Solvent-Free Synthesis of Zeolitic Imidazolate Frameworks and the Catalytic Properties of Their Carbon Materials

Zeolitic imidazolate frameworks (ZIFs) are traditionally synthesized solvothermally by using cost- and waste-incurring organic solvents. Here, a direct synthesis method is reported for ZIF-8, ZIF-67, and their heterometallic versions from solid precursors only. This solvent-free crystallization method not only completely avoids organic solvents, but also provides an effective path for the synthesis of homogeneous mixed-metal ZIFs. Furthermore, under templating by NaCl/ZnCl₂ eutectic salt, carbonization of the ZIF materials gives rise to a series of N-containing high-surface-area carbon materials with impressive catalytic properties for the oxygen reduction reaction.     

Host-Guest Interaction in Ethylene and Ethane Separation on Zeolitic Imidazolate Frameworks as Revealed by Solid-State NMR Spectroscopy

The separation of ethane/ethylene mixture by using metal-organic frameworks (MOFs) as adsorbents is strongly associated with the pore size-sieving effect and the adsorbent-adsorbate interaction. Herein, solid-state NMR spectroscopy is utilized to explore the host-guest interaction and ethane/ethylene separation mechanism on zeolitic imidazolate frameworks (ZIFs). Preferential access to the ZIF-8 and ZIF-8-90 frameworks by ethane compared to ethylene is directly visualized from two-dimensional ¹H-¹H spin diffusion MAS NMR spectroscopy and further verified by computational density distributions. The ¹H MAS NMR spectroscopy provides an alternative for straightforwardly extracting the adsorption selectivity of ethane/ethylene mixture at 1.1∼9.6 bar in ZIFs, which is consistent with the IAST predictions.     

Synthesis and Optimization of Zeolitic Imidazolate Frameworks for the Oxygen Evolution Reaction

Metal–organic frameworks/zeolitic imidazolate frameworks (MOFs/ZIFs) and their post-synthesis modified nanostructures, such as oxides, hydroxides, and carbons have generated significant interest for electrocatalytic reactions. In this work, a high and durable oxygen evolution reaction (OER) performance directly from bimetallic Zn_100−xCo_x-ZIF samples is reported, without carrying out high-temperature calcination and/or carbonization. ZIFs can be reproducibly and readily synthesized in large scale at ambient conditions. The bimetallic ZIFs show a systematic and gradually improved OER activity with increasing cobalt concentration. A further increase in OER activity is evidenced in ZIF-67 polyhedrons with controlled particle size of <200 nm among samples of different sizes between 50 nm and 2 μm. Building on this, a significantly enhanced, >50 %, OER activity is obtained with ZIF-67/carbon black, which shows a low overpotential of approximately 320 mV in 1.0 m KOH electrolyte. Such activity is comparable to or better than numerous MOF/ZIF-derived electrocatalysts. The optimized ZIF-67 sample also exhibits increased activity and durability over 24 h, which is attributed to an in situ developed active cobalt oxide/oxyhydroxide related nanophase.     

ZIF-8原位负载Pd纳米粒子及其在Suzuki-Miyaura反应中的应用(英文)

将PdCl2与ZIF-8的反应原料ZnO和2-甲基咪唑按照一定的比例,采用机械化学法原位将Pd2+负载在ZIF-8上(Pd2+/ZIF-8)。然后用NaBH4将Pd2+/ZIF-8进行还原,得到均匀分散的Pd纳米颗粒(Pd/ZIF-8)。通过XRD、N2吸附、透射电镜、ICP-AES、XPS等对Pd/ZIF-8的结构、形貌、价态等进行了表征。结果表明用机械化学法原位制备的Pd/ZIF-8具有分散均匀、容易大量制备的优点。该催化剂不仅能高效催化Suzuki-Miyaura交叉偶联反应,并且能够多次循环利用。     

Zeolitic Imidazolate Frameworks: Synthesis,Functionalization, and Catalytic/Adsorption Applications

Zeolitic imidazolate frameworks (ZIFs) are comprised of transition metal ions (Zn, Co) and a range of imidazolate linkers in a tetrahedral coordination similar to that in crystalline aluminosilicate zeolites. The high surface area, tunable nanoporosity that can be subject to functionalization and the excellent thermal/chemical stability of ZIFs are attractive for heterogeneous catalysis and selective gas adsorption/separation. This review presents the current trends in synthesis, surface modification and catalytic reactions/adsorption of ZIF-based materials with particular emphasis on ZIF-8, which is the most widely studied structure among ZIFs.     

