Synthesis Of Zeolitic Imidazolate Frameworks Research Articles

Controllable synthesis of zeolitic imidazolate frameworks and the peanut shell carbon composite for sensitive and selective detection of Pb2+ and Cd2+ ions

Zeolitic imidazolate frameworks (ZIF) and the peanut shell carbon (PSC) composite (ZIF-8 @PSC) nanocomposite is successfully fabricated and exhibits superior current response for simultaneously detecting Pb2+ and Cd2+. The obtained composite has been characterized via SEM, TEM, XRD, FTIR, N2 adsorption-desorption methods. The suitable pore structure of ZIF-8 @PSC with the highest mesoporous ratio (ca. 11%) is conducive to mass transportation and charge transfer. The available specific surface area (236.6 m2 g−1), the lowest internal resistance (81.8 Ohm) as well as the synergistic effect between ZIF and PSC in ZIF-8 @PSC(4−1) electrode contribute to the enhanced current signals for the detection of Pb2+ and Cd2+ in aqueous solution. Additionally, the cyclic voltammetry investigation reveals that the kinetic process of the target heavy metal ions on the surface of the ZIF-8 @PSC(4−1) electrode is controlled by diffusion, which is verified by the Warburg impedance in low frequency region. Under the optimum conditions, the peak currents are linearly related with the concentration of Pb2+ and Cd2+ in the range of 0.1–8 µM (Pb2+) and 0.06–9 µM (Cd2+), and the corresponding limit of detection is 8.25 nM (S/N = 3) and 16 nM (S/N = 3), respectively, which are superior to other reported results. Based on the outstanding selectivity, stability, repeatability, and reproducibility, the analytical performance for the detection of the metal ions is assessed individually and simultaneously. It is found that the obtained method exhibits simultaneous sensing ability toward Cd(II) and Pb(II). During the multi-component sample, the detection and quantification of Pb(II) is more sensitive. Finally, the proposed method is applied to detect Pb2+ and Cd2+ in domestic sewage and satisfactory results have been achieved.

ZIF-8 and Its Magnetic Functionalization as Vehicle for the Transport and Release of Ciprofloxacin.

The use of nanomaterials for the controlled release of drugs aims to enhance their effectiveness, especially when poorly soluble in water, and achieve their rapid, localized, and effective administration. The present study focuses on the use of a Zeolitic Imidazolate Framework-8 (ZIF-8) as vehicle for the transport and controlled release of the antibiotic ciprofloxacin (CIP) as model due to its favorable physicochemical characteristics. The objective is to synthesize the ZIF-8 material loaded with CIP through encapsulation for subsequent release of the drug in neutral and acid physiological media. In addition, functionalization of the CIP/ZIF compound with magnetic nanoparticles (NP) was sought to increase its traceability through the possible use of magnetic fields. Characterizations by XRD, FT-IR, SEM-EDX, and TGA showed a satisfactory synthesis of both pure ZIF-8 and ciprofloxacin-loaded ZIF-8, with high crystallinity and thermal stability. The release profiles showed an abrupt initial release that stabilized over time. A much higher release (20-80% greater) was obtained in acid versus neutral pH in all cases, attributable to the collapse of the ZIF-8 structure in acid media. In addition, functionalization of the material with iron NPs did not affect the behavior of the system during drug release. Antimicrobial activity tests against E. coli and S. aureus showed that ZIF-8 per se exerts antimicrobial activity, while the compounds CIP/ZIF and magnetic CIP/ZIF increased the antimicrobial capacity of pure CIP by 10-20%. The ZIF-8 system has high potential as a drug carrier and release agent for the treatment of diseases, especially those that cause acidification of the cellular environment, achieving a rapid, localized, and targeted action with the possibility of achieving traceability of the system after its magnetic functionalization.

