Zeolitic Imidazolate Framework Research Articles

Fish freshness monitoring based on bilayer cellulose acetate/polyvinylidene fluoride membranes containing ZIF-8 loaded curcumin

This study presented a dual-layer freshness indicator film produced through electrospinning, combining cellulose acetate and polyvinylidene fluoride with zeolitic imidazolate framework-8 (ZIF-8) loaded with curcumin as the indicator. Our findings demonstrated that ZIF-8 effectively preserved its metal-organic framework structure during curcumin loading, ensuring the inherent color-changing ability of curcumin. The resulting colorimetric film exhibited altered tensile properties and increased water vapor permeability. Improved light stability and storage performance were observed. Compared to single-layer films, the dual-layer structure improved the hydrophilicity and stability of the indicator film. Importantly, the introduced indicator label efficiently captured the dynamic changes of TVB-N during freshness monitoring, providing comprehensive visual information for assessing fish freshness. The synergistic properties of ZIF-8, curcumin, and the dual-layer film structure contributed to an advanced freshness indicator system, providing a multifunctional and effective approach for real-time freshness assessment of fish freshness.

Zeolitic imidazolate framework-8 as a high-affinity adsorbent for dispersive solid-phase extraction in the analysis of plant growth regulators in fruits.

Facile and sensitive determination of plant growth regulators (PGRs) in food samples is crucial but still poses a significant challenge. In this study, to enhance the sensitivity of the HPLC-DAD method for PGR detection, a dispersive solid phase extraction (d-SPE) method using zeolitic imidazolate framework-8 (ZIF-8) as the highly effective adsorbent is developed. ZIF-8 nanoparticles are formed through the coordination of Zn2+ with 2-methylimidazole. Due to its high porosity, large surface area, abundant π electronics and nitrogen electronics, ZIF-8 exhibits a strong affinity to PGRs due to the synergistic effects of π-π interaction, van der Waals force, H-bond, and surface effect. Under the optimal d-SPE conditions, the sensitivity of the method is significantly enhanced with outstanding performances, including a wide range of linearity (2.0-200 ng g-1) with high correlation coefficients (R ≥ 0.9989), low limits of detection (LODs, 0.9-8.0 ng g-1 for all PGRs), satisfactory precision (intra-day RSDs ≤ 3.3%, inter-day RSDs ≤ 4.2%), and high accuracy (recovery: 86.6-101.5%). The developed method was successfully applied to quantitatively detect 9 PGRs in fruit samples, yielding satisfactory results. This d-SPE-HPLC-DAD method, characterized by high sensitivity, simplicity, efficiency, ease of practice and cost-effectiveness for PGR detection, shows potential for detecting PGRs in other complex samples and provides a strategy for designing target-affinity adsorbents.

Upconversion-based chiral nanoprobe for highly selective dual-mode sensing and bioimaging of hydrogen sulfide in vitro and in vivo

Chiral assemblies have become one of the most active research areas due to their versatility, playing an increasingly important role in bio-detection, imaging and therapy. In this work, chiral UCNPs/CuxOS@ZIF nanoprobes are prepared by encapsulating upconversion nanoparticles (UCNPs) and CuxOS nanoparticles (NPs) into zeolitic imidazolate framework-8 (ZIF-8). The novel excited-state energy distribution-modulated upconversion nanostructure (NaYbF4@NaYF4: Yb, Er) is selected as the fluorescence source and energy donor for highly efficient fluorescence resonance energy transfer (FRET). CuxOS NP is employed as chiral source and energy acceptor to quench upconversion luminescence (UCL) and provide circular dichroism (CD) signal. Utilizing the natural adsorption and sorting advantages of ZIF-8, the designed nanoprobe can isolate the influence of other common disruptors, thus achieve ultra-sensitive and highly selective UCL/CD dual-mode quantification of H2S in aqueous solution and in living cells. Notably, the nanoprobe is also capable of in vivo intra-tumoral H2S tracking. Our work highlights the multifunctional properties of chiral nanocomposites in sensing and opens a new vision and idea for the preparation and application of chiral nanomaterials in biomedical and biological analysis.

