Zeolitic Imidazolate Framework Research Articles

Reshaped Local and Systemic Immune Responses Triggered by a Biomimetic Multifunctional Nanoplatform Coordinating Multi-Pathways for Cancer Therapy.

Immunotherapy has fundamentally transformed the clinical cancer treatment landscape; however, achieving intricate and multifaceted modulation of the immune systems remains challenging. Here, a multipathway coordination of immunogenic cell death (ICD), autophagy, and indoleamine 2,3-dioxygenase-1 (IDO1) was achieved by a biomimetic nano-immunomodulator assembled from a chemotherapeutic agent (doxorubicin, DOX), small interfering RNA (siRNA) molecules targeting IDO1 (siIDO1), and the zeolitic imidazolate framework-8 (ZIF-8). After being camouflaged with a macrophage membrane, the biomimetic nanosystem, named mRDZ, enriched in tumors, which allowed synergistic actions of its components within tumor cells. The chemotherapeutic intervention led to a compensatory upregulation in the expression of IDO1, consequently exerting an inhibitory effect on the reactive oxygen species (ROS) and autophagic responses triggered by DOX and ZIF-8. Precise gene silencing of IDO1 by siIDO1 alleviated its suppressive influence, thereby facilitating increased ROS production and improved autophagy, ultimately bolstering tumor immunogenicity. mRDZ exhibited strong capability to boost potent local and systemic antitumor immune responses with a feature of memory, which led to the effective suppression of the growth, lung metastasis, and recurrence of the tumor. Serving as an exemplary model for the straightforward and potent reshaping of the immune system against tumors, mRDZ offers valuable insights into the development of immunomodulatory nanomaterials for cancer therapy.

Tuning of Particle Size of Zeolitic Imidazolate Framework-7 via Rapid Synthesis Duration for CH4 Adsorption

In this work, zeolite imidazolate framework-7 (ZIF-7) nanoparticles are synthesized via a solvothermal method and rapid synthesis durations of 1 h and 3 h. The effect of the synthesis duration on the structural properties of ZIF-7 was characterized by XRD and FESEM analyses. Subsequently, CH4 single gas adsorption over ZIF-7 nanoparticles was examined using the volumetric method at room temperature and pressure ranging from 2 to 9 bar. The results showed that the synthesized ZIF-7 adsorbents were highly crystalline with a well-defined and homogeneous particle size distribution of 50–60 nm. It was found that increasing the synthesis duration from 1 h to 3 h did not amend the structure and morphology of the resultant samples significantly, mainly due to the short synthesis duration. Meanwhile, the CH4 adsorbed by ZIF-7 nanoparticles increased with rising pressure for both samples, and the ZIF-7 nanoparticles synthesized at 3 h showed a greater adsorption capacity than that of 1 h, mainly due to its higher crystallinity and well-developed pore structure. The ZIF-7 synthesized at 3 h demonstrated an adsorption capacity up to 2.2 mol/kg, which was higher than those values reported in the literature for micron-sized ZIF-7 samples. The CH4 gas adsorption behavior of ZIF-7 nanoparticles synthesized at 1 h and 3 h were well predicted by the Langmuir isotherm model, with coefficients of determination, R2, of 0.9994 and 0.9982, respectively.

Three birds with one stone: A nano zeolitic imidazolate framework-luciferase-antimicrobial peptide biocomposite-based biosensing platform for improving enzyme stability, detection sensitivity, and sterilization effect

