Energetic Performances of ZIF-8 Derivatives: Impact of the Substitution (Me, Cl, or Br) on Imidazolate Linker

Abstract

The energetic performances of three isomorphic ZIF materials, i.e., ZIF-8_CH 3 (Basolite Z1200), ZIF-8_Cl, and ZIF-8_Br, of SOD topology are studied with high-pressure intrusion−extrusion experiments using water and aqueous electrolyte solutions (KCl 4 M and LiCl 20 M) as nonwetting liquids. This work represents an important progress in the field of energetic applications, as the "ZIF-8_Cl−LiCl 20 M" system exhibits a spring behavior with a stored energy of 77 J g −1 . To the best of our knowledge, this is the highest value for the stored energy obtained using intrusion−extrusion experiments. Experimental results reveal that the intrusion pressure increases with the addition of electrolytes. The systems evolve from a bumper to a shock-absorber or spring behavior with the decrease in the strength of the interactions between the cation of the salt and the imidazolate linker. This explains the bumper or rather the shock-absorber behavior observed for the "ZIF-8_Br−KCl 4 M" and "ZIF-8_CH 3 −LiCl 20 M" systems compared to the spring behavior observed with the other systems reported in this work.

Ab Initio Derived Force Fields for Zeolitic Imidazolate Frameworks: MOF-FF for ZIFs

“…Interestingly they found that ZIF-8(Cl) exhibits a spring behavior with the highest amount of energy stored ever in high pressure intrusion-extrusion experiments. 11 These findings underline the potential of ZIFs for technical application. To exploit this potential, it is pivotal to gain an atomistic understanding of the underlying mechanisms, making molecular simulations a valuable tool, and the accurate description of the frameworks' flexibility a crucial goal.…”

Impacts of the Imidazolate Linker Substitution (CH3, Cl, or Br) on the Structural and Adsorptive Properties of ZIF-8

“…Since few years, we have developed a new type of application, i.e., energetic applications involving such materials from both experimental and modelling approches. [21][22][23][24][25][26][27][28] In a recent study, 27 These two halogenated hybrids were reported for the first time by Li et al [29][30] for the assessment of their kinetic separation properties of propane/propene. Even if the authors listed the related crystal data and structure refinement parameters and deposited the information in the Cambridge Structural Database, 31 as referenced as AWIWEJ and AWIWIN, actually for only the crude compounds, namely the hybrid matrixes with remaining occluded solvent molecules, no further details about the needed atomic positions were provided from the two sources.…”

Structure, Dynamics, and Thermodynamics of Intruded Electrolytes in ZIF-8

“…18 ZIF-8 behavior can also be tuned chemically, by modifying the nature of the linkers, for example changing the 2-methylimidazolate to a 2-chloroimidazolate increases the intrusion pressure. 29 However, the exact mechanism and behavior at the molecular level upon intrusion of electrolytes in ZIF-8 are still unknown. In this work, we used classical molecular simulations to study the structure, dynamics and energetic implications of confining water and aqueous solutions of LiCl in ZIF-8.…”