Synergistic Photothermal Tumor Immunotherapy by 1-MT Based on Zeolitic Imidazolate Framework-8 with pH-High Sensitivity.

A successful immune response against tumors depends on various cellular processes. Hence, there is an urgent need to construct a proficient nanoplatform for immunotherapy that can concurrently regulate the activities of various cells participating in the immune process. We have developed zeolitic imidazolate framework-8 (ZIF-8) formula, with good pH sensitivity, which is conducive to the release of drugs in the tumor site (acidic environment) and significantly improves immunotherapy. This is achieved through the coordinated action of different therapeutic agents, such as the photothermal agent polydopamine (PDA), the chemodrug camptothecin (CPT), and the immunomodulator 1-methyl-D-tryptophan (1-MT). In this study, we evaluated the antitumor effect of PDA/(CPT + 1-MT) @ZIF-8 (PCMZ) nanoparticles (NPs) in vitro and in vivo and investigated the molecular mechanism of PCMZ NPs in tumor suppression via photothermal-chemo-immunotherapy. MTT and Annexin V-FITC/PI double staining apoptosis test showed that PCMZ NPs could induce apoptosis of 4T1 cell, and PCMZ NPs could cause 4T1 cell necrosis under 808 nm laser irradiation. The objective is to establish a unilateral breast cancer model in mice and investigate the effect of PCMZ NPs on tumor growth and tumor suppression in tumor bearing mice. The results showed that PCMZ NPs showed good heating effect in vivo and effectively inhibited tumor growth under 808 nm laser irradiation. In addition, PCMZ NPs could induce the immunogenic death of tumor cells, promote the maturation of DCs, inhibit IDO pathway, and finally differentiate T cells into cytotoxic T cells and helper T cells, so as to effectively activate the anti-tumor immune response. The PCMZ NPs, possessing good photothermal conversion capabilities due to join of PDA, effectively overcome two main challenges in immunotherapy: insufficient stimulation of the immune response and evasion of the immune system. This provides a robust platform against invasive cancer and recurrent tumors.

Artificial Neutrophils Against Vascular Graft Infection.

Efficient neutrophil migration to infection sites plays a vital role in the body's defense against bacterial infections and natural immune responses. Neutrophils have a short lifespan and cannot be mass-cultured in vitro. Therefore, developing more stable artificial neutrophils (AN) in a controllable manner has become a research focus. However, existing AN lack chemotaxis, which is the ability to migrate toward high-signal-concentration positions in a dynamic blood- flow environment. Supplying AN with chemotaxis is key to designing AN that are more similar to natural neutrophils in terms of morphology and function. In this study, micrometer-sized, spherical, biocompatible AN are developed. These AN consist of zeolitic imidazolate framework-8 nanoparticles encapsulating two enzymes, coacervate droplet frameworks, and outer phospholipid bilayers carrying enzymes. The AN exhibit responsiveness to elevated hydrogen peroxide levels at inflammation sites, actively chemotaxing toward these sites along concentration gradients. They also demonstrate effective combat against Staphylococcus aureus infections. The capabilities of the AN are further validated through in vitro experiments and in vivo evaluations using vascular graft infection models. This study replicates natural neutrophils in terms of chemical composition, functionality, and physiological impact. It introduces new ideas for advancing the development of advanced artificial cells.

Rh, Co, and N-doped titanium mesh-based carbon nanosheet arrays for enhanced nitrite reduction reaction and ammonia generation

