Giorgia Confalonieri, Andrey Ryzhikov, Rossella Arletti, Frederico Alabarse, Habiba Nouali, Riccardo Fantini, Jean Daou
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The results are compared with those obtained for systems involving the same zeolite but intruded with solutions containing only single salts (CaCl<sub>2</sub> or KCl). The porosimetric results of the three Si-CHA systems intruded by simple and complex electrolyte solutions (KCl 2 <i>M</i>, CaCl<sub>2</sub> 2 <i>M</i> and the mixture KCl 1 <i>M</i> + CaCl<sub>2</sub> 1 <i>M</i>) suggest that the intrusion pressure is mainly influenced by the nature of the cations. The CaCl<sub>2</sub> 2 <i>M</i> solution shows the highest intrusion pressure and KCl 2 <i>M</i> the lowest, whereas the mixture KCl 1 <i>M</i> + CaCl<sub>2</sub> 1 <i>M</i> is almost in the middle. These differences are probably related to the higher hydration enthalpy and Gibbs energy of Ca<sup>2+</sup> compared with those of K<sup>+</sup>. It has been demonstrated that partial ion desolvation is needed to promote the penetration of the species, and a higher solvation energy requires higher pressure. The `intermediate' value of intrusion pressure shown by the complex electrolyte solution arises from the fact that, statistically, the second/third solvation cation shells can be assumed to be partially shared between K<sup>+</sup> and Ca<sup>2+</sup>. The stronger interaction of Ca<sup>2+</sup> with H<sub>2</sub>O molecules thus also influences the desolvation of K<sup>+</sup>, increasing the pressure needed to activate the process compared with the pure KCl 2 <i>M</i> solution. This is confirmed by the structural investigation, which shows that at the beginning of intrusion only K<sup>+</sup>, Cl<sup>−</sup> and H<sub>2</sub>O penetrate the pores, whereas the intrusion of Ca<sup>2+</sup> requires higher pressure, in agreement with the hydration enthalpies of the two cations.</p>","PeriodicalId":48737,"journal":{"name":"Journal of Applied Crystallography","volume":null,"pages":null},"PeriodicalIF":5.2000,"publicationDate":"2024-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"High-pressure intrusion of double salt aqueous solution in pure silica chabazite: searching for cation selectivity\",\"authors\":\"Giorgia Confalonieri, Andrey Ryzhikov, Rossella Arletti, Frederico Alabarse, Habiba Nouali, Riccardo Fantini, Jean Daou\",\"doi\":\"10.1107/S1600576724002863\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Heterogeneous lyophobic systems (HLSs), <i>i.e.</i> systems composed of a nanoporous solid and a non-wetting liquid, have attracted much attention as promising candidates for innovative mechanical energy storage and dissipation devices. 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引用次数: 0
摘要
异质疏水性体系(HLS),即由纳米多孔固体和非润湿液体组成的体系,作为创新机械储能和耗能设备的候选材料,已引起广泛关注。在这项研究中,我们从孔隙模拟和晶体学的角度研究了一种基于纯硅石(Si-CHA)和三元电解质溶液(KCl + CaCl2)的新型 HLS。这项研究采用的综合方法对于揭示该体系的特性至关重要。孔隙比拟实验有助于确定能量行为,而高压原位结晶分析则有助于阐明侵入机制。实验结果与涉及相同沸石但只用含有单一盐类(CaCl2 或 KCl)的溶液侵入的系统所获得的结果进行了比较。由简单和复杂电解质溶液(KCl 2 M、CaCl2 2 M 和 KCl 1 M + CaCl2 1 M 混合溶液)侵入的三种 Si-CHA 系统的孔隙模拟结果表明,侵入压力主要受阳离子性质的影响。CaCl2 2 M 溶液的侵入压力最高,KCl 2 M 溶液的侵入压力最低,而 KCl 1 M + CaCl2 1 M 混合溶液的侵入压力几乎处于中间位置。这些差异可能与 Ca2+ 的水合焓和吉布斯能高于 K+ 有关。事实证明,需要部分离子脱溶来促进物种的渗透,而较高的溶解能需要较高的压力。复合电解质溶液所显示的 "中间 "侵入压力值源于这样一个事实,即从统计学角度来看,可以假定 K+ 和 Ca2+ 部分共享第二/第三溶解阳离子壳。因此,与纯 KCl 2 M 溶液相比,Ca2+ 与 H2O 分子更强的相互作用也会影响 K+ 的解溶解,增加激活过程所需的压力。结构研究也证实了这一点,该研究表明,在侵入开始时,只有 K+、Cl- 和 H2O 能穿透孔隙,而 Ca2+ 的侵入则需要更高的压力,这与两种阳离子的水合焓一致。
High-pressure intrusion of double salt aqueous solution in pure silica chabazite: searching for cation selectivity
Heterogeneous lyophobic systems (HLSs), i.e. systems composed of a nanoporous solid and a non-wetting liquid, have attracted much attention as promising candidates for innovative mechanical energy storage and dissipation devices. In this work, a new HLS based on a pure silica chabazite (Si-CHA) and a ternary electrolyte solution (KCl + CaCl2) is studied from porosimetric and crystallographic points of view. The combined approach of this study has been fundamental in unravelling the properties of the system. The porosimetric experiments allowed the determination of the energetic behaviour, while high-pressure in situ crystallographic analyses helped elucidate the mechanism of intrusion. The results are compared with those obtained for systems involving the same zeolite but intruded with solutions containing only single salts (CaCl2 or KCl). The porosimetric results of the three Si-CHA systems intruded by simple and complex electrolyte solutions (KCl 2 M, CaCl2 2 M and the mixture KCl 1 M + CaCl2 1 M) suggest that the intrusion pressure is mainly influenced by the nature of the cations. The CaCl2 2 M solution shows the highest intrusion pressure and KCl 2 M the lowest, whereas the mixture KCl 1 M + CaCl2 1 M is almost in the middle. These differences are probably related to the higher hydration enthalpy and Gibbs energy of Ca2+ compared with those of K+. It has been demonstrated that partial ion desolvation is needed to promote the penetration of the species, and a higher solvation energy requires higher pressure. The `intermediate' value of intrusion pressure shown by the complex electrolyte solution arises from the fact that, statistically, the second/third solvation cation shells can be assumed to be partially shared between K+ and Ca2+. The stronger interaction of Ca2+ with H2O molecules thus also influences the desolvation of K+, increasing the pressure needed to activate the process compared with the pure KCl 2 M solution. This is confirmed by the structural investigation, which shows that at the beginning of intrusion only K+, Cl− and H2O penetrate the pores, whereas the intrusion of Ca2+ requires higher pressure, in agreement with the hydration enthalpies of the two cations.
期刊介绍:
Many research topics in condensed matter research, materials science and the life sciences make use of crystallographic methods to study crystalline and non-crystalline matter with neutrons, X-rays and electrons. Articles published in the Journal of Applied Crystallography focus on these methods and their use in identifying structural and diffusion-controlled phase transformations, structure-property relationships, structural changes of defects, interfaces and surfaces, etc. Developments of instrumentation and crystallographic apparatus, theory and interpretation, numerical analysis and other related subjects are also covered. The journal is the primary place where crystallographic computer program information is published.