Adenosine triphosphate-driven bioluminescence (ATP-BL) biosensors were widely employed for on-site screening of bacteria. However, unstable luciferase with strict storage conditions limited its field detection. Moreover, the traditional ATP-BL biosensors lacked the sterilization effect. In this study, a robust and multifunctional zeolitic imidazolate framework-90 decorated with luciferase and polyethylene glycol–antimicrobial peptides (ZIF-90@Luc-AMP) was prepared. It could not only enhance the activity and stability of luciferase at ambient temperatures (≥1 month) but also sensitively detect target bacteria via the bioluminescence (BL) method and kill them (three birds with one stone). During the detection process, the target pathogen Escherichia coli O157:H7 (E. coli O157:H7) was specifically captured on a phage-modified stir bar and formed a sandwich complex with ZIF-90@Luc-AMP. With the synergistic bacteriolysis of ZIF-90@Luc-AMP and the phage, the captured E. coli O157:H7 was decomposed and emitted adenosine triphosphate (ATP), achieving the sterilization effect. Meanwhile, the introduced luciferase catalyzed ATP to produce a BL signal, which was proportional to the concentration of E. coli O157:H7. Combining ZIF-90@Luc-AMP and a phage-labeled stir bar for target recognition and enrichment, the entire analytical process could be easily manipulated within 30 min with a low limit of detection (20 CFU/mL) through a portable ATP bioluminescent meter. The multifunctional ZIF-90@Luc-AMP biosensor with high stability, specificity, and sensitivity was also appropriate for rapid pathogen screening and antibacterial application in the wild.

Balanced adsorption and oxidation in a porous P, N-doped carbon prepared by melt-salt-mediated strategy for enhanced fenton-like reaction

The activation of persulfate oxidation processes using carbon-based catalysts is attractive for eliminating persistent aromatic organic pollutants in wastewater treatment. Herein, N and P co-doped carbonaceous (NPC) catalysts with an ultrahigh surface area were synthesized using a melt-salt-mediated strategy, employing Zeolitic Imidazolate Framework-8 as a self-sacrificing template. The NPC(1:1) carbon, prepared under optimized conditions, exhibited the highest surface area of 2001.5 m2/g, characterized by the highest number of defects and a high dispersion of N (1.89 %) and P (0.30 %) atoms on the carbon. This carbon catalyst exhibited a high capacity for adsorption and potential for activating persulfates in the removal of p-Nitrophenol (p-NP). Experimental data indicate a balance between adsorption and oxidation in the NPC(1:1)/PDS/p-NP system, with the highest catalytic removal rate achieved through moderate pre-adsorption of p-NP. Evidence from quenching, electron paramagnetic resonance (EPR), and amperometric i-t experiments suggests that the NPC(1:1)/PDS system primarily degrades p-NP through an electron transfer pathway. Defects in carbon and graphitic N were identified as catalytic sites. These defects resulted in an electron-deficient state, which leads to the activation of PDS and graphitic N was more reactive than both pyridinic and pyrrolic N in the adsorption of PDS molecules. Additionally, P-containing groups such as C-P-O, C-O-P, and C3-P were pinpointed as active sites on the carbons through DFT calculations. The intermediates during p-NP degradation were identified, and possible degradation pathways were proposed. A toxicity analysis indicated a significant reduction in overall toxicity following the oxidation treatment. This study provides innovative insights into the balance between adsorption and catalytic activity in porous carbon-activated persulfate oxidation reactions, thereby aiding in the development of enhanced oxidation catalysts for environmental remediation.

Molten salt approach of zeolitic imidazole framework derived strontium doped porous carbon based bifunctional electrocatalysts for direct methanol fuel cell

Direct Methanol Fuel Cells (DMFCs) have sparked widespread interest and offer a viable approach for generating power. It has a number of commercial advantages, including low price, compact construction, and a quick refilling process that directly convert the chemical energy of methanol into electrical energy through an electrochemical reaction. However, direct methanol fuel cells (DMFCs) frequently rely on platinum catalysts, which are expensive and limited in scalability. Platinum catalysts can be poisoned by carbon monoxide (CO) thus preventing their widespread commercialization. Due to these drawbacks, there is growing interest in developing catalysts based on non-noble metals to improve DMFC technology's deployment. Herein, we report a facile synthesis method using a molten salt approach, which involves the solvent-free mixing of strontium nitrate tetrahydrate with ZIF-67, followed by direct pyrolysis in an Ar/H2 atmosphere at 800 °C. For methanol oxidation the strontium oxide loaded catalytic materials i.e., CoxOy SrO/C (1:1) exhibited a peak current density of 161 mA/cm2 and stability of 71 % over 28800s and for ORR it exhibit current density of −5.86 mA/cm2 and half wave potential of 0.87 V. The facile MOF synthesis strategy, enhanced by molten salt processing, shows great potential for creating non-noble catalytic materials for high-performance fuel cells.