The electrocatalytic transformation of nitrite pollutants into valuable ammonia is crucial for the nitrogen cycle. However, the complex multi-reaction process necessitates the development of highly efficient and selective electrocatalysts. This study focuses on the creation of Rh-doped Co@NC anchored on a titanium mesh as an electrocatalyst to enhance the electrocatalytic nitrite reduction reaction (eNO2RR) for NH3 synthesis. By doping a trace amount of Rh within zeolitic imidazolate framework-67 nanosheets and subsequently pyrolyzing the material, uniformly distributed Rh and Co nanoparticles are anchored onto N-functionalized porous carbon nanosheet arrays. Consequently, the three-dimensional electrode enhances mass and electron transfer while providing abundant surface-exposed active sites for NH3 generation through eNO2RR. The Rh0.6 wt%–Co@NC/TM electrocatalyst, with a minimal Rh loading of 0.6 wt%, exhibits the highest Faradaic efficiency of 98.8 ± 0.7 % at −0.3 V, along with an NH3 yield of 1777.1 ± 7.0 μmol h−1 cm−2 at −0.7 V. Additionally, the electrocatalyst demonstrates exceptional durability over 20 consecutive cycles and remarkable environmental adaptability. Extensive experimental studies reveal that the superior performance of Rh0.6 wt%–Co@NC/TM arises from the synergistic catalysis between Co and Rh, which enhances NO2– adsorption and the production of active hydrogen for eNO2RR to NH3 synthesis. This research highlights that Rh incorporation facilitates the kinetics of eNO2RR and offers valuable insights for the development of efficient electrocatalysts towards NH3 synthesis.

Nickel foam-decorated hollow-Co3O4/GO nanocomposites: A highly sensitive non-enzymatic electrochemical sensor for glucose detection

Cobalt-based nanomaterials, characterized by multiple oxidation states and high stability in alkaline environments, have been found extensive applications in glucose detection. In this study, a cobalt-based zeolitic imidazolate framework (ZIF-67) was employed as a precursor, where Co2+ was coordinated with carboxyl groups of oxidized graphene oxide (GO), resulting in the formation of cobalt-based nanoparticles. The integration of Co2+ with GO established a novel cobalt-based nanomaterial with potential implications for glucose detection. At a calcination temperature of 260 °C, the calcination process extended for 4 h, fulfilling the synthesis of Hollow-Co3O4/GO nanocomposites. These nanocomposites were subsequently engaged as electrochemical electrodes for glucose detection through the impregnation method. The distinctive structure of Hollow-Co3O4/GO has spurred mutual promotion of the reoxidation reactions at the interface, culminating in a substantial augmentation of the specific surface area and a consequent considerable surge in the glucose oxidation current. In addition, due to the retention of the structure of MOFs, the pores can be used to adsorb glucose molecules, which is conducive to the accurate detection of the reaction. Under optimal conditions, the sensitivity of the Hollow-Co3O4/GO modified electrode hits 1582.7 μA mmol−1 cm−2, with a detection limit of 0.49 μmol/L (S/N = 3) and a response time of approximately 2 s. These achievements have emphasized the promising applicability of Hollow-Co3O4/GO nanocomposites as an active material for practical electrochemical biosensors.

Regulating coordinatively unsaturated Co active sites in TA@ZIF-L(Co) via tannic acid for efficient photoelectrochemical water oxidation

Metal-organic frameworks (MOFs) as a cocatalyst can enhance the photoelectrochemical (PEC) water oxidation performance to a certain extent, but still suffer from deficient exposure of active sites and low electron mobility. In this work, 2D Leaf-like zeolitic imidazolate frameworks (ZIF-L) were selected as a precursor for the generation of defective structures by tannic acid (TA) functionalization-assisted etching, and then coupling it with BiVO4 to prepare a novel and highly efficient TA@ZIF-L(Co)/BiVO4 photoanode by a simple impregnation method. The photocurrent density of TA@ZIF-L(Co)/BiVO4 composite photoanode achieves 4.21 mA cm−2 at 1.23 VRHE under AM 1.5 G illumination, which is superior to that of ZIF-L(Co)/BiVO4, and three times that of the bare BiVO4, with a charge injection efficiency of up to 80 %, and its stability is also remarkably improved. Experimental results and DFT calculations showed that the introduction of TA not only improved the light absorption efficiency, but also exposed more active sites, increased the electron density of the coordinatively unsaturated Co active sites, and enhanced the polarized electric field on the surface, thus accelerating electron mobility. This work demonstrates that TA as a surface modifier has great potential to activate metal sites and change the electronic environment of MOFs for BiVO4-based photoanode in PEC water oxidation, providing valuable insights into the rational design of photoanodes.

