Design and synthesis of zeolitic tetrazolate-imidazolate frameworks

Li, Minyu; Liu, Juan; Lin, Duoyu; Wang, Fei; Zhang, Jian

doi:10.1016/j.mtadv.2021.100145

Cited by 14 publications

(10 citation statements)

References 47 publications

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“…It is challenging to liquefy metal–organic frameworks (MOFs) because these materials typically decompose upon heating, even in an inert atmosphere, before they melt. − However, the liquid state of MOFs is of highest interest, as it allows molding and shaping of these functional porous materials and the generation of MOF glasses by quenching the MOF melt below its glass transition temperature ( T g ). , MOF glasses have been classified as the 4th generation of MOFs as they possess the potential to address some of the key challenges in materials development for applications in gas separation, solid electrolytes, battery materials, and many more. − However, out of the enormous number of crystalline MOF structures reported so far, only a very few derivatives have been shown to melt and form a porous glass after melt-quenching. Among these are some derivatives of the subfamily of zeolitic imidazolate frameworks (ZIFs). ,,− ZIFs typically are crystalline materials constructed from M 2+ cations (e.g., Zn 2+ or Co 2+ ), which are tetrahedrally coordinated by imidazolate-type linkers, forming network topologies similar to zeolites and silicates. − The rather high thermal stability of some ZIFs, predominantly a consequence of the relatively high thermal stability of imidazolate-type linkers, is a key feature for accessing their liquid and glassy states.…”

Section: Introductionmentioning

confidence: 99%

Modulating Liquid–Liquid Transitions and Glass Formation in Zeolitic Imidazolate Frameworks by Decoration with Electron-Withdrawing Cyano Groups

et al. 2023

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The liquid phase of metal–organic frameworks (MOFs) is key for the preparation of melt-quenched bulk glasses as well as the shaping of these materials for various applications; however, only very few MOFs can be melted and transformed into stable glasses. Here, the solvothermal and mechanochemical preparation of a new series of functionalized derivatives of ZIF-4 (Zn(im)2, where im– = imidazolate and ZIF = zeolitic imidazolate framework) containing the cyano-functionalized imidazolate linkers CNim– (4-cynanoimidazolate) and dCNim– (4,5-dicyanoimidazolate) is reported. The strongly electron-withdrawing nature of the CN groups facilitates low-temperature melting of the materials (below 310 °C for some derivatives) and the formation of microporous ZIF glasses with remarkably low glass-transition temperatures (down to only about 250 °C) and strong resistance against recrystallization. Besides conventional ZIF-4, the CN-functionalized ZIFs are so far the only MOFs to show an exothermic framework collapse to a low-density liquid phase and a subsequent transition to a high-density liquid phase. By systematic adjustment of the fraction of cyano-functionalized linkers in the ZIFs, we derive fundamental insights into the thermodynamics of the unique polyamorphic nature of these glass formers as well as further design rules for the porosity of the ZIF glasses and the viscosity of their corresponding liquids. The results provide new insights into the unusual phenomenon of liquid–liquid transitions as well as a guide for the chemical diversification of meltable MOFs, likely with implications beyond the archetypal ZIF glass formers.

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Section: Introductionmentioning

confidence: 99%

Modulating Liquid–Liquid Transitions and Glass Formation in Zeolitic Imidazolate Frameworks by Decoration with Electron-Withdrawing Cyano Groups

et al. 2023

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“…The structural arrangement and bonding between the mtz linker and Zn(II) metal center in the SOD topology are the most stable of all N-donor ligands. 50 These two properties of ZTF-8 prevent it from acid/base/H 2 O attacks and achieve superior stability relative to all ZIFs and ZTFs reported so far. S12, Supporting Information.…”

Section: Resultsmentioning

confidence: 94%

“…Surprisingly, all acid- and base-treated samples maintained their original crystal structure, as evidenced by their unshifted PXRD profiles in comparison to the parent framework (Figures S10 and S11, Supporting Information). The structural arrangement and bonding between the mtz linker and Zn(II) metal center in the SOD topology are the most stable of all N-donor ligands . These two properties of ZTF-8 prevent it from acid/base/H 2 O attacks and achieve superior stability relative to all ZIFs and ZTFs reported so far.…”

Section: Resultsmentioning

confidence: 96%

A Novel Mechano-Synthesized Zeolitic Tetrazolate Framework for a High-Performance Triboelectric Nanogenerator and Self-Powered Selective Neurochemical Detection