Synthesis of zeolitic imidazolate framework-8 (ZIF-8) using different solvents for lead and cadmium adsorption

Synthesis of zeolitic imidazolate framework-8 (ZIF-8) using different solvents for lead and cadmium adsorption

Influence of Salt Doping on the In Situ Synthesis of Zeolitic Imidazolate Framework-8 in Poly(diallyldimethylammonium chloride)/Poly(sodium-p-styrenesulfonate) Polyelectrolytes Complexes

Influence of Salt Doping on the In Situ Synthesis of Zeolitic Imidazolate Framework-8 in Poly(diallyldimethylammonium chloride)/Poly(sodium-p-styrenesulfonate) Polyelectrolytes Complexes

In Situ Synthesis of Multivariate Zeolitic Imidazolate Frameworks for C2 H4 /C2 H6 Kinetic Separation.

Herein, a new approach for the in situ synthesis of zeolitic imidazolate framework (ZIF) nanoparticles with triple ligands, referred to as Sogang ZIF-8 (SZIF-8), is reported for enhanced C2 H4 /C2 H6 kinetic separation. SZIF-8 consists of tetrahedral zinc metals coordinated with tri-butyl amine (TBA), 2,4-dimethylimidazole (DIm), and 2-methylimidazole (MIm). SZIF-8(x) with different DIm contents in x (up to 23.2 mol%) are synthesized in situ because TBA preferably deprotonates DIm ligands due to the much lower pKa of DIm over MIm, allowing for the Zn-DIm coordination. The Zn-DIm coordination reduces the window size of ZIF-8 with suppressed linker flipping motion due to bulky DIm ligands and simultaneously enhances the interfacial interaction between 6FDA-DAM polyimide (6FDA) and SZIF-8 via electron donor-acceptor interactions. Consequently, 6FDA/SZIF-8(13) mixed matrix membrane exhibits an excellent C2 H4 permeability of 60.3 Barrer and C2 H4 /C2 H6 selectivity of 4.5. The temperature-dependent transport characterization reveals that such excellent C2 H4 /C2 H6 kinetic separation is attained by the enhancement in size discrimination-based energetic selectivity. Our hybrid multi-ligand approach can offer a useful tool for the fine-tuning of molecular structures and textural properties of other metal organic frameworks.

Comparative life cycle assessment on zeolitic imidazolate framework-8 (ZIF-8) production for CO2 capture

Metal-organic frameworks (MOFs) combine the advantages of both organic and inorganic materials. Among the synthesized MOFs, ZIF-8 is promising for CO2 capture, raising the need for its sustainable production. The life cycle assessment (LCA) of various ZIF-8 synthesis methods such as solvothermal (DMF), solvothermal (MeOH), microwave, sonochemical, mechanochemical, dry-gel conversion and aqueous system was investigated. The findings indicated that the seven production methods have the highest impact on marine ecotoxicity, followed by human toxicity non-carcinogenic, and terrestrial ecotoxicity among the 18 categories of evaluation studies. The main contributor towards environmental degradation was the solvent for washing, N, N-dimethylformamide (DMF) in most of the methods. It is also revealed that replacing the solvent of DMF with methanol remarkably reduced the influence on human health, ecosystem and resources in the solvothermal (MeOH) method as compared to the solvothermal (DMF) method. As a whole, the mechanochemical method has the least impact on the environment because it has fewer production steps and is easy to operate. Therefore, this work delineates comprehensive environmental influences of different ZIF-8 synthesis methods to lay the groundwork for its mass and sustainable production.

Surfactant regulated synthesis of ZIF-8 crystals as carbonic anhydrase-mimicking nanozyme

Zeolitic imidazolate framework-8 (ZIF-8) nanozymes were successfully synthesized by using non-ionic surfactant Triton X-100 as regulator. The surfactant molecules can bind on ZIF-8 surface to modulate the nucleation and facet growth, which therefore produces ZIF-8 crystals with controlled morphology and size. The as-prepared ZIF-8 crystals reproduce the functional property of natural carbonic anhydrase (CA) by showing excellent CA-like esterase activity. The catalytic activity of ZIF-8 nanozymes was greatly enhanced at high temperature, which is superior to natural CA and is of great potential for practical applications. Moreover, the esterase activity of ZIF-8 shows great dependence on the crystal size. Basically, smaller ZIF-8 nanozymes had higher catalytic activity at a specified temperature, except for the smallest ZIF-8 crystals with size of ~50 nm that gave reduced activity due to aggregation at high temperatures of 60 or 80 °C. In addition, colorimetric experiments showed that ZIF-8 nanozymes showed similar hydration activity to that of natural CA. The study probes into the effect of nonionic surfactant on ZIF-8 synthesis as well as the abnormal size effect at higher temperature, which is of great help for the development of suitable nano-enzymes for industry applications.

