Steam-stable zeolitic imidazolate framework ZIF-90 membrane with hydrogen selectivity through covalent functionalization

A novel covalent functionalization strategy was developed to prepare reproducible ZIF-90 molecular sieve membranes by using 3-aminopropyltriethoxysilane as a covalent linker between the ZIF-90 layer and Al(2)O(3) support via imines condensation. The ZIF-90 membranes show high thermal and hydrothermal stabilities, and they allow the separation of hydrogen from larger gases by molecular sieving.     

Heat capacities and thermodynamic properties of a Zn-based zeolitic imidazolate framework

Journal of Thermal Analysis and Calorimetry - The molar heat capacities of one–three-dimensional zeolitic imidazolate frameworks Zn(C4H6N2)2 (ZIF-8) were measured by temperature-modulated...     

Multivariate sodalite zeolitic imidazolate frameworks: a direct solvent-free synthesis

Different mixed-ligand Zeolitic Imidazolate Frameworks (ZIFs) with sodalite topology, i.e. isoreticular to ZIF-8, unachievable by conventional synthetic routes, have been prepared using a solvent-free methodology. In particular, the versatility of this method is demonstrated with three different metal centres (Zn, Co and Fe) and binary combinations of three different ligands (2-methylimidazole, 2-ethylimidazole and 2-methylbenzimidazole). One combination of ligands, 2-ethylimidazole and 2-methylbenzimidazole, results in the formation of SOD frameworks for the three metal centres despite this topology not being obtained for the individual ligands. Theoretical calculations confirm that this topology is the lowest in energy upon ligand mixing.

Different mixed-ligand Zeolitic Imidazolate Frameworks (ZIFs) with sodalite topology, i.e. isoreticular to ZIF-8, unachievable by conventional synthetic routes, have been prepared using a solvent-free methodology.     

The Henry reaction catalyzed by zeolitic imidazolate framework ZIF-8

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Reversible pressure-induced amorphization of a zeolitic imidazolate framework (ZIF-4)

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.     

Nanoporous carbons obtained by carbonization of copolymers impregnated by salts

This paper demonstrates the results of research on influence of types of polymer and kinds of salts used for impregnation of the polymer on porous structure formation in the final carbonaceous product. The studies were performed in two stages. In the first stage, the role of polymer structure were mainly studied. To achieve the aim, three different porous copolymers (polyimide and two types of polyester) were impregnated with the same salts (NiSO₄, and the mixture of AgNO₃ and Gd(NO₃)₃). In the second part of the study, only one polymer (polyimide) was impregnated by three mixtures of salts (chlorides, nitrates and sulphates of K, Cu(II) and Fe(III)). This approach allowed to evaluate the impact of the mixture of salts on porosity of the carbons, which were to be prepared. The obtained results revealed that when the impregnation was applied as a method for activation and moulding of porosity of carbonaceous materials prepared from polymers, several factors should be taken into account. First of all, initial decomposition temperatures of the polymers and the salts should be compared to find out if carbonization and activation processes proceed simultaneously or not. If the copolymer was carbonized and gases were released from decomposing salts, they reacted each other and synergic effect of polymer and salts properties were observed. Such conditions favored the development of microporous structure of the obtained carbon. On the contrary, if the processes were separated in time because of high temperature of melting point of the salts more mesopores were retained.     

Amorphization of the prototypical zeolitic imidazolate framework ZIF-8 by ball-milling

We report the rapid amorphization of the prototypical substituted zeolitic imidazolate framework, ZIF-8, by ball-milling. The resultant amorphous ZIF-8 (a(m)ZIF-8) possesses a continuous random network (CRN) topology with a higher density and a lower porosity than its crystalline counterpart. A decrease in thermal stability upon amorphization is also evident.     

Tuning electrochemical transformation process of zeolitic imidazolate framework for efficient water oxidation activity

Metal-organic frameworks(MOFs)have been widely studied as efficient electrocatalysts for water oxidation due to their tunable structure and easy preparation.However,the rational design of MOFs-based electrocatalysts and fundamental understanding of their structural evolution during oxygen evolution reaction(OER)remain critical challenges.Here,we report a facile approach to tune the structural transformation process of the Co-based zeolitic imidazolate framework(ZIF)during the OER process by using water molecules as a vacancy promoter.The modified ZIF catalyst accelerates the structural transformation from MOF precursor to electrochemical active species and simultaneously enhances the vacancy density during the electrochemical activation process.The optimized electrocatalyst exhibits an extremely low overpotential 175 mV to deliver 10 mA cm^-2 and superior durability(100 h)at 100 mA cm^-2.The comprehensive characterization results reveal the structural transformation from the initial tetrahedral Co sites to cobalt oxyhydroxide(CoOOH)and the formation process of oxygen vacancies(CoOOH-Vo)at a high anodic potential.These findings represent a promising way to achieve highly active MOF-based electrocatalysts for water oxidation.     

Top-down patterning of zeolitic imidazolate framework composite thin films by deep X-ray lithography

For the first time a top-down process was used to control the spatial location of Metal-Organic Frameworks on a surface. Deep X-ray lithography was utilised to micropattern a Zeolitic Imidazolate Framework layer on a sol-gel surface, with exposure hardening the sol-gel by inducing crosslinking while leaving the frameworks intact.     