Electrospun zeolitic imidazole framework-8 loaded silk fibroin/polycaprolactone nanofibrous scaffolds for biomedical application

The development of electrospun nanofibrous scaffolds (NFSs) have aroused much attraction in the field of biomedical engineering, due to their small fiber diameter, high specific surface area, and excellent extracellular matrix comparability. The main focus of this study is to design and fabricate novel zeolitic imidazole framework-8 (ZIF-8)-loaded silk fibrin/polycaprolactone (SF/PCL) nanofiber composite scaffolds by using the electrospinning strategy. Firstly, ZIF-8 was synthesized and characterized, which showed remarkable features in terms of shape, size, chemical and physical properties. Then, three different amounts of ZIF-8 were encapsulated into SF/PCL nanofibers during electrospinning, to investigate how the addition of ZIF-8 affected the morphology, and structure, as well as physical, mechanical, and biological properties of the nanofiber composite scaffolds. It was found that the addition of ZIF-8 didn't change the nanofibrous morphology of the composite scaffold, and no bead-like structure were found for the SF/PCL composite scaffolds loading with or without ZIF-8. The appropriate addition of ZIF-8 could significantly increase the mechanical properties of SF/PCL NFSs. The SF/PCL NFS containing 5% ZIF-8 showed high ultimate stress and initial modulus, which were 40.31 ± 2.31 MPa, and 569.19 ± 21.38 MPa, respectively. Furthermore, the MTT assay indicated that the pure SF/PCL scaffold and one with 1% ZIF-8 exhibited nearly identical cell compatibility toward human dermal fibroblast (HDF) cells, but some obvious cytotoxicity was observed with the increase of ZIF-8 content. However, the incorporation of ZIF-8 into SF/PCL NFSs was found to have excellent antibacterial rate against both E. coli and S. aureus. In all, the incorporation of 1% ZIF-8 could impart the SF/PCL NFS with balanced bio-function, making it a promising candidate for diverse biomedical applications such as tissue engineering and wound healing.

Capture and Protection of Environmental DNA in a Metal‐Organic Framework

Environmental DNA (eDNA) is released by organisms into their surroundings, enabling non‐invasive species detection and biodiversity assessments without the need for direct observation. However, collection poses challenges due to the generally low abundance of eDNA and the presence of degradation agents, including enzymes, UV radiation, and microorganisms, rendering samples unstable. Active filtration, which is frequently used to capture eDNA in water, can be time‐consuming and cumbersome in field conditions. Herein, a filter‐free one‐pot procedure for capturing eDNA with the metal‐organic framework (MOF), zeolitic imidazolate framework 8 (ZIF‐8), is examined. The method is evaluated on 15 mL water samples from diverse sources (aquarium, river, and sea). ZIF‐8 forms in all with high capture efficiency (>98%) using spiked salmon DNA to represent eDNA. The DNA is resistant to degradation by endonucleases and UV light. In addition, it remains stable over time as a species‐specific salmon quantitative polymerase chain reaction detected genomic DNA in all samples captured with the MOF to a maximum of 28 days at 37 °C while the untreated control samples were below the assay detection limit by day 6. These results highlight the efficacy of ZIF‐8 capture in overcoming challenges associated with the preservation of eDNA obtained from aquatic environments.

