1. A Review of the Effect of Porous Media on Gas Hydrate Formation
Lanyun Wang, Mengyue Dou, Yan Wang, Yongliang Xu, Yao Li, Yu Chen, Lingshuang Li ACS Omega. 2022 Sep 19;7(38):33666-33679. doi: 10.1021/acsomega.2c03048. eCollection 2022 Sep 27.
Most gas hydrates on the earth are in sediments and permafrost areas, and porous media are often used industrially as additives to improve gas hydrate formation. For further understanding its exploration and exploitation under natural conditions and its application in industry, it is necessary to study the effect of porous media on hydrate formation. The results show that the stacked porous media affects the phase equilibrium of hydrate formation depending on the competition water activity and large specific surface areas, while integrated porous media, such as metal foam, can transfer the hydration heat rapidly and moderate the hydrate phase equilibrium. A supersaturated metal-organic framework is able to significantly improve gas storage performance and can be used as a new material to promote hydrate formation. However, the critical particle size should be studied further for approaching the best promotion effect. In addition, together with the kinetic accelerators, porous media has a synergistic effect on gas hydrate formation. The carboxyl and hydroxyl groups on the surface of porous media can stabilize hydrate crystals through hydrogen bonding. However, the hydroxyl radicals on the silica surface inhibit the combination of CH4 and free water, making the phase equilibrium conditions more demanding.
2. Hydration of Hofmeister ions
Chang Q Sun, Yongli Huang, Xi Zhang Adv Colloid Interface Sci. 2019 Jun;268:1-24. doi: 10.1016/j.cis.2019.03.003. Epub 2019 Mar 20.
Water dissolves salt into ions and then hydrates the ions to form an aqueous solution. Hydration of ions deforms the hydrogen bonding network and triggers the solution with what the pure water never shows such as conductivity, molecular diffusivity, thermal stability, surface stress, solubility, and viscosity, having enormous impact to many branches in biochemistry, chemistry, physics, and energy and environmental industry sectors. However, regulations for the solute-solute-solvent interactions are still open for exploration. From the perspective of the screened ionic polarization and O:H-O bond relaxation, this treatise features the recent progress and a perspective in understanding the hydration dynamics of Hofmeister ions in the typical YI, NaX, ZX2, and NaT salt solutions (Y = Li, Na, K, Rb, Cs; X = F, Cl, Br, I; Z = Mg, Ca, Ba, Sr; T = ClO4, NO3, HSO4, SCN). Phonon spectrometric analysis turned out the f(C) number fraction of bonds transition from the mode of deionized water to the hydrating. The linear f(C) ∝ C form features the invariant hydration volume of small cations that are fully-screened by their hydration H2O dipoles. The nonlinear f(C) ∝ 1 - exp.(-C/C0) form describes that the number insufficiency of the ordered hydrating H2O dipoles partially screens the anions. Molecular anions show stronger yet shorter electric field of dipoles. The screened ionic polarization, inter-solute interaction, and O:H-O bond transition unify the solution conductivity, surface stress, viscosity, and critical energies for phase transition.
3. Designing the structure and relevant properties of semiclathrate hydrates by partly asymmetric alkylammonium salts
Sanehiro Muromachi, Masato Kida, Masato Morimoto, Shogo Yamane, Satoshi Takeya Phys Chem Chem Phys. 2022 Aug 3;24(30):18198-18204. doi: 10.1039/d2cp02625b.
Semiclathrate hydrates are host-guest materials that form from ionic guests and water. There are numerous options for ionic guests, such as quaternary ammonium salts, to tune the functional properties of these materials such as melting temperature, fusion heat, and gas capacity and selectivity. To design these materials, the stabilization mechanism of the side chains of quaternary ammonium salts must be understood based on both thermodynamic and crystallographic properties and relevant host-guest dynamics. In this paper, we studied semiclathrate hydrates formed from n-propyl, tri-n-butylammonium bromide (N3444Br) and tri-n-butyl, n-pentylammonium bromide (N4445Br). Their cation side chains are decremented or incremented from tetra-n-butylammonium (N4444 or TBA), which is one of the best fits for semiclathrate hydrate structures. The use of the widely used tetra-n-butylammonium bromide (N4444Br or TBAB) as an ionic guest, an increment of the carbon chain, i.e., N4445Br, caused disorders in its hydrate structure due to the oversizing of the cation. This suitably oversized cation selectively stabilized the orthorhombic structure, whose hydration number is relatively high. As a result, the fusion heat at the congruent composition of the hydrate phase was higher than that of the widely used N4444Br (TBAB) hydrates. The N3444Br hydrate showed both significantly decreased melting temperature and fusion heat compared to the N4444Br (TBAB) hydrates. The phase behaviour of the N3444Br hydrate was found to be analogous to that of the N4444Br (TBAB) hydrates. It was demonstrated that the semiclathrate hydrate structures and relevant properties can be modified by adjusting the alkyl side chain length of quaternary ammonium salts.