The calcined zeolitic imidazolate framework-8 (ZIF-8) under different conditions as electrode for supercapacitor applications

Zeolitic imidazolate framework-8 (ZIF-8) is synthesized by typical solvothermal method and subsequently calcined under air and nitrogen atmosphere, respectively. The carbon in the calcined ZIF-8 under nitrogen atmosphere was from the carbonization of the guest molecules, without adding any other carbon sources. The samples are characterized by X-ray diffraction, Fourier transform infrared spectroscopy, and electrochemical analyzer system. When the ZIF-8 is used as electrode materials for a supercapacitor in 6 M KOH electrolyte, it displays a pseudocapacitive behavior. The untreated ZIF-8 and calcined ZIF-8 under air and nitrogen atmosphere electrodes exhibit a specific capacitance of 96, 156, and 185 F g^?1, respectively, at a scan rate of 5 mV s^?1 and good stability over 1,500 cycles. These results indicate that the ZIF-8 is a promising material for supercapacitors.     

Efficient oxidation of ethylbenzene catalyzed by cobalt zeolitic imidazolate framework ZIF-67 and NHPI

Efficient catalytic oxidation of ethylbenzene to acetophenone was realized using the catalytic system of cobalt zeolitic imidazolate framework ZIF-67/N-hydroxyphthalimide （NHPI） under mild conditions. 95.2% conversion of ethylbenzene with 90.3% selectivity to acetophenone could be obtained at 373 K under 0.3 MPa 02 for 9 h. The results show that there exists synergetic effect between ZIF-67 and NHPI. 1-Phenylethyl hydroperoxide （PEHP） was generated via a radical process involving the hydrogen abstraction from ethylbenzene by phthalimide N-oxyl, and subsequently effectively decomposed to acetophenone by ZIF-67.     

From interpenetrating polymer networks to hierarchical porous carbons for advanced supercapacitor electrodes

A novel and effective strategy to fabricate hierarchical porous carbons for supercapacitors is developed via in-situ activation of interpenetrating polymer networks obtained from simultaneous polymerization of the monomers for two polymeric networks.     

Uptake and separation of Xe and Kr by a zeolitic imidazolate framework with a desirable pore window

Journal of Radioanalytical and Nuclear Chemistry - Crystalline solids of zeolitic imidazolate framework (ZIF)-69 with a suitable pore window size matching with atomic diameter of xenon is utilized...     

Zinc tartrate oriented hydrothermal synthesis of microporous carbons for high performance supercapacitor electrodes

A novel zinc tartrate oriented hydrothermal synthesis of microporous carbons was reported. Zinc–organic complex obtained via a simple chelation reaction of zinc ions and tartaric acid is introduced into the networks of resorcinol/formaldehyde polymer under hydrothermal condition. After carbonization process, the resultant microporous carbons achieve high surface area(up to 1255 m~2/g) and large mean pore size(1.99 nm) which guarantee both high specific capacitance(225 F/g at 1.0 A/g) and fast charge/discharge operation(20 A/g) when used as a supercapacitor electrode. Besides, the carbon electrode shows good cycling stability, with 93% capacitance retention at 1.0 A/g after 1000 cycles. The welldesigned and high-performance microporous carbons provide important prospects for supercapacitor applications.     

Structural evolution of zeolitic imidazolate framework-8

We report the structural evolution of zeolitic imidazolate framework-8 (ZIF-8) as a function of time at room temperature. We have identified the different stages of ZIF-8 formation (nucleation, crystallization, growth, and stationary periods) and elucidated its kinetics of transformation. We hypothesize that the observed semicrystalline-to-crystalline transformation may take place via solution- and solid-mediated mechanisms, as suggested by the observed phase transformation evolution and Avrami's kinetics, respectively. A fundamental understanding of ZIF-8 structural evolution as demonstrated in this study should facilitate the preparation of functional metal-organic framework phases with controlled crystal size and extent of crystallinity.     

Facile mechanosynthesis of amorphous zeolitic imidazolate frameworks

A fast and efficient mechanosynthesis (ball-milling) method of preparing amorphous zeolitic imidazolate frameworks (ZIFs) from different starting materials is discussed. Using X-ray total scattering, N(2) sorption analysis, and gas pycnometry, these frameworks are indistinguishable from one another and from temperature-amorphized ZIFs. Gas sorption analysis also confirms that they are nonporous once formed, in contrast to activated ZIF-4, which displays interesting gate-opening behavior. Nanoparticles of a prototypical nanoporous substituted ZIF, ZIF-8, were also prepared and shown to undergo amorphization.     

A hybrid monolithic column based on flower-shaped zeolitic imidazolate framework for efficient capillary microextraction of brominated flame retardants

A novel flower-shaped zeolitic imidazolate framework (ZIF) doped organic-inorganic hybrid monolithic column (ZIF-HMC) was prepared by a simple sol-gel “one-step” method and utilized for efficient capillary microextraction (CME) of four brominated flame retardants. The prepared monolithic was characterized by Fourier transform infrared, scanning electron microscopy, X-ray photoelectron spectroscopy, energy disperse spectroscopy, and N₂ adsorption-desorption. The parameters of CME were optimized by orthogonal array design. Under the optimal conditions, the ZIF-HMC showed excellent extraction efficiency, the limit of detection (LODs) and the limit of quantification (LOQs) were in the range of 0.52∼3.1 μg/L and 1.7∼10 μg/L, respectively, and the proposed method demonstrated good recovery (88.8%–116.6%) with the RSD less than 13.6% and a reusability of at least 30 times. The ZIF-HMC possessed great potential for separating organic pollutants and the strategy used here could be extended to prepare other derivatized HMC functionalized monoliths.