Facile synthesis of multifunctional zeolitic imidazolate framework-8 coatings on diverse bare substrates using a one-step strategy

Rational growth of metal–organic frameworks (MOFs) with controllable morphology and surface properties has been challenging. In this study, facile synthesis of zeolitic imidazolate framework-8 (ZIF-8) in solutions as well as direct in-situ growth of ZIF-8 on various untreated substrates was studied systematically. ZIF crystals with controllable morphology and size were prepared by simply adjusting the ethanol content in the co-solvent system, achieving a rational synthesis of ZIFs in controlled environments. More importantly, co-solvent content was proved to be crucial in the inter-dimensional topotactic phase transformation from a 2-dimensional ZIF-L to a three-dimensional ZIF-8. Then, the facile in-situ crystallization of ZIF-8 on a variety of untreated substrates was studied. With the use of co-solvents, ZIF-8 crystals were formed uniformly and continuously on all substrates regardless of the nature of the support material, including organic supports such as nylon membranes, 3D printed meshes, melamine sponges, mask filter layers, fabric, metallic support stainless-steel meshes, and ceramic pellet. This facile coating strategy provided controllable crystal coating morphology, size, and coating density, without surface modification/pre-treatment steps which are commonly used in the synthesis of high-quality ZIF coatings/membranes. The ZIF-8 coated substrates prepared in a co-solvent system displayed superior performance in some environmental remediation and biomedical applications. For example, the ZIF-8-coated nylon membrane achieved an impressive 96 ∼ 98 % small oil droplet removal from emulsions while maintaining a high water flux of ∼ 1200 L m−2h−1 bar−1. The superhydrophobic ZIF-8-coated melamine sponges were effective for fast oil adsorption. Last but not least, the ZIF-8-coated masks demonstrated greatly improved antibacterial activities. Overall, the co-solvent synthesis method reported in this work has enabled a one-step universal strategy for the direct growth of zeolitic imidazolate framework coating on diverse bare substrates with controlled surface properties and thus showed significant commercial potential in environmental and biological applications.

Insights into the thermal stabilization mechanism of zeolitic imidazolate framework-8 for poly(vinyl chloride)

The thermal stability of zeolitic imidazolate framework-8 (ZIF-8) for poly(vinyl chloride) (PVC) has received attention, but its thermal stabilization mechanism needs further clarification. Herein, the stearic acid-modified ZIF-8 with high specific surface area and large pore volume was effectively synthesized by using zinc stearate as the zinc source for the first time. Modification of stearic acid results in larger adsorption capacity of ZIF-8 for HCl and better thermal stability effect for PVC, especially long-term thermal stability. Moreover, the thermal stability mechanism of ZIF-8 for PVC was demonstrated by experiments and theoretical calculations. In addition to absorbing HCl to eliminate autocatalytic degradation of PVC, ZIF-8 disintegrates and may form 2-methylimidazole-Zn-Cl salt complex instead of free ZnCl2, avoiding the negative zinc burning effect. Furthermore, the Diels-Alder reaction between imidazole ring and degraded PVC prevents the extension of the conjugated double bonds of PVC and delays the deepening of the color of PVC.

A novel ZIF-8 mediated nanocomposite colorimetric sensor array for rapid identification of matcha grades, validated by density functional theory

The rapid and intelligent assessment of matcha grades remains crucial in quality control. This study proposed a colorimetric sensor array (CSA) mediated with zeolitic imidazolate framework-8 (ZIF-8) to identify matcha grades. The ZIF-8 mediated CSA was innovatively developed by encapsulating the pH indicator and metal porphyrin within the ZIF-8 structure, improving their stability and functionality. ZIF-8 mediated CSA exhibited significantly increased sensitivity towards matcha samples driven by the preconcentration of volatile organic compounds (VOCs) facilitated by ZIF-8. As a result, the response signal values of the CSA increased by 1.13–4.75 times after ZIF-8 mediation. Subsequently, qualitative models for identifying matcha grades were established using K-Nearest Neighbor and Artificial Neural Network (ANN). The ANN model showed the higher discrimination accuracy. Compared with common CSA, the ANN model based on ZIF-8 mediated CSA achieved a better identification rate of 95 %, and recognition accuracy was improved by 7.5 % in the model. These results indicated that the ZIF-8 mediated CSA with a porous structure demonstrated enhanced specificity in capturing VOCs. Ultimately, the density functional theory has confirmed that the ZIF-8-mediated CSA exhibits high selectivity towards matcha's characteristic VOCs. These results highlight the potential of this novel CSA for the rapid identification and grading of matcha.