Sarfudeen,

P K,

Basith

et al. 2024

ACS Appl. Mater. Interfaces

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Designing a high-performing triboelectric novel material with eco-friendly, rapid, and cost-effective synthesis is the future of material research in triboelectric nanogenerators (TENG). We report a mechanochemical ball mill synthesis of a zeolitic tetrazolate framework (ZTF-8) that is isostructural with the wellknown zeolitic imidazolate framework ZIF-8. ZTF-8 is extremely stable in water, 0.1 M aqueous acid/base solutions for 75 days at 25 °C, and boiling water (100 °C) for 7 days. Kelvin probe force microscopy and molecular electrostatic surface potential computational analysis exhibited that ZTF-8 has a very high positive surface potential. Atomic force microscopy and three-dimensional digital microscopy studies reveal the high roughness profile in the ZTF-8 film. The unique structure, exceptional acid/base stability, good dielectric property, and high roughness profile combined with the extremely electropositive nature of ZTF-8 make it a suitable candidate as a polymer-free triboelectric positive material in TENG with outstanding performance (power density of 720 mW/m 2 ). High triboelectric output was further validated using the COMSOL Multiphysics simulation tool. Simple mechanical hand tapping of the ZTF-based TENG (ZTF-TENG) device generates high electric output, which was practically used to power numerous low-powered devices like tally counter, clinical thermometer, and digital clock and also illuminates 125 light-emitting diodes. In addition, the efficiency of ZTF-TENG was utilized as a self-powered device for a selective dopamine (DA) sensor with good sensitivity (377.76 mV/μM/cm 2 ), wide range linearity (5−120 μM), and excellent limit of detection (0.42 μM).

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“…However, the stability and colloidal stability of ZIF‐7 under biological conditions remain an important challenge. Moreover, 5‐FU is a water‐soluble hydrophilic acidic drug, whereas ZIFs are less stable in water, acid solutions and phosphate ion [14] . Consequently, ZIF decomposition and early drug release are inevitable in the circulation [15] .…”

Section: Introductionmentioning

confidence: 99%

Incorporating Fluorescent Organosilica and Zeolitic Imidazolate Frameworks into Periodic Mesoporous Organosilica for the Enhanced Cargo Delivery of 5‐Fluorouracil

Huynh,

Nguyen,

Mai

et al. 2024

ChemistrySelect

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Nanosized zeolitic imidazolate frameworks (nZIFs) are being researched as 5‐fluorouracil (5‐FU) carriers for the treatment of cancer. The surface functionalization of ZIFs with periodic mesoporous organosilicas (PMOs) is expected to enhance stability and prevent the flocculation of nZIFs. In this study, ZIF‐7 nanomaterials and fluorescent organosilicas (FITC−APTES) were effectively introduced into PMO nanoparticles, and the resulting product was named ZIF‐7@PMO. The surface functionalization with the PMO nanoparticles enhanced the chemical stability of ZIF‐7 nanoparticles in ethanol. The study examined the impact of temperature on the synthesis of ZIF‐7@PMO and found that low temperatures were more conducive to the encapsulation of ZIF‐7 nanoparticles and fluorescent organosilica, as well as pore size retention. Moreover, the drug storage capacity of the ZIF‐7@PMO nanoparticles was evaluated via their loading and release of 5‐FU. The results revealed that the ZIF‐7@PMO nanoparticles could adsorb 5‐FU with a loading capacity of 100–140 mg g−1 for 24 h. ZIF‐7@PMO released half of 5‐FU amount within 8 h before releasing a maximum of 75 % within 3 days. Therefore, the fluorescent ZIF‐7@PMO nanoparticles could be a potential drug carrier in the field of controlled drug delivery.

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Design and synthesis of zeolitic tetrazolate-imidazolate frameworks

Cited by 14 publications

References 47 publications

Modulating Liquid–Liquid Transitions and Glass Formation in Zeolitic Imidazolate Frameworks by Decoration with Electron-Withdrawing Cyano Groups

Modulating Liquid–Liquid Transitions and Glass Formation in Zeolitic Imidazolate Frameworks by Decoration with Electron-Withdrawing Cyano Groups

A Novel Mechano-Synthesized Zeolitic Tetrazolate Framework for a High-Performance Triboelectric Nanogenerator and Self-Powered Selective Neurochemical Detection

Incorporating Fluorescent Organosilica and Zeolitic Imidazolate Frameworks into Periodic Mesoporous Organosilica for the Enhanced Cargo Delivery of 5‐Fluorouracil

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