Fluorinated Nanosized Zeolitic-Imidazolate Frameworks as Potential Devices for Mechanical Energy Storage

Fluorination is one of the most efficient and universal strategies to increase the hydrophobicity of materials and consequently their water stability. Zeolitic-imidazolate frameworks (ZIFs), which have limited stability in aqueous media and even lower stability when synthesized on a nanometric scale, can greatly benefit from the incorporation of fluorine atoms, not only to improve their stability but also to provide additional properties. Herein, we report the preparation of two different fluorinated ZIFs through a simple and scalable approach by using mixed ligands [2-methylimidazole, as a common ligand, and 4-(4-fluorophenyl)-1<i>H</i>-imidazole (<i>monofluorinated</i> linker) or 2-methyl-5-(trifluoromethyl)-1<i>H</i>-imidazole (<i>trifluorinated</i> linker) as a dopant], demonstrating the high versatility of the synthetic method developed to incorporate different fluorine-containing imidazole-based ligands. Second, we demonstrate <i>for the first time</i> that these nanoscale fluorinated ZIFs outperform the pristine ZIF-8 for water intrusion/extrusion, i.e., for storing mechanical energy via forced intrusion of nonwetting water due to the improved hydrophobicity and modified framework dynamics. Moreover, we also show that by varying the nature of the F-imidazole ligand, the performance of the resulting ZIFs, including the pressure thresholds and stored/dissipated energy, can be finely tuned, thus opening the path for the design of a library of fluorine-modified ZIFs with unique behavior.