Fast tailoring the ZIF-8 surface microenvironment at ambient temperature to boost glucose oxidase-like activity of AuNPs for biosensing

Rational design and tailoring of the surface microenvironment surrounding the catalytic sites, such as noble metal nanoparticles, is an effective way to enhance the catalytic activity of mimicking enzymes. However, it remains on-going challenges to regulate the microenvironment of the catalytic sites due to the lack of tunable variability in structural precision of conventional solid catalysts. Herein, three types of zeolitic imidazolate framework-8 (ZIF-8) with different major crystal facet orientations, i.e., cubic with (100) facets (denoted ZIF-8c), truncated dodecahedral with (100), (110) facets (denoted ZIF-8tr), and dodecahedral with (110) facets (denoted ZIF-8r), were developed facilely using an electrochemical method by switching the potential at ambient temperature. Because the Zn2+ nodes were predominantly exposed on the (100) facets of ZIF-8, while the ligands were mainly exposed on the (110) facets. Hence, gold nanoparticles (AuNPs) showed differential glucose oxidase (GOx)-like activities when anchored in situ on different crystal facets of ZIF-8 and obeyed the following order ZIF-8c/Au>ZIF-8tr/Au>ZIF-8r/Au. Notably, both the metal nodes and aromatic linkers of ZIF-8 interacted with AuNPs through coordination and π-π interactions. The Zn2+ nodes facilitated the formation of the electron-deficient Au species. The electron transfer from AuNPs to Zn2+ sites effectively boosted the catalytic activity. It was known that directly tailoring the microenvironment at the supporting sites of noble metal catalysts to boost catalysis through a facile electrochemical method was not reported. Based on the favorable GOx-like activity and long-term stability of ZIF-8tr/Au, a highly sensitive electrochemical biosensing platform for assaying squamous cell carcinoma antigen (SCCA) was developed. It enabled fg-level detection of cancer marker.

Recent advances in immunotherapy-involved combination cancer therapy based on ZIF-8

This paper introduces and briefly describes the tumor immune cycle to clarify the action mechanisms and principles of classical immunotherapy. We then focus on the classification of immunotherapies. Immunotherapy strategies can be classified into three categories according to the target of action: immunotherapy based on the regulation of dendritic cells, immunotherapy based on polarized tumor-associated macrophages, and immunotherapy based on the suppression of regulatory T cells. Subsequently, the latest research progress in the use of Zeolitic Imidazolate Framework-8 (ZIF-8) as a vehicle to combine immunotherapy with other therapeutic approaches is examined. Finally, prospects for the application of nanocomposites in combination therapy for tumor immunotherapy are outlined.

Accelerating the Hydrogen Evolution Kinetics with a Pulsed Laser-Synthesized Platinum Nanocluster-Decorated Nitrogen-Doped Carbon Electrocatalyst for Alkaline Seawater Electrolysis.

