this work shows that, below a THF mole fraction of 0.01, H(2) molecules can occupy the large cages of the THF+H(2) structure II hydrate. As a result, by manipulating the promoter THF content, the hydrogen storage capacity was increased to approximately 3.4 wt % in the THF+H(2) hydrate system. This study shows the tuning effect may be used and developed for future science and practical applications.

Storage of greenhouse gases in the form of gas hydrates is attractive and is being pursued rigorously in recent times. However, slow formation rate and inefficient water to hydrate conversion are the main hindering factors. In this report, we examine the role of two amino acids (0.5 wt%), l-methionine (l-met) and l-phenylalanine (l-phe) on the formation of gas hydrates using methane (CH4), carbon dioxide (CO2) and their mixtures as guest molecules. Experiments are conducted under non-stirred and isochoric configurations. The hydrate conversion efficiency of both amino acids is identical for hydrates formed with CH4 and mixture of (CO2+CH4). However, the hydrate conversion is significantly less in CO2 hydrates in l-phe system. Addition of amino acids to the water dramatically improved the kinetics of hydrate formation and 90% of maximum gas uptake in hydrate phase occurred in less than an hour. The water to hydrate conversion is also very efficient (>85%) in the presence of amino acids. Therefore, the amino acids containing systems are suitable for storing both CH4 and CO2 gases. The gas hydrates were characterised using powder x-ray diffraction (XRD) and Raman spectroscopic measurements. These measurements indicate the formation of sI hydrates and encasing of gas molecules as guests.

The gypsum-bassanite-anhydrite phase transition sequence was followed up to 550 K at ambient pressure in a naturally occurring gypsum using Raman spectroscopy. The spectral variations of the internal (CaSO 4 AE 2H 2 O) modes of sulphate tetrahedra and were used to probe the structural phase transitions. A new Raman mode (m 1 m 2 ) emerged at 1026 cm-1, in the mode region, at around 388 » 5 K, indicating the onset of the bassanite m 1 phase. This mode became weaker after showing an initial increase. The anhydrite (CaSO 4 AE 0.5H 2 O) (CaSO 4 ) phase, with an onset temperature of around 448 » 5 K, was also characterized by the appearance of the Raman mode at 1016 cm-1. From the Arrhenius-type changes in the reduced intensity, the activation energies associated with the gypsum to bassanite and bassanite to anhydrite transitions were estimated to be 92.25 and 32.94 kJ mol-1, respectively. The observed spectral anomalies in the mode clearly corroborate the transition sequence. m 2

The first proof-of-concept of the formation of a double tert-butylamine (t-BuNH(2)) + hydrogen (H(2)) clathrate hydrate has been demonstrated. Binary clathrate hydrates with different molar concentrations of the large guest t-BuNH(2) (0.98-9.31 mol %) were synthesized at 13.8 MPa and 250 K, and characterized by powder X-ray diffraction and Raman microscopy. A structural transformation from sVI to sII of t-BuNH(2) hydrate was clearly observed under hydrogen pressures. Raman spectroscopic data suggested that the hydrogen molecules occupied the small cages and had similar occupancy to hydrogen in the double tetrahydrofuran (THF) + H(2) clathrate hydrate. The hydrogen storage capacity in this system was approximately 0.7 H(2) wt % at the molar concentration of t-BuNH(2) close to the sII stoichiometry.

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