The adsorption property of in-situ synthesis of MOF in alginate gel for ofloxacin in the wastewater

ABSTRACT Although metal-organic frameworks (MOFs) are advantageous to the removal of organic pollutants, the general MOFs in powder form is disadvantageous to their practical applications. In-situ MOF synthesis in alginate gel is a good way to fabricate an MOF composite for many applications, which is different from blending MOF particles with polymers. In-situ synthesis of Zeolitic Imidazolate Framework-8 (ZIF-8) in alginate gel is in the form of beads with rough wrinkles and has many pores inside. When used as an absorbent, in-situ synthesis of ZIF-8 in alginate gel could remove 97.7±0.9% of ofloxacin from ofloxacin solution and the equilibrium adsorption capacity is up to 160.6±1.3 mg/g. During the adsorption, ofloxacin is first brought into the gel by the solvent exchange and gel microchannel adsorption, and it can then be absorbed by in-situ ZIF-8. Moreover, the adsorption efficiency can reach 85.5% even after four cycles of adsorption. We believe that in-situ synthesis of ZIF-8 in alginate gel will be an appropriate material for the removal of ofloxacin in the wastewater.

Green Synthesis of Zeolitic Imidazolate Frameworks: A Review of Their Characterization and Industrial and Medical Applications.

Metal organic frameworks (MOF) are a class of hybrid networks of supramolecular solid materials comprising a large number of inorganic and organic linkers, all bound to metal ions in a well-organized fashion. Zeolitic imidazolate frameworks (ZIFs) are a sub-group of MOFs with imidazole as an organic linker to metals; it is rich in carbon, nitrogen, and transition metals. ZIFs combine the classical zeolite characteristics of thermal and chemical stability with pore-size tunability and the rich topological diversity of MOFs. Due to the energy crisis and the existence of organic solvents that lead to environmental hazards, considerable research efforts have been devoted to devising clean and sustainable synthesis routes for ZIFs to reduce the environmental impact of their preparation. Green chemistry is the key to sustainable development, as it will lead to new solutions to existing problems. Moreover, it will present opportunities for new processes and products and, at its heart, is scientific and technological innovation. The green chemistry approach seeks to redesign the materials that make up the basis of our society and our economy, including the materials that generate, store, and transport our energy, in ways that are benign for humans and the environment and that possess intrinsic sustainability. This study covers the principles of green chemistry as used in designing strategies for synthesizing greener, less toxic ZIFs the consume less energy to produce. First, the necessity of green methods in today’s society, their replacement of the usual non-green methods and their benefits are discussed; then, various methods for the green synthesis of ZIF compounds, such as hydrothermally, ionothermally, and by the electrospray technique, are considered. These methods use the least harmful and toxic substances, especially concerning organic solvents, and are also more economical. When a compound is synthesized by a green method, a question arises as to whether these compounds can replace the same compounds as synthesized by non-green methods. For example, is the thermal stability of these compounds (which is one of the most important features of ZIFs) preserved? Therefore, after studying the methods of identifying these compounds, in the last part, there is an in-depth discussion on the various applications of these green-synthesized compounds.

Synthesis of zeolitic imidazolate framework-8 and gold nanoparticles in a sustained out-of-equilibrium state

The design and synthesis of crystalline materials are challenging due to the proper control over the size and polydispersity of the samples, which determine their physical and chemical properties and thus applicability. Metal − organic frameworks (MOFs) are promising materials in many applications due to their unique structure. MOFs have been predominantly synthesized by bulk methods, where the concentration of the reagents gradually decreased, which affected the further nucleation and crystal growth. Here we show an out-of-equilibrium method for the generation of zeolitic imidazolate framework-8 (ZIF-8) crystals, where the non-equilibrium crystal growth is maintained by a continuous two-side feed of the reagents in a hydrogel matrix. The size and the polydispersity of the crystals are controlled by the fixed and antagonistic constant mass fluxes of the reagents and by the reaction time. We also present that our approach can be extended to synthesize gold nanoparticles in a redox process.

