Fluoride-incorporated ionic clathrate hydrates

Ionic clathrate hydrates are promising materials for hydrate-based gas storage and separation processes. Here, we demonstrated that the hydroxide ion in the cubic structure-II (CS-II) and hexagonal structure-III (HS-III) ionic clathrate hydrates can be replaced by fluoride. Me4N+ and Et2Me2N+ cations were selected as guest species for the CS-II and HS-III hydrates, respectively. The crystal structure of each hydrate was identified through Rietveld analysis of the PXRD pattern. The Fd3¯m\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$F\overline {d3} m$$\end{document} structure (CS-II) of Me4NF+N2 or O2 hydrates and the P6/mmm structure (HS-III) of Et2Me2NF+CH4 hydrate were confirmed. We also investigated the phase equilibria of hydroxide or fluoride-incorporated CS-II and HS-III hydrate systems, and found that incorporating fluoride destabilizes the hydrate lattice to a greater extent than hydroxide. The present findings will provide better understanding of the guest-host interactions in ionic clathrate hydrates, and suggest their potential for practical applications in gas storage and separation technologies.