A drastic influence of the anion nature and concentration on high pressure intrusion–extrusion of electrolyte solutions in Silicalite-1

Abstract

High pressure intrusion–extrusion of concentrated solutions of sodium salts in a pure-silica MFI-type zeolite (Silicalite-1) was studied for potential applications in mechanical energy absorption and storage. It was discovered that the anion nature has a drastic influence on the behavior and the energetic performances of “Silicalite-1 – concentrated Na⁺X⁻ solution” systems, where X = Cl⁻, Br⁻, I⁻, NO₂⁻, NO₃⁻, ClO₄⁻ and CrO₄²⁻. In the case of NaNO₂, NaClO₄, Na₂CrO₄, and NaI a combination of bumper and shock-absorber behaviors with a partial irreversible solution intrusion was observed, whereas a fully reversible spring behavior is demonstrated for the intrusion–extrusion of NaBr, NaCl and NaNO₃ solutions. In comparison with water, the intrusion pressure increases for all the solutions except for NaClO₄ one. The irreversibility of intrusion decreases with a dilution rate, and the behavior of the corresponding systems with diluted solutions becomes very close. The variation of the system behavior and intrusion pressure values can be related to a different affinity of the corresponding anions for the pores of Silicalite-1. The samples before and after intrusion–extrusion experiments were characterized using several structural and physicochemical methods (XRD, TGA, solid-state NMR, and N₂ physisorption), but no significant structural difference was observed.