Efficient and durable electrocatalysts for the hydrogen evolution reaction (HER) in alkaline seawater environments are essential for sustainable hydrogen production. Zeolitic imidazolate framework-8 (ZIF-8) is synthesized through pulsed laser ablation in liquid, followed by pyrolysis, producing N-doped porous carbon (NC). NC matrix serves as a self-template, enabling Pt nanocluster decoration (NC-Pt) via pulsed laser irradiation in liquid. NC-Pt exhibits a large surface area, porous structure, high conductivity, N-rich carbon, abundant active sites, low Pt content, and a strong NC-Pt interaction. These properties enhance efficient mass transport during the HER. Remarkably, the optimized NC-Pt-4 catalyst achieves low HER overpotentials of 52, 57, and 53mV to attain 10mA cm-2 in alkaline, alkaline seawater, and simulated seawater, surpassing commercial Pt/C catalysts. In a two-electrode system with NC-Pt-4(-)ǀǀIrO2(+) as cathode and anode, it demonstrates excellent direct seawater electrolysis performance, with a low cell voltage of 1.63mV to attain 10mA cm-2 and remarkable stability. This study presents a rapid and efficient method for fabricating cost-effective and highly effective electrocatalysts for hydrogen production in alkaline and alkaline seawater environments.

Zeolitic imidazolate framework-67/barium zirconate titanate nanocomposite, Part I: Synthesis, characterization, and boosted photocatalytic activity

Using BaTi0.85Zr0.15O3/ZIF-67 (BTZ/ZIF-67) nanocomposite, tetracycline (TC) was photodegraded. Characterization of the samples was carried out using a variety of techniques, including XRD, FESEM-EDS (Field Emission Scanning Electron Microscopy – Energy Dispersive X-ray Spectroscopy), FT-IR (Fourier Transform Infra-Red), TEM (Transmission Electron Microscopy), BET (Brunauer-Emmett-Teller), BJH (Barrett-Joyner-Halenda), PL (Photoluminescence), TG-DTG (Thermogravimetry and Derivative Thermogravimetry), and UV–Vis DRS (Diffuse Reflectance Spectroscopy). BTZ/ZIF-67 nano-composites were synthesized using a one-step co-precipitation method. BTZ (30 %wt)/ZIF-67 showed the most impressive photocatalytic ability among the binary photocatalysts. Averaging the crystallite sizes of the nanocomposite samples identified by Scherrer and Williamson-Hall methods was 43.3 nm and 65.0 nm, respectively. The pHpzc values of samples of BTZ and BTZ (30 %wt)/ZIF-67 were approximately 6.7 and 10.0, respectively. Using the proposed method, we measured 357, 414, and 377 nm absorption edges for ZIF-67, BTZ, and BTZ (30 %wt)/ZIF-67 samples, which correspond to 3.47, 2.99, and 3.28 eV bandgap energies, respectively. The specific surface areas of BTZ, ZIF-67, and BTZ (30 %wt)/ZIF-67 nanocomposite are 122.15, 1218, and 1509 m2g−1, respectively. Under optimum conditions (0.8 g/L of the catalyst, CTC: 30 mg/L, and a pH 5), 89.5 % of total organic carbon (TOC) was removed within 180 min. Compared to BTZ photocatalyst, the BTZ (30 %wt)/ZIF-67 nanocomposite has a significantly larger surface area, thus enhancing photocatalytic activity. A synergistic effect was observed in the photodegradation of TC under Hg-lamp irradiation with the proposed BTZ/ZIF-67 composite. It is possible to alter the photocatalytic activity of the catalyst by changing the BTZ (30 %wt)/ZIF-67 ratio.

Rationally tailored configuration of multifunctional scavengers by encapsulating nanoscale Fe0 and FeS into zeolite imidazole framework–8 with reinforced perrhenate/pertechnetate confinement

