Astafan Amir, Nouali Habiba, Chaplais Gérald, Daou T Jean, Ryzhikov Andrey
Université de Haute-Alsace, CNRS, Institut de Science des Matériaux de Mulhouse (IS2M), UMR 7361, Axe Matériaux à Porosité Contrôlée (MPC), F-68100, Mulhouse, France.
Université de Strasbourg, F-67000 Strasbourg, France.
Phys Chem Chem Phys. 2025 Apr 16;27(16):8552-8558. doi: 10.1039/d5cp00540j.
High pressure intrusion-extrusion of water and aqueous salt solutions in hydrophobic porous solids such as pure silica zeolites (zeosils) is a promising way to absorb and store mechanical energy. The intrusion pressure has already been shown to be increased with salt concentration, but the influence of cation nature is not yet fully understood. The intrusion-extrusion experiments of aqueous chloride solutions of alkali, alkaline-earth and transition metals (MCl, where M = Li, Na, K, Rb, Cs, Ca, Mg, Sr, Al, Mn, Ni Co, Cu, Zn, Cd) in MFI-type zeosil (silicalite-1) have been performed to study this effect. In contrast to the anions, the reported results indicate that the cation nature does not have a significant influence on intrusion behavior. All the systems demonstrate a spring behavior with fully reversible intrusion except the ones with highly concentrated ZnCl and CsCl solutions, where a small part of the liquid remains trapped in the pores in the first intrusion-extrusion cycle. At fixed HO/salt molar ratio, a strong influence of cation nature on intrusion pressure is observed. For alkali, alkaline-earth metal and aluminium cations, the intrusion pressure rises with cation charge, whereas the increase of cation size leads to a pressure decrease. These trends are also in agreement with cation hydration enthalpy value for alkali and alkaline-earth metal cations, but no correlation is observed for the most part of the transition metal ones except Zn and Cd.
在诸如纯硅沸石（硅质沸石）等疏水性多孔固体中对水和盐水溶液进行高压侵入-挤出是吸收和存储机械能的一种很有前景的方法。侵入压力已被证明会随着盐浓度的增加而升高，但阳离子性质的影响尚未完全明确。已开展了碱金属、碱土金属和过渡金属（MCl，其中M = Li、Na、K、Rb、Cs、Ca、Mg、Sr、Al、Mn、Ni、Co、Cu、Zn、Cd）的氯化物水溶液在MFI型硅质沸石（硅沸石-1）中的侵入-挤出实验来研究这种影响。与阴离子不同，所报道的结果表明阳离子性质对侵入行为没有显著影响。除了高浓度ZnCl和CsCl溶液的体系外，所有体系均表现出完全可逆侵入的弹簧行为，在高浓度ZnCl和CsCl溶液体系中，在第一次侵入-挤出循环中有一小部分液体被困在孔隙中。在固定的H₂O/盐摩尔比下，可以观察到阳离子性质对侵入压力有强烈影响。对于碱金属、碱土金属和铝阳离子，侵入压力随阳离子电荷增加而升高，而阳离子尺寸的增大则导致压力降低。这些趋势也与碱金属和碱土金属阳离子的阳离子水合焓值一致，但除了Zn和Cd外，大多数过渡金属阳离子未观察到相关性。