Electric current-assisted synthesis of ZIF-8 with stoichiometric metal and ligand precursors for CO2 adsorption

Zeolitic imidazolate framework-8 (ZIF-8) crystals were obtained by an electric current-assisted synthesis method with stoichiometric Zn2+ and 2-methylimidazole precursors. The resulting ZIF-8-CS2 shows enhanced CO2 adsorption performance (31.2 cm3/g) with CO2/N2 selectivity of 9 at 273 K, while ZIF-8 prepared without electric current assistance shows CO2 adsorption of 18.4 cm3/g and CO2/N2 selectivity of 5. The increased CO2 adsorption ability is ascribed to the high specific surface area and total pore volume of ZIF-8-CS2.

Peptide-Mediated Synthesis of Zeolitic Imidazolate Framework-8: Effect of Molecular Hydrophobicity, Charge Number and Charge Location.

Three amphiphilic peptides with varied molecular hydrophobicity, charge number and charge location have been designed as regulators to modulate the crystal growth of zeolitic imidazolate framework-8 (ZIF-8). All three peptides can interact with ZIF-8 to inhibit {100} facet growth and produce truncated cubic crystals. The peptide’s molecular hydrophobicity plays a dominant role in defining the final morphology and size of the ZIF-8 crystals. The peptides with less charge and higher hydrophobicity can promote nuclei formation and crystal growth to give smaller ZIF-8 crystals. However, the charge located in the center of the molecular hydrophobic region has little effect on the crystal nucleation and growth due to the shielding of its charge by molecular aggregation. The study provides insights into the effect of molecular charge and hydrophobicity on ZIF-8 crystal growth and is helpful for guiding the molecular design for regulating the synthesis of metal-organic framework materials.

Template-directed synthesis of zeolitic imidazolate framework-8 derived Zn–Al layered double oxides decorated on the electrochemically anodized nanoporous aluminum substrate for thin film microextraction of chlorophenols followed by determination with high-performance liquid chromatography

In this work, hierarchical ZIF-8 coated anodized aluminum foil was prepared through in situ template-directed method without addition of any zinc salt. The hierarchical sorbent was synthesized by the formation of the final HZIF-8 on the previously created layered double oxide (LDO) template. The LDO template was created by calcining the firstly in situ prepared desired layered double hydroxide (LDH) precursor coated on the electrochemically anodized porous Al foil in an air atmosphere. The microextraction ability of the extracting device was studied through direct immersion thin film microextraction (DI-TFME). The extracted analytes were quantified by high-performance liquid chromatography equipped by UV detector (HPLC-UV). The present strategy was used for the simultaneous extraction and quantification of four selected chlorophenols (CPs) (as model analyte). The variables of the TFME were optimized using response surface methodology (Plackett-Burman and Box-Behnken design). Under the obtained optimum condition, the prepared film presented acceptable extraction properties including low limits of detection (0.03-0.22 µgL−1), good linear ranges (0.2–200 µgL−1, r2 > 0.9918) and satisfactory reproducibility (relative standard deviation, 3.6 < RSD < 5.8% for one film as inter- and intra-day RSD, 4.8 < RSD < 5.3% for film to film). Moreover, the obtained enrichment factors were in the range of 56-76. The kinetics and adsorption isotherm of the selected analytes adsorption to the prepared sorbent were also investigated. The maximum adsorption capacities of the selected analytes on the prepared sorbent were in the range of 26.4-80.1 mg g−1. The adsorption isotherm obeyed the Langmuir and Freundlich models. Moreover, the adsorption of the selected chlorophenols on the prepared film followed the pseudo-second-order kinetic model. Finally, the HZIF-8 film was utilized for the quantification of selected CPs in different types of water and wastewater samples. The results showed satisfactory relative recoveries (93–102%) and acceptable precisions (3.6 < RSD < 9.2%).