Seed-assisted two-step ZIF-67 growth on CS/PVA nanofibers for high-efficiency cadmium and tetracycline adsorption

Herein, novel ZIF-67/CS/PVA (CNF-2) nanofiber composites using a two-step seed-assisted in situ electrospinning method, with cobalt-based zeolitic imidazolate framework (ZIF-67) as the precursor was prepared. SEM, EDX, AFM, FTIR, and XRD analyses revealed the optimal formation of ZIF-67 nanoparticles both inside and on the surface of CS/PVA nanofibers without compromising the structure of these electrospun nanofibers. The unique porous structure and heterointerfaces of the ZIF-67/CS/PVA (CNF-2) nanofiber composites demonstrated remarkable adsorption capacities for cadmium (Cd) and tetracycline hydrochloride (TCH), achieving 1137.94 and 1029.5 mg/g, respectively. The adsorption effectiveness for Cd and TCH was 94.83 % and 85.79 %, respectively, under optimal adsorption conditions: pH 8, adsorbent dosage of 0.01 g, initial Cd and TCH concentration of 80 mg/L, and a contact time of 120 min. The study of coexisting Cd and TCH adsorption on CNF-2 under varying pH conditions (4–8) reveals a significant enhancement in Cd adsorption efficiency, increasing from 41.91 % to 97.49 %. Conversely, TCH exhibits a more modest improvement, with its adsorption efficiency rising from 72.53 % to 85.96 %. Kinetic and equilibrium studies revealed that the adsorption followed pseudo-second-order kinetics and the Langmuir isotherm. The prepared nanofiber adsorbed 60 % of Malachite green dye. The engineered adsorbent demonstrated impressive regeneration potential, maintaining its efficiency over three successive adsorption–desorption cycles.

Supporting silver on ZnCo-ZIFs as an efficient heterogeneous catalyst for oxytetracycline antibiotic removal

Abstract Water pollution by antibiotic residues negatively affects the ecosystem and seriously threatens public health. Therefore, finding a sustainable technology to remove antibiotics from water resources is extremely necessary. This work synthesized bimetallic Zn-Co based zeolite imidazolate frameworks (ZnCo-ZIFs) and integrated them with Ag via the impregnation method to obtain Ag/ZnCo-ZIFs. This material demonstrated a remarkable capability to remove oxytetracycline (OTC). The results showed that it could remove 94% OTC at an initial concentration of 30 mg.L−1 using H2O2 concentration of 0.015 mol.L−1, Ag/ZnCo-ZIFs catalyst dose of 400 mg.L−1 at room temperature for 40 min. Besides, the catalyst could be reused and recycled after four times. This promises that Ag/ZnCo-ZIFs could be approached as a heterogeneous catalytic material for removing antibiotics from aquatic environments.

Rational construction of a hollow bimetallic porous composite derived zeolite imidazole framework based reduced graphene oxide nanosheets for supercapacitor applications

Rational construction of a hollow bimetallic porous composite derived zeolite imidazole framework based reduced graphene oxide nanosheets for supercapacitor applications

Antimicrobial polymer-based zeolite imidazolate framework composite membranes for uranium extraction from wastewater and seawater

Extraction uranium (VI) (U(VI)) from wastewater and seawater is highly important for environmental protection and life safety, but it remains a great challenge. In this work, the growth of the zeolitic imidazolate framework-8 (ZIF-8) nanoparticles on the tannic acid (TA)-3-aminopropyltriethoxysilane (APTES) modified PVDF (TAP) membrane was designed to obtain an excellent U(VI) adsorbent. The zeolite imidazolate framework composite membrane (TAPP-ZIF-60) was prepared through polyethyleneimine (PEI) bridging strategy and temperature regulation strategy in solvothermal method. The coordination bond between PEI and ZIF-8 and the covalent bond between PEI and TAP are essential in forming stable composite membrane. TAPP-ZIF with different properties was synthesized through a temperature regulation process and the TAPP-ZIF prepared at 60 °C has the uniform morphology and good performance. The adsorption capacity of TAPP-ZIF-60 is 153.68 mg/g (C0 = 95.01 mg/L and pH = 8.0) and water permeability is 5459 L m−2 h−1 bar−1. After ten adsorption–desorption cycles, it is proved that TAPP-ZIF-60 has good repeatability and stability. In addition, the TAPP-ZIF-60 composites membrane has a good inhibitory effect on Staphylococcus aureus and Escherichia coli. X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) analysis reveal that the coordination between TAPP-ZIF-60 and uranyl ions is the primary factor contributing to the high adsorption capacity.