In order to probe into the potential application prospects of multifunctional scavengers in remediating nuclear wastewater, we combined versatile functionality of nanoscale Fe0 and FeS with tailorable porosity of zeolitic imidazole frameworks–8 (ZIF–8) to manufacture two multifunctional scavengers for ReO4– confinement i.e., NZVI@ZIF–8 by reduction approach and FeS@ZIF–8 by coprecipitation approach. Batch approaches unveiled that as–manufactured scavengers illustrated an reinforced performance towards ReO4– confinement. The pseudo-second-order model was well simulated with the kinetic of ReO4– confinement. Thermodynamic analysis unraveled that ReO4– confinement was endothermic and spontaneous. The mechanism was explored via characterization alters of structure and composition of NZVI@ZIF–8 and FeS@ZIF–8 before and after ReO4– confinement. Specifically, fourier transform infrared spectrometer (FTIR) and X-ray diffraction (XRD) indicated that NZVI and FeS were successfully encapsulated into ZIF–8, and NZVI@ZIF–8 and FeS@ZIF–8 remained stable after ReO4– confinement. X–ray absorption fine structure (XAFS) unveiled that various Fe mineral phases were formed on the scavenger surfaces under various reaction conditions. X-ray photoelectron spectroscopy (XPS) unraveled existence of Re(VI)/Re(IV) on scavengers surfaces, unveiling ReO4– was initially enriched NZVI@ZIF–8 and FeS@ZIF–8 surfaces with subsequent reduction into Re(VI)/Re(IV). This work proposed an innovative perspective to tailored multifunctional scavengers in nuclear waste management.

Robust ZIF-8 based superhydrophobic coating with anti-icing, anti-corrosion, and substrate universality

The design of superhydrophobic materials based on zeolite imidazolate frameworks (ZIF) has attracted considerable attention due to their exceptional chemical stability, high specific surface area, and environmental friendliness. However, research in the fields of anti-corrosion and anti-icing remains in its infancy, and the mechanical stability of reported ZIF-based superhydrophobic surfaces is generally poor. In this study, we synthesized ZIF-8@PDA materials in an aqueous system and followed with stearic acid (STA) modification to achieve low surface energy, resulting in ZIF-8@PDA@STA. Subsequently, we applied a spray-coating method to sequentially construct WPU and ZIF-8@PDA@STA layer on aluminum alloy substrates, achieving a ZIF-8@PDA@STA/WPU superhydrophobic coating with exceptional mechanical stability. This coating retained its superhydrophobicity even after 5600 cm of abrasion distance. Furthermore, results from surface wettability, electrochemical and anti-icing tests demonstrated that the coated aluminum alloy exhibited excellent interfacial non-wetting, self-cleaning, anti-fouling, and significantly enhanced corrosion resistance and delayed icing properties. Additionally, the facile preparation of this coating on various substrates facilitates the large-scale application of such materials. The construction of this multifunctional ZIF-8 based superhydrophobic coating is expected to greatly expand the application of ZIF materials across diverse fields.

Ammonium perchlorate catalyzed with novel n-Al modified on ZIF-67 with silane coupling agent: Superior catalytic activity, advanced decomposition kinetics and mechanisms

Ammonium perchlorate (AP) is commonly utilized as an oxidizer in composite solid propellants (CSPs), and the thermal decomposition of AP has a significant impact on the combustion behaviour of CSPs. Aluminum nanoparticles (n-Al) as a prospective metal fuel have received a lot of interest, however properly extracting energy from n-Al remains a great challenge. Native oxide layer limits the energetic performance of n-Al by impeding sufficient combustion and slowing down mass/heat transport. Development of the high energy storage based on metastable intermolecular composite (MIC) is always a desirable way. This group of hybrid materials uses zeolitic imidazole framework (ZIF) as the precursors of the metal oxides as the oxidizers in conventional nanothermite. Coating n-Al on the surface of ZIF-67 with a silane coupling agent to erase or disturb the oxide layer on the n-Al surface improves n-Al combustion. n-Al@ZIF-67 was synthesized and integrated into AP matrix. The catalytic activity of n-Al@ZIF-67 on AP decomposition was assessed via DSC and TGA/DTG. Whereas n-Al@ZIF-67/AP nanocomposite demonstrated decomposition enthalpy of 2350 J/g; pure AP demonstrated 836 J/g, ZIF-67/AP demonstrated 1680 J/g, and n-Al/AP demonstrated 1170 J/g. While Al@ZIF-67/AP nanocomposite demonstrated one decomposition temperature at 327 oC; pure AP decompose at two decomposition stages at 298 oC, and 453 oC. n-Al@ZIF-67/AP showed a violent reaction with high intensity of flame, and micro-explosion occurred due to rapidly disrupted oxide layer that covered Al core. Decomposition kinetics was investigated. n-Al@ZIF-67/AP demonstrated apparent activation energy of 125.3 ± 1.23 kJ/mol compared with 173.16 ± 1.95 kJ/mol for pure AP. Co3O4 NPs as the combustion product from ZIF-67 can expose active surface sites; the ability of adsorption of released NH3 gas, which inhibition AP from decomposition, offering efficient combustion. This work provides a new strategy for advanced CSPs by introducing ZIF-67 to construct bifunctional properties for AP decomposition, and n-Al combustion.