In Situ Thermal Solvent-Free Synthesis of Zeolitic Imidazolate Frameworks with High Crystallinity and Porosity for Effective Adsorption and Catalytic Applications

In Situ Thermal Solvent-Free Synthesis of Zeolitic Imidazolate Frameworks with High Crystallinity and Porosity for Effective Adsorption and Catalytic Applications

Ultrasound-Assisted Rapid ZIF-8 Synthesis, Porous ZnO Preparation by Heating ZIF-8, and Their Photocatalytic Activity

Zeolitic imidazolate framework-8 (ZIF-8) is synthesized quickly at room temperature in methanol with the support of ultrasound. Porous ZnO is also prepared via the thermal treatment of ZIF-8. The photocatalytic activities of the obtained materials are demonstrated via methylene blue (MB) decomposition under UV radiation. The obtained materials are characterized by means of X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), nitrogen adsorption/desorption isotherms, UV-Vis diffuse reflectance spectra (DR-UV-Vis), and photoluminescence spectra. The results indicate that ZIF-8 and the materials obtained from ZIF-8 by heating in the air have photocatalytic activity under UV irradiation. The ZnO sample obtained by ZIF-8 calcination at 660°C for 5 h has the highest photocatalytic activity. However, the MB degradation photocatalytic efficiency of the ZnO samples is even lower than that of the ZIF-8 samples, indicating that ZIF-8 is an effective photocatalyst in the treatment of environmental pollution.

An environmental-friendly pesticide-fertilizer combination fabricated by in-situ synthesis of ZIF-8

Stimulus-responsive pesticide or fertilizer systems have been emerged to improve the use efficiency of agrochemicals, reduce over-application and ensuing environmental problems. However, environmental-friendly synthesis of these systems still remain challenging. In this work, an environmental-friendly synthesis strategy has been developed to form a pesticide and fertilizer combination to achieve the integration of plant protection and nutrient supply. This pesticide-fertilizer combination system was fabricated using ammonium zinc phosphate (ZNP) and in-situ synthesized zeolitic imidazolate framework-8 (ZIF-8) as nutrients resources, and dinotefuran (DNF) as a pesticide. DNF was encapsulated in-situ (loading capacity of 12.32 ± 0.46%) during the ZIF-8 crystal synthesis process, rather than loaded by further adsorption, which improved its stability and prevented premature or rapid release. The hydrophobic ZIF-8 provided a pH-responsive slow-release behavior. The cumulative released DNF within seven days at pH 4.0, 7.0 and 10.0 was 66.30%, 40.41%, and 37.44%, respectively. The pesticide-fertilizer combination system showed significant effects on corn seed pre-cultivation, soil cultivation and pest control. This work provides a strategy for the integration of pesticide and fertilizer, which will reduce negative environmental effects caused by their over-applications and have great potential in modern sustainable agriculture.

Zeolitic Imidazolate Framework-8 Nanoparticles for Rhodamine B Adsorption

Background: Dye removal from effluents is one of the major problems faced in the world. It is a very important environmental issue and it is crucial to solve this problem. In this sense, ZIFs are increasingly becoming important in the environmental area. Objective: This work presents the synthesis of metalorganic framework Zeolitic Imidazolate Framework- 8 (ZIF-8) nanoparticles, characterization, and then determines the potential to remove Rhodamine B (RhB) from an aqueous solution. Methods: ZIF-8 was synthesized under solvothermal treatment at 25°C and it was characterized by X-ray diffraction, N2 adsorption-desorption, scanning electron microscopy, and infrared spectroscopy. To evaluate the capacity of the RhB, pH-influence and kinetic studies were carried out. The pseudo first- and second-order kinetic models were used to describe the kinetic data, and the rate constants were evaluated. Results: ZIF-8 had an average particle size of 47 ± 4.6 nm. The removal percentage increased significantly when the pH was in the range of 7.0-9.0. A pseudo-second-order kinetic of 13.00 mg/g was found for the RhB removal. The adsorption capacity at equilibrium was found to be 11.8 mg/g. Conclusion: According to the characterization results, the ZIF-8 synthesis was effective and produced a crystalline material. The ZIF-8 presented an affinity to the RhB dye. A pseudo-second- order kinetic model represented well the mechanism of interaction involved during RhB adsorption and ZIF-8.