Bimetallic Nanoplatforms for Prostate Cancer Treatment by Interfering Cellular Communication.

Cellular communication mediated by messenger molecules plays an important role in the progression of cancer. Herein, pH-sensitive zeolitic imidazolate framework-8 (ZIF-8) loaded with PtCl2(OH)2(NH3)2 [i.e., Pt(IV)] bimetallic nanoplatforms were developed for prostate cancer therapy by interfering inositol-1, 4, 5-trisphosphate (IP3)-mediated cellular communication. As an important messenger in cells, the function of IP3 was found to be efficiently interfered with by the Pt(IV)-binding inositol unit. This finding effect of Pt(IV) is totally different from its traditional function as a prodrug of cis-platinum for chemotherapy. The decreased IP3 signal further downregulated the cytoplasmic Ca2+ concentration and downstream signal transduction to inhibit proliferation and invasion of tumor cells. Meanwhile, Zn2+ released from ZIF-8 under an acidic tumor microenvironment decreased adenosine triphosphate biosynthesis, which could further limit the cellular communication. Such a proposed strategy of interfering cellular communication has demonstrated its feasibility in this study, which may provide new perspectives for cancer therapy.

CsPbBr3 NCs Confined and In Situ Grown in ZIF-8: A Stable, Sensitive, Reliable Fluorescent Sensor for Evaluating the Acid Value of Edible Oils.

Rapidly and sensitively evaluating the acid value (AV) of edible oils is significant to ensuring food quality and safety. Cesium lead bromide perovskite nanocrystals (CsPbBr3 NCs) are an effective candidate for AV detection; however, their instability restricts wide applications. Herein, CsPbBr3@ZIF-8 was prepared by confining and growing CsPbBr3 NCs in situ into zeolitic imidazolate framework-8 (ZIF-8) to improve the stability, and a fluorescence sensor was established to evaluate the AV of edible oils. The results present that CsPbBr3 NCs (below 5 nm) with excellent optical properties were confined and grown in situ in micropores and mesopores of ZIF-8. Meanwhile, CsPbBr3@ZIF-8 had better long-term storage, ultraviolet-irradiation, and water-exposure stabilities, compared with CsPbBr3 NCs. Given the fact that free fatty acids (the major contributor of AV) decrease the fluorescence of CsPbBr3 NCs, the fluorescence intensities of CsPbBr3@ZIF-8 were negative-linearly related to oil AV (R2 = 0.9902) in 0.04-6.00 mg of KOH/g with a 0.06 mg of KOH/g limit of detection. Besides, the practical AV recovery was 92-101% with an average relative standard deviation of 2%. Furthermore, the detection time was 20 min. The response mechanism revealed that free fatty acids could remove surface ligands and increase surface defects to prompt the aggregation of CsPbBr3 NCs and the formation of lattice fringe dislocations, inducing a decrease in the fluorescence. Thus, a stable, sensitive, reliable sensor was established to evaluate the AV of edible oils.

Flexible Scaffold Modulation of Spatial Structure and Function of Hierarchically Porous Nanoparticle@ZIF-8 Composites to Enhance Field Deployable Disease Diagnostics.