ZIF-67衍生的离子掺杂材料制备及电催化性能研究进展

钴基沸石咪唑酯骨架材料(ZIFs)结构和功能的多样化使其在电化学领域得到了广泛应用。然而,ZIF-67的低固有电导率和容易自聚集的性质,通常会导致高过电位。因此,有必要通过其他离子掺杂进行优化,以提高ZIF-67衍生物的电催化性能。本文概述了ZIF-67的合成及其析氧性能,总结了常见的通过离子掺杂提高ZIF-67析氧性能的方法,并梳理了其在催化电解水析氧方面的应用。最后对ZIF-67及其衍生物的发展方向和前景进行展望,为今后的研究提供参考。     

沸石咪唑酯骨架-67高效催化L-丙交酯的开环聚合反应

为了探究沸石咪唑酯骨架材料(Zeolitic Imidazolate Frameworks,ZIFs)结构中的金属单元对其催化活性的影响,我们采用室温法合成了ZIF-8、Zn/Co-ZIF和ZIF-67,并用其催化L-丙交酯的本体开环聚合反应。 在相同的反应条件下,ZIF-67具有最高的催化活性。 与2-甲基咪唑(配体)作为催化剂相比,ZIF-67催化得到的聚乳酸具有高度全同立构结构。 此外,基质辅助激光解吸-飞行时间(MALDI-TOF)质谱表明,ZIF-67催化得到的聚乳酸主要为线状结构。 经过3次循环反应后,ZIF-67的催化活性没有明显降低。     

Fischer–Tropsch synthesis using zeolitic imidazolate framework (ZIF-7 and ZIF-8)-supported cobalt catalysts

The Fischer–Tropsch synthesis using cobalt catalysts supported on zeolitic imidazolate frameworks (ZIFs), ZIF-7 and ZIF-8, has been investigated. ZIF-7, ZIF-8 and corresponding cobalt-containing catalysts, after preparation, were characterized using various techniques. Thermogravimetric analysis results show that ZIF-7 and ZIF-8 supports have good thermal stability for the Fischer–Tropsch synthesis reaction, and weaker interaction between cobalt and zinc in the ZIF-7 and ZIF-8 supports results in more cobalt reduction. The catalytic performance was evaluated in Fischer–Tropsch synthesis and compared with that of a cobalt catalyst supported on SBA-15 promoted with zinc. The pore structure of the ZIF supports plays an essential role in product selectivity for the prepared catalysts. The carbon number in hydrocarbon products and olefin selectivity depend on cobalt dispersion and support structure owing to the impacts of site density and carrier skeleton on the speed of diffusion-enhanced olefin re-adsorption reactions.     

Water stability of cobalt doped ZIF-8: a quantitative study using optical analyses

Zeolitic imidazolate frameworks (ZIFs), in particular ZIF-8 (made of Zn²⁺ and 2-methyilimidazolate) and cobalt-doped-ZIF-8, are found important for many energy and environmental applications. It was reported that ZIFs show excellent structural stability in water and thus ideal for aqueous applications. However, recent studies also found some evidence that ZIF-8 undergoes hydrolysis in water. Despite the importance of ZIF's stability in many aqueous applications, the extent of ZIFs' degradation in water is still not yet fully understood. In this study, we report a quantitative study of the water stability of 0–100 at% cobalt-doped ZIF-8, using a new combination of analytical tools. The study demonstrated the importance of analyzing both filtered powders and the filtrate liquid systematically, in particular by using UV–Vis spectroscopy and thermogravimetric analysis. The combination of analytical tools allowed the study on the effects of ZIF concentrations in water, cobalt doping levels, and amounts of ligands in water on the water stability of ZIF samples. The effect of cobalt-doping was investigated by using ZIF particles with identical sizes (200–400 nm), in order to eliminate the effects of particle size on hydrolysis. Unlike other synthesis methods, a mechanochemical ball milling method allowed the production of nano-scale ZIF-8 particles with similar sizes, independent of cobalt-doping levels. The proposed combination of analytical tools including UV–Vis spectroscopy can be applied to the study of the water stability of other MOF materials.     

