Interfacial Bonding between a Crystalline Metal–Organic Framework and an Inorganic Glass
Celia Castillo‐BlasAshleigh M. ChesterRonan P. CosquerAdam F. SapnikLucia CortiRoman SajzewBruno Poletto RodriguesGeorgina RobertsonDaniel IrvingLauren McHughLothar WondraczekFrédéric BlancDavid A. KeenThomas D. Bennett
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Abstract:
The interface within a composite is critically important for the chemical and physical properties of these materials. However, experimental structural studies of the interfacial regions within metal-organic framework (MOF) composites are extremely challenging. Here, we provide the first example of a new MOF composite family, i.e., using an inorganic glass matrix host in place of the commonly used organic polymers. Crucially, we also decipher atom-atom interactions at the interface. In particular, we dispersed a zeolitic imidazolate framework (ZIF-8) within a phosphate glass matrix and identified interactions at the interface using several different analysis methods of pair distribution function and multinuclear multidimensional magic angle spinning nuclear magnetic resonance spectroscopy. These demonstrated glass-ZIF atom-atom correlations. Additionally, carbon dioxide uptake and stability tests were also performed to check the increment of the surface area and the stability and durability of the material in different media. This opens up possibilities for creating new composites that include the intrinsic chemical properties of the constituent MOFs and inorganic glasses.Keywords:
Zeolitic imidazolate framework
Magic angle spinning
Chemical Stability
Imidazolate
We report the reversible pressure-induced amorphization of a zeolitic imidazolate framework (ZIF-4, [Zn(Im)(2)]). This occurs irrespective of pore occupancy and takes place via a novel high pressure phase (ZIF-4-I) when solvent molecules are present in the pores. A significant reduction in bulk modulus upon framework evacuation is also observed for both ZIF-4 and ZIF-4-I.
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Presented here is an SOD-type zeolitic tetrazolate–imidazolate framework (ZTIF-8) based on 5-methyltetrazole (5-Hmtz) and 2-methyimidazole (2-Hmim) ligands. Owing to the uncoordinated N-sites on the framework, ZTIF-8 has shown high chemical fixation of CO2 to cyclic carbonates at room temperature and ambient pressure.
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Simultaneous removal of microplastics and endocrine disruptors was performed with high yields using Zeolitic imidazolate/Fe3O4 nanocomposite. Polystyrene and 4-tert-butylphenol were used to indicate the microplastic and endocrine disruptors. Under optimal conditions for maximum yields, the matrix was as follows: 1.5 mg/l Zeolitic imidazolate/Fe3O4 nanocomposite, 30 min adsorption time at a Zeolitic imidazolate to Fe3O4 ratio of 1/1, and 6 mg/l individual polystyrene 4-tert-butylphenol concentrations. Under these conditions, 99% and 98% removals were detected for polystyrene and 4-tert-butylphenol, respectively via adsorption. An excellent reproducibility was found for Zeolitic imidazolate/Fe3O4 nanocomposite under steadystate operational conditions. The FESEM analyses showed that Zeolitic imidazolate/Fe3O4 nanocomposite diameter was around 30 nm at a Zeolitic imidazolate to Fe3O4 nanocomposite ratio of 1/1 while some larger dodecahedral particles size was ≤ 300 nm. N2 adsorption–desorption measurements exhibited the porosity of Zeolitic imidazolate/Fe3O4 nanocomposite and the decrease of size is attributed to the incorporation of a nonporous magnetic phase via the addition of Fe2+ to the nanocomposite. BET results showed a specific surface area with a BET isotherm of 5000 m2 /g, and a pore size of 30 nm for Zeolitic imidazolate/Fe3O4 nanocomposite. In the XRD spectra of Zeolitic imidazolate/Fe3O4 nanocomposite, the structure of nanocomposite was not changed by the addition of imidazolate and Fe3O4 nanocomposite. HRTEM analysis indicated some crystal agglomerations by doping of zeolitic imidazolate to Fe3O4. The reusability of the Zeolitic imidazolate/Fe3O4 nanocomposite was excellent even after 60 times utilization. The yields were 88% and 85% after 60 runs while the nanocomposite was reused 20 times during runs with yields as high as 97% and 98%.