Catalytic nanoparticle@metal-organic framework (MOF) composites have attracted significant interest in point-of-care testing (POCT) owing to their prominent catalytic activity. However, the trade-off between high loading efficiency and high catalytic activity remains challenging because high concentrations of nanoparticles tend to cause the misjoining and collapse of the MOFs. Herein, a facile strategy is reported to encapsulate high concentrations of platinum (Pt) nanoparticles into zeolitic imidazolate framework-8 (ZIF-8) using polydopamine (PDA) as a support for Pt@ZIF-8 and as a flexible scaffold for further immobilization of Pt nanoparticles. The resulting composite (Pt@ZIF-8@PDA@Pt) exhibits ultrahigh Pt nanoparticle loading efficiency, exceptional catalytic activity, stability, and a bright colorimetric signal. Following integration with lateral flow immunoassay (LFIA), the detection limits for pre- and post-catalysis detection of B-type natriuretic peptide (NT-proBNP) are 0.18 and 0.015ng mL-1, respectively, representing a 6-fold and 70-fold improvement compared to gold nanoparticle-based LFIA. Moreover, Pt@ZIF-8@PDA@Pt-based LFIA achieves 100% diagnostic sensitivity for NT-proBNP in a cohort of 184 clinical samples.

Flexible, breathable, and durable superhydrophobic cotton fabric modified by behenic acid, tung oil, and ZIF-8 with anti-icing and self-cleaning properties

Textiles with self-cleaning and anti-icing capabilities in cold climates are essential for outdoor workers and enthusiasts. Superhydrophobic modification of textile surfaces is effective in imparting these characteristics. Although there are numerous methods available for manufacturing superhydrophobic textiles, careful consideration is warranted for environmental concerns over fluorochemicals, stability of superhydrophobic coatings, and fabric breathability. In this work, we utilized biomass resources such as tung oil and behenic acid, along with zeolitic imidazolate framework (ZIF-8), to modify cotton fabrics, thereby creating an innovative behenic acid/tung oil/ZIF-8 modified cotton (BTZC) fabric with anti-icing and self-cleaning features. This material manifests a unique nanoflower-shaped surface morphology, demonstrating exceptional superhydrophobicity with a static water contact angle (CA) of 162° and a sliding angle (SA) of 2°. Moreover, BTZC excels in its thermal stability, breathability, and resistance to icing. Equally impressive is its robust stability, as evidenced through rigorous testing under continuous washing and abrasion, sustained high and low temperatures, extreme pH environments, and immersion in various chemical solvents. BTZC presents as a fluorine-free, durable, economically viable alternative for outdoor textile applications, marking substantial progress in the utilization of biomass and metal-organic framework materials in the textile industry and promising implications for value enhancement.

Metal-polyphenol network loaded ZIF-8 for efficient removal of fluoroquinolone antibiotics

A metal-polyphenol network functionalized on surface of zeolitic imidazolate framework-8 (MPN@ZIF-8) were fabricated for efficient removal of fluoroquinolones (FQs) antibiotics. Polyphenol as one kind versatile molecular glue was employed as organic ligand as well as linkage for growth and deposition of metal-polyphenol network (MPN) on ZIF-8 supporter. The prepared MPN@ZIF-8 composite was characterized by various methods. The parameters including the dosage of adsorbents, pH value, adsorption time and salt concentration affecting the adsorption process were systematically investigated. FQs adsorption isotherms and kinetics best fitted the Langmuir isotherm (R2 > 0.980) and pseudo-second-order model (R2 > 0.987), respectively. Thermodynamic studies showed that adsorption process of norfloxacin (NOR), ciprofloxacin (CIP) and enrofloxacin (ENR) were all spontaneous. The adsorption capacity of MPN@ZIF-8 were 104.60, 86.23 and 66.21 mg g−1 for NOR, CIP and ENR, respectively, which were significantly higher than those of precursor ZIF-8. The potential adsorption mechanism was stated, most likely involved in π-π interaction, hydrogen-bond and electrostatic interaction between the FQs and the MPN@ZIF-8. In addition, the removal efficiency of the three FQs on MPN@ZIF-8 was still above 95 % after recycle for four times. The recoveries of the three FQs were in the range of 77.1–100.1 % with RSDs below 7.8 % in real sample analysis. Compared with the methods in preparation of MOF-based composite, the fabrication method mentioned in this study is versatile, very easy, environmental friendly and low cost, which has potential in large-scale production for application in environmental remediation.