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.     

Two-step pyrolysis of ZIF-8 functionalized with ammonium ferric citrate for efficient oxygen reduction reaction

Zeolitic imidazolate frameworks(ZIFs) are widely employed in catalyst synthesis as parental materials for electrochemical energy storage and conversion. Herein, we have demonstrated a facile synthesis of highly efficient catalyst for oxygen reduction reaction in both alkaline and acidic medium, which is derived from ZIF-8 functionalized with ammonium ferric citrate via two-step pyrolysis in Ar and NH_3 atmosphere.The results reveal that the catalytic activity improvement after NH3 pyrolysis benefits from mesoporedominated morphology and high utilization of Fe-containing active sites. The optimum catalyst shows excellent performance in zinc-air battery and polymer electrolyte membrane fuel cell tests.     

Selective synthesis of ZIFs from zinc and nickel nitrate solution for photocatalytic H2O2 production

Hydrogen peroxide (H₂O₂) is one of the most promising, green, and effective oxidants that can be used in different applications. In this study, zeolitic imidazolate frameworks (ZIFs), consisting of organic ligands and metal sites, were selectively prepared from zinc or nickel nitrate solutions for use in photocatalytic H₂O₂ production. High concentrations of zinc nitrate solution provided more metal sites to coordinate with 2-methylimidazole, producing ZIF-8 with larger particle size, whereas low zinc nitrate concentrations resulted in more interconnected N–H⋯N hydrogen bonds, forming 2D-layered ZIF-L, with smaller particle size. Various concentrations of zinc and nickel nitrate solutions produced ZIFs that exhibited ZIF-8 or ZIF-L topology, with bandgap energies of 5.45 and 4.85 eV, respectively. These samples could serve as promising photocatalyst for the successful production of H₂O₂ under Xenon lamp irradiation.     

Crystals as molecules: postsynthesis covalent functionalization of zeolitic imidazolate frameworks

A new crystalline zeolitic imidazolate framework, ZIF-90, was prepared from zinc(II) nitrate and imidazolate-2-carboxyaldehyde (ICA) and found to have the sodalite-type topology. Its 3D porous framework has an aperture of 3.5 A and a pore size of 11.2 A. The pores are decorated by the aldehyde functionality of ICA which has allowed its transformation to the alcohol functionality by reduction with NaBH4 and its conversion to imine functionality by reaction with ethanolamine to give ZIF-91 and ZIF-92, respectively. The N2 adsorption isotherm of ZIF-90 shows a highly porous material with calculated Langmuir and BET surface areas of 1320 and 1270 m2 g(-1). Both functionalized ZIFs retained high crystallinity and in addition ZIF-91 maintained permanent porosity (surface areas: 1070 and 1010 m2 g(-1)).     

Zeolitic Imidazolate framework-8 as efficient pH-sensitive drug delivery vehicle

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.     

Vapor‐Phase Linker Exchange of the Metal–Organic Framework ZIF‐8: A Solvent‐Free Approach to Post‐synthetic Modification

Zeolitic imidazolate frameworks (ZIFs) are a sub‐class of metal–organic frameworks (MOFs). Although generally stable, ZIFs can undergo post‐synthetic linker exchange (PSLE) in solution under mild conditions. Herein, we present a novel, solvent‐free approach to post‐synthetic linker exchange through exposure to linker vapor.     

Facile synthesis of size-tunable ZIF-8 nanocrystals using reverse micelles as nanoreactors

This paper describes a robust method for the synthesis of high-quality ZIF-8 nanocrystals using reverse micelles as discrete nanoscale reactors.The precise size control of ZIF-8 nanocrystals is conveniently achieved by tuning the concentration of precursors,reaction temperatures,the amount of water,and the structure of surfactants.The as-synthesized ZIF-8 nanocrystals are of narrow distribution and tunable size.A size-dependent catalytic activity for Knoevenagel condensation reaction is further demonstrated by using ZIF-8 nanocrystals with different sizes as the catalysts.This facile method opens up a new opportunity in the synthesis of various ZIFs nanocrystals.     