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금속유기구조체(metal-organic frameworks, MOF)는 넓은 비표면적, 규칙적인 구조 및 높게 분산된 금속 성분 등 뛰어난 물리화학적 특성으로 인해 활발한 연구가 이뤄지고 있는 다공성 물질이며, 특히 가스의 흡착, 분리 매체로서 뛰어난 성능이 보고되고 있다. MOF를 이용한 온실가스 이산화탄소의 흡착 연구는 상온 고압 영역에서 이산화탄소 저장 공정과 상온 저압 영역에서 이산화탄소 흡착 공정의 두 범주로 나눌 수 있으며, MOF의 넓은 비표면적 외에도 (1) MOF의 빈 배위결합 자리, (2) MOF의 기능화, (3) MOF의 상호 침투 효과, 및 (4) 이온 교환 효과를 이용한 연구 결과가 보고되고 있다. MOF 물질들은 비교적 낮은 수분 및 열에 대한 안정성이 문제로 제기되고 있으며, 제올라이트 유사 구조체(zeolitic imidazolate frameworks, ZIF) 또는 유기 골격 구조체(covalent organic frameworks, COF) 물질의 이산화탄소 흡착 특성이 거론되고 있다. 본 소고에서는 MOF를 이용한 이산화탄소 흡착에 대한 최근의 연구 결과를 본 연구실의 실험 결과를 중심으로 간략히 소개하고자 한다. Metal organic frameworks (MOFs) are a class of crystalline organic-inorganic hybrid compounds formed by coordination of metal clusters or ions with organic linkers. MOFs have recently attracted intense research interest due to their permanent porous structures, large surface areas and pore volume, high-dispersed metal species, and potential applications in gas adsorption, separation, and catalysis. $CO_2$ adsorption in MOFs has been investigated in two areas of $CO_2$ storage at high pressures and $CO_2$ adsorption at atmospheric pressure conditions. In this short review, $CO_2$ adsorption/separation results using MOFs conducted in our laboratory was explained in terms of four contributing effects; (1) coordinatively unsaturated open metal sites, (2) functionalization, (3) interpenetration/catenation, and (4) ion-exchange. Zeolitic imidazolate frameworks (ZIFs) and covalent organic frameworks (COFs) were also considered as a candidate material.
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The rates of adsorbate diffusion in zeolitic imidazolate frameworks (ZIFs) can be varied by several orders of magnitude by incorporating two different imidazolate linkers in the ZIF crystals. Although some prior measurements of short-range order in these mixed-linker materials have been reported, it is unclear how this short-range order impacts the net diffusion of adsorbates. We introduce a lattice diffusion model that treats diffusion in ZIF-8x-90100-x crystals as a series of activated hops between cages, allowing us to assess the effects of short-range imidazolate order on molecular diffusion.
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Metal-organic frameworks (MOFs) have exciting properties and promising applications in different fields. In this work, novel zeolitic imidazolate frameworks (ZIFs) have been synthesized by encapsulating N-doped carbon quantum dots (N-CDs) with a blue FL into the zeolitic imidazolate framework materials core-shell structure (ZIF-8@ZIF-67). The functionalized core-shell MOFs maintained their crystal structure, morphology, and enhanced UV-vis absorbance. The properties of these new composites exhibit excellent potential for different applications including sensing, photo-catalysis, and selective adsorption.
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A novel composite (CDs@ZIF-8) based on carbon dots (CDs) and a zeolitic imidazolate framework (ZIF-8) was successfully synthesized by encapsulating CDs into the pores of ZIF-8 through a simple one-pot solvothermal method.
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Condensations and cycloadditions can be catalyzed by newly synthesized Cu-doped zeolitic imidazolate frameworks (ZIFs). The catalysts were well characterized and reusable.
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A high-throughput protocol was developed for the synthesis of zeolitic imidazolate frameworks (ZIFs). Twenty-five different ZIF crystals were synthesized from only 9600 microreactions of either zinc(II)/cobalt(II) and imidazolate/imidazolate-type linkers. All of the ZIF structures have tetrahedral frameworks: 10 of which have two different links (heterolinks), 16 of which are previously unobserved compositions and structures, and 5 of which have topologies as yet unobserved in zeolites. Members of a selection of these ZIFs (termed ZIF-68, ZIF-69, and ZIF-70) have high thermal stability (up to 390 degrees C) and chemical stability in refluxing organic and aqueous media. Their frameworks have high porosity (with surface areas up to 1970 square meters per gram), and they exhibit unusual selectivity for CO2 capture from CO2/CO mixtures and extraordinary capacity for storing CO2: 1 liter of ZIF-69 can hold approximately 83 liters of CO2 at 273 kelvin under ambient pressure.
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Zeolitic Imidazolate Framework-8 (ZIF-8), for the first time for ZIFs, exhibits a remarkable capacity for the anticancer drug 5-fluorouracil (5-FU), around 660 mg of 5-FU/g of ZIF-8, and presents a pH-triggered controlled drug release property. These prove ZIF-8 to be a valuable candidate for delivery of anticancer agents and reveal its potential applications in the treatment of cancer.
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