Mechanical Energy Storage and Absorption in Microporous Materials by High-Pressure Intrusion of Electrolyte Solutions – MESAMM

The project includes three main approaches:
1) High pressure intrusion-extrusion tests of aqueous salt solutions in hydrophobic zeolites and Zeolitic Imidazolate Frameworks synthesized in IS2M-MPC team. The porous solids are characterized by various physicochemical, structural and textural methods to better understand the interactions of solution species with porous frameworks.
2) Measurements of intrusion-extrusion thermal effects by calorimetry in situ in special experimental setup developed by ICB-ASP team in the frame of the project in order to better understand the thermodynamics of intrusion-extrusion process.
3) Molecular simulation of intrusion-extrusion process at atomistic scale by Molecular Dynamics and Monte-Carlo methods performed by IRCP and ENS-PASTEUR teams.

A study of intrusion-extrusion of aqueous solutions of different metal chlorides in MFI-type zeosil has been performed. It has been shown that the cation nature has a small impact on the behavior of “MFi-type zeosil – solution” systems, but it influences considerably on intrusion pressure values. Comparing alkaline and alkali-earth metals, it has been observed that the decrease of cation size and the increase of its charge lead to the rise of intrusion pressure. The systmes using highly concentrated LiCl and ZnCl2 solutions show the highest values of stored mechanical energy.
Intrusion-extrusion experiments of aqueous solutions of potassium halides in ZIF-8 type MOF has been performed. It has been shown that the nature of anion influences on intrusion pressure. The decrease of anion size leads to an increase of the pressure.
New experimental setup was built by ICB-ASP team. It allows to perform the measurements of thermal effects of intrusion-extrusion of concentrated salt solutions in hydrophobic nanoporous solids.

In the frame of the project, the intrusion-extrusion experiments will be performed for many new “zeolite – salt solution” and “ZIF – salt solution” systems in order to determine the influence of different parameters of solution and porous material on intrusion-extrusion characteristics: topology of zeolite and ZIF framework, its composition (only in the case of ZIFs – nature of cation and imidazolate ligand), the nature of salt cation and anion in the solutions as well as solution concentration. New systems “porous solid – salt solution” with high energetic performance will be obtained.
Thermal effects of intrusion-extrusion of aqueous salt solutions in several zeolites and ZIFs will be studied by clomrimetry is situ. The obtained results should allow to understand the thermodynamics of intrusion-extrusion process of electrolyte solutions in hydrophobic microporous materials.
Theoretical models of intrusion-extrusion will be developed by molecular simulation of the process by Molecular Dynamics and Monte-Carlo methods. This should allow to understand the intrusion process of electrolyte solutions in hydrophobic micropores at atomistic level.

Article:
F.X. Coudert, A. Boutin, A.H. Fuchs, “Open questions on water confined in nanoporous materials”, Communications Chemistry, 2021, in press
Conferences:
1. A. Ryzhikov, A. Astafan, T.J. Daou, H. Nouali, G. Chaplais, C. Marichal, High pressure intrusion of aqueous chloride salt solutions in silicalite-1 for mechanical energy storage: influence of cation nature, 8th Conference of the Federation of European Zeolite Associations (FEZA 2021), 5-9 Juillet 2021 (virtual, poster)

2. A. Astafan, H. Nouali, A. Ryzhikov, T.J. Daou, C. Marichal, G. Chaplais, High pressure intrusion of non-wetting liquid in hydrophobic Zeolitic Imidazolate Frameworks for mechanical energy storage/absorption, 15ème Journées d’Etudes de Milieux Poreux, 26-27 Octobre Strasbourg 2021.
3. A. Astafan, T.J. Daou, H. Nouali, G. Chaplais, C. Marichal, A. Ryzhikov, High Pressure Intrusion of Aqueous Salt Solutions in MFI-type Zeosil: Influence of Cation Nature, 15ème Journées d’Etudes de Milieux Poreux, Strasbourg, 26-27 Octobre 2021.

The project is devoted to development of new highly efficient heterogeneous lyophobic systems for mechanical energy storage and absorption based on high pressure intrusion-extrusion of electrolyte solutions in hydrophobic microporous materials such as pure-silica zeolites (zeosils) and Metal-Organic Frameworks. The understanding of intrusion mechanism at the atomistic and thermodynamic level is the main objective. The project includes the experiments on highly concentrated electrolyte aqueous solutions intrusion-extrusion in the porous solids with varying of cation and anion nature, the study of intrusion process by in situ calorimetry and molecular simulation of the process by Molecular Dynamics and Monte-Carlo methods.