In situ growth of ZIF-8 on cellulose microspheres with high doxorubicin loading capacity and pH-sensitive for oral drug delivery

Metal-organic framework (MOF) nanoparticles are a class of porous nanomaterials with wide application prospects. Zeolitic imidazolate framework (ZIF) materials have high loading performance and pH-sensitive characteristics, which means they have great development prospects in the development of drug carrier systems. Herein, cellulose microspheres (CM) were used as a carrier for the nucleation and growth of ZIF-8 nanocrystals. CM@ZIF-8 was prepared in situ, which was more convenient, flexible, cost-effective, and highly safe. CM@ZIF-8, as a novel carrier, was used to monitor the release of the anticancer drug Doxorubicin (DOX) and prevent it from dissipating before reaching its goal. The designed DOX-loaded CM@ZIF-8 (CM@ZIF-8-DOX) system was characterized by FTIR, SEM, N2 sorption isotherm, XRD, and Cytotoxicity assay (cells survival rate 95.08 %). CM@ZIF-8-DOX exhibited controlled drug release behavior in simulated in-vitro tumor microenvironments (81.2 % drug release throughout 72h). CM@ZIF-8 simultaneously had a high loading capacity of DOX (Qe = 159.71 mg∙g−1), and the amount released under acidic conditions (pH 5.0) was greater (63.4 % after 15 h) than under neutral conditions (pH 7.4) due to the detachment of the coordination between metal ions and ligands (37.6 % after 15 h).

Visible light-induced photocatalytic degradation of anticancer drugs via zeolitic imidazole framework (ZIF-8@ZIF-67): mechanistic insights

Visible light-induced photocatalytic degradation of anticancer drugs via zeolitic imidazole framework (ZIF-8@ZIF-67): mechanistic insights

Bimetal-organic framework derived single-atom-like Co/Fe catalysts for peroxydisulfate activation: The dual amplification of radical and nonradical pathways

A novel single-atom-like Co/Fe catalyst (i.e., Co/Fe-N-C) was synthesized by pyrolysis of a Zn/Co/Fe zeolitic imidazolate framework, and applied in peroxydisulfate (PDS) activation for removal of organic contaminants from wastewater. The isolated diatomic metal-nitrogen sites were detected by X-ray adsorption fine-structure. The degradation of four contaminants (i.e., phenol, bisphenol A, 2,4-dichlorophenol, and N-methyl-2-pyrrolidone) with a concentration of 100 mg/L could be degraded separately within 20 min by the Co/Fe-N-C system with 10 mmol/L of PDS, 0.5 g/L of catalyst dosage, and initial pH of 3. Besides, 79.2 % of phenol could be mineralized in 120 min, and the turn-over frequency value of the catalyst was calculated to be 27.17 min−1, which was higher than the commonly reported homogeneous PS-AOPs. Moreover, the Co/Fe-N-C exhibited high stability (mineralization rate over 70 % after 5 cycles), a wide initial pH range (3−9), and high catalytic performance at 5–20 mmol/L of PDS concentrations. Based on the analysis of radical scavenging experiments and electron spin resonance spectra, the radical and non-radical pathways for PDS activation were proved in the system, and the contribution of phenol degradation by each pathway was clarified.