A Facile and In-situ Methanol-mediated Fabrication of Low Pd Loading,High-efficiency and Size-selectivity Pd@ZIF-8 Hydrogenation Catalyst

In-situ encapsulation of tiny and well-dispersed Pd nanoparticles (Pd NPs) in zeolitic imidazolate frameworks (ZIFs) was firstly achieved using a one-pot and facile methanol-mediated growth approach, in which methanol served as both solvent and a mild reductant. The microstructure, morphology, crystallinity, porosity as well as evolution process of the catalysts were determined by TEM, XRD, N₂ adsorption and UV-vis spectra. Due to the complete encapsulation of such Pd NPs combined with ultrahigh surface area and uniform microporous structure of ZIF-8, the resulting Pd@ZIF-8-60 min nanocomposite exhibited more superior catalytic activity for olefins hydrogenation with TOF of 7436 h⁻¹ and excellent size selectivity than previously reported catalysts. Furthermore, the catalyst displays excellent recyclability for 1-octene hydrogenation and without any loss of the Pd active species.     

Ionic electro-active polymer actuator based on cobalt-containing nitrogen-doped carbon/conducting polymer soft electrode

Nanoscale cobalt-containing nitrogen-doped porous carbon (CoNC) materials were prepared by thermolysis of a zeolitic imidazolate framework (ZIF), ZIF-67, at different temperatures and their application for ionic electro-active polymer (EAP) actuator was evaluated. CoNC-700, which was obtained from ZIF-67 pyrolysis at 700 °C, exhibits specific surface area of 753.86 m² g⁻¹, pore volume of 0.5768 cm³ g⁻¹, and specific capacitance of 120.7 F∙g⁻¹. CoNC/conducting polymer soft electrode were fabricated by unitizing effective interaction of CoNC with poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS). High-performance ionic actuators were developed for the first time using this CoNC/PEDOT:PSS soft electrode. The developed ionic EAP actuator exhibited large peak-to-peak displacement of 20.4 mm and high bending strain of 0.28% (3 V and 0.1 Hz). Therefore, ZIFs or metal organic frameworks (MOFs) can be applied to provide significant improvements in EAP actuators, which can play key roles as technological advances toward bioinspired actuating devices required for next-generation soft and wearable electronics.     

Enumeration of not-yet-synthesized zeolitic zinc imidazolate MOF networks: a topological and DFT approach

Twenty-one zeolitic imidazolate metal-organic frameworks based on Zn connectors (ZIFs) are derived and compared to known imidazolate networks. Not-yet-synthesized zinc imidazolates are identified on the basis of DFT total energy scoring. The structure with lowest energy is not porous and represents an unusual structure type with zni topology. Total energy scoring indicates the lcs and pcb networks as reliable ZIF candidates. The intrinsic channel chirality of the lcs network makes this rare topology an attractive target for the synthetic effort. Among the porous ZIFs candidates, the sodalite type, sod, is also found.     

Development of a force field for zeolitic imidazolate framework-8 with structural flexibility

A force field is developed for zeolitic imidazolate framework-8 (ZIF-8) with structural flexibility by combining quantum chemical calculations and classical Amber force field. The predicted crystalline properties of ZIF-8 (lattice constants, bond lengths, angles, dihedrals, and x-ray diffraction patterns) agree well with experimental results. A structural transition from crystalline to amorphous as found in experiment is observed. The mechanical properties of ZIF-8 are also described fairly well by the force field, particularly the Young's modulus predicted matches perfectly with measured value. Furthermore, the heat capacity of ZIF-8 as a typical thermophysical property is predicted and close to experimental data available for other metal-organic frameworks. It is revealed the structural flexibility of ZIF-8 exerts a significant effect on gas diffusion. In rigid ZIF-8, no diffusive behavior is observed for CH(4) within the simulation time scale of current study. With the structural flexibility, however, the predicted diffusivities of CH(4) and CO(2) are close to reported data in the literature. The density distributions and free energy profiles of CH(4) and CO(2) in the pore of ZIF-8 are estimated to analyze the mechanism of gas diffusion.