Quality-dependent performance of hydrophobic ZIF-67 upon high-pressure water intrusion–extrusion process

Amayuelas, Eder; Bartolomé, Luis; Zhang, Yan; López del Amo, Juan Miguel; Bondarchuk, Oleksandr; Nikulin, Artem; Bonilla, Francisco; del Barrio, Elena Palomo; Zajdel, Paweł; Grosu, Yaroslav

doi:10.1039/d3cp03519k

Phys. Chem. Chem. Phys.

2024

DOI: 10.1039/d3cp03519k

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Quality-dependent performance of hydrophobic ZIF-67 upon high-pressure water intrusion–extrusion process

Eder Amayuelas,

Luis Bartolomé,

Yan Zhang

et al.

Abstract: Zeolitic imidazolate framework (ZIF) microporous materials have already been present in many fields of energetic and environmental interest since the last decade. The commercial scale production of some of these...

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Cited by 2 publications

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

Amayuelas,

Farrando-Perez,

Missyul

et al. 2024

ACS Appl. Mater. Interfaces

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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)-1H-imidazole (monof luorinated linker) or 2-methyl-5-(trifluoromethyl)-1H-imidazole (trifluorinated linker) as a dopant], demonstrating the high versatility of the synthetic method developed to incorporate different fluorine-containing imidazole-based ligands. Second, we demonstrate for the first time 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.

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

Amayuelas,

Farrando-Perez,

Missyul

et al. 2024

ACS Appl. Mater. Interfaces

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Bubbles enable volumetric negative compressibility in metastable elastocapillary systems

Caprini,

Battista,

Zajdel

et al. 2024

Nat Commun

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Although coveted in applications, few materials expand when subject to compression or contract under decompression, i.e., exhibit negative compressibility. A key step to achieve such counterintuitive behaviour is the destabilisations of (meta)stable equilibria of the constituents. Here, we propose a simple strategy to obtain negative compressibility exploiting capillary forces both to precompress the elastic material and to release such precompression by a threshold phenomenon – the reversible formation of a bubble in a hydrophobic flexible cavity. We demonstrate that the solid part of such metastable elastocapillary systems displays negative compressibility across different scales: hydrophobic microporous materials, proteins, and millimetre-sized laminae. This concept is applicable to fields such as porous materials, biomolecules, sensors and may be easily extended to create unexpected material susceptibilities.

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Quality-dependent performance of hydrophobic ZIF-67 upon high-pressure water intrusion–extrusion process

Abstract: Zeolitic imidazolate framework (ZIF) microporous materials have already been present in many fields of energetic and environmental interest since the last decade. The commercial scale production of some of these...

Cited by 2 publications

References 59 publications

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

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

Bubbles enable volumetric negative compressibility in metastable elastocapillary systems

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