Patterned design of porous carbon materials as microporous layers to enhance fuel cell performance over a wide humidity range

Microporous layers play a crucial role as one of the main components of the membrane electrode assembly (MEA) in facilitating effective water management for proton exchange membrane fuel cells (PEMFCs), which is vital for maintaining optimal performance in a wide humidity range. Herein, Zn-based zeolitic imidazolate framework-8 (ZIF-8)-derived material (ZDM) as a porous carbon material is first developed to construct the microporous layer (MPL). With higher gas permeability, improved water management, and increased electrical conductivity, the MPL equipped with a ZDM layer, denoted as MPL-Z, exhibits superior performance, surpassing commercial MPLs throughout the range of 30–100% relative humidity (RH). The peak power density of an H2/air PEMFC at 70% RH utilizing a MPL-Z is 3.3 times that of commercial MPL. Furthermore, a unique patterned dual MPL is designed to boost the performance, ultimately achieving a peak power density of 1.50 W cm−2 (H2/air) with a low total Pt loading of 0.3 mgPt cm−2 at 100 % RH. Even at only 30% RH, the peak power density can reach 0.72 W cm−2 (H2/air). The results demonstrate that the material and structural design of the MPL allows for the efficient operation of low Pt loading PEMFCs over a wide humidity range.

A facile acid-etching defect-rich leaf-like zeolitic-imidazolate framework adsorbent for simultaneous removal of organic/inorganic phosphorus pollutants from wastewater

Organophosphorus herbicide glyphosate and inorganic phosphate usually coexist in wastewater, leading to water eutrophication and posing risks to human health. In this study, acid-etching defect-rich leaf-like zeolitic-imidazolate framework (ae-ZIF-L) adsorbent was developed by a facile etching method to investigate its simultaneous removal performance of glyphosate and phosphate. Compared to ZIF-L precursor, ae-ZIF-L displayed a maximum adsorption capacity for phosphate and glyphosate of 164.4 mg g–1 and 12.7 mg g–1, respectively. The overall enhanced adsorption performance of ae-ZIF-L was primarily attributed to abundant Zn defects, resulting in higher positive zeta potentials to enhance electrostatic attraction. Notably, in the phosphate/glyphosate coexistence system, ae-ZIF-L has extremely high removal rates of 99.1 % and 90.9 %, while ZIF-L has removal rates of 97.7 % and 39.4 %, respectively. Furthermore, after four adsorption-desorption cycles, the removal rates of phosphate/glyphosate by ae-ZIF-L remained at 84.8 % and 82.5 %, respectively. In conclusion, ae-ZIF-L proved to be an efficient and reusable adsorbent with promising application for the treatment of organic/inorganic phosphorus pollution in wastewater.

Vibrational dynamics dictate heat transport in metal-organic frameworks with gas adsorbates

Understanding the thermal conductivity (κ) of metal-organic frameworks (MOFs) with adsorbates is critical for tailoring their heat dissipation in practical applications. However, a detailed description of how adsorbates influence the heat transport of MOFs is still lacking. In this work, we employ molecular dynamics simulations combined with lattice dynamics calculations to investigate the effect of gas adsorbates on κ of representative crystalline and glassy zeolitic imidazolate frameworks (ZIFs). We identify that the diffusive adsorbate motions in the crystalline ZIFs with large pores can enhance lattice anharmonicity, serving as a source of phonon scattering and significantly suppressing κ. Conversely, the adsorbates with restricted dynamics in limited space (i.e., in the dense ZIF crystals or glasses) behave more like a heat transfer medium and facilitate heat transport. Besides pore size, gas dynamics are also proved to vary upon gas-lattice interaction strength, and dictate if gas adsorbates serve as a heat conduction suppressor or promoter. We anticipate that this governing role of gas dynamics is applicable to a diverse range of MOF-adsorbate systems. As such, our work offers guidance for the practical thermal management of MOF porous materials to ensure their desired storage or separation performance.