Effect of new metal–organic framework (zeolitic imidazolate framework [ZIF-12]) in mixed matrix membranes on structure, morphology, and gas separation properties

Abstract In our study, the synthesis of zeolitic imidazolate framework (ZIF-12) crystals and the preparation of mixed matrix membranes (MMMs) with various ZIF-12 loadings were targeted. The characterization of ZIF-12 and MMMs were carried out by Fourier transform infrared spectroscopy analysis, thermogravimetric analysis, scanning electron microscopy (SEM), and thermomechanical analysis. The performance of MMMs was measured by the ability of binary gas separation. Commercial polyetherimide (PEI-Ultem® 1000) polymer was used as the polymer matrix. The solution casting method was utilized to obtain dense MMMs. In the SEM images of ZIF-12 particles, the particles with a rhombic dodecahedron structure were identified. From SEM images, it was observed that the distribution of ZIF-12 particles in the MMMs was homogeneous and no agglomeration was present. Gas permeability experiments of MMMs were measured for H2, CO2, and CH4 gases at steady state, at 4 bar and 35 °C by constant volume-variable pressure method. PEI/ZIF-12-30 wt% MMM exhibited high permeability and ideal selectivity values for H2/CH4 and CO2/CH4 were P H 2 / CH 4 = 331.41 ${P}_{{\text{H}}_{2}/{\text{CH}}_{4}}=331.41$ and P CO 2 / CH 4 = 53.75 ${P}_{{\text{CO}}_{2}/{\text{CH}}_{4}}=53.75$ gas pair.

Flow Microreactor Synthesis of Zeolitic Imidazolate Framework (ZIF)@ZIF Core-Shell Metal-Organic Framework Particles and Their Adsorption Properties.

Metal-organic frameworks (MOFs) with core-shell structures enable to enhance intrinsic properties of constituent MOFs and impart additional functional activities. Although shell thickness is a key factor for regulating the properties of core-shell MOF particles, controlling it has been challenging. The widely used batch reactor synthesis cannot produce core-shell particles with uniform shell thickness because of poor reactant mixing. A microreactor could ensure excellent mixing, and that would allow to control shell thickness. In this study, we synthesized zeolitic imidazolate framework-8 (ZIF-8)@ZIF-67 and ZIF-67@ZIF-8 core-shell particles using a microreactor and investigated the effects of the mixing performance on the shell thickness of the obtained particles. Our results demonstrated that rapid mixing was critical for the uniformity of the synthesized particles. The concentration of core particles is another key factor that can preferentially induce heterogeneous nucleation on the surface of the core particles without inducing self-nucleation in the bulk solution, particularly when the self-nucleation rate of the shell MOF is high. The N2 adsorption isotherms of the synthesized particles revealed their unique adsorption properties, which were ascribed to the core-shell structures obtained at low shell formation rates. Our simple and versatile synthesis technique not only allowed the preparation of ZIF@ZIF particles with novel functionalities but also can be extended to synthesize core-shell MOF particles with different combinations of core particles and shells.

Peptide-Mediated Synthesis of Zeolitic Imidazolate Framework-8 with Controllable Morphology and Size.

Peptides with a sequence of Nap-Ix-GPLGLAG-R4-NH2 (x = 2, 4, and 6, shorted as I2R4, I4R4, and I6R4) were used as capping agents for the synthesis of zeolitic imidazolate framework-8 (ZIF-8) in water. Peptide addition can significantly inhibit the growth of ZIF-8 crystals. The shape and size of ZIF-8 crystals was related closely to the number of isoleucine (Ile, I) residues as well as concentration of the peptide. The shape of ZIF-8 crystals changes from rhomboid dodecahedron to truncated rhombic dodecahedron to cube with the decreasing number of isoleucine residues from six to two. At a peptide concentration of 1.0 mM, the morphology of ZIF-8 crystals was cubic, truncated rhombic dodecahedron, and typical rhombic dodecahedron in the cases of I2R4, I4R4, and I6R4, respectively. Also, the particle size can be regulated from ca. 1.7 μm to <100 nm by controlling the peptide concentration from 0 to 2.0 mM. This work develops a simple and green method for the synthesis of ZIF-8 crystals with controllable shape and size in water, which shows high potential for biomedical and biological applications.