Metal-organic Framework Materials Research Articles

Synthesis Strategies, Preparation Methods, and Applications of Chiral Metal-Organic Frameworks.

Chiral metal-organic framework (CMOFs) is a kind of material with great application value in recent years. Formed by the coordination of metal ions or metal clusters with organic ligands. It is widely used in chemistry, biology, medicine and materials science because of its ordered and adjustable pores, multi-dimensional network structure, large specific surface area and excellent adsorption properties. In this paper, the synthesis strategies and preparation methods of chiral metal-organic frameworks are reviewed. In addition, the applications of chiral metal-organic framework materials in enantiomer recognition and separation, circularly polarized luminescence and asymmetric catalysis are systematically summarized. Finally, the challenges and prospects of the development of chiral metal-organic frame materials are analyzed in detail.

Recent Developments in Porphyrin-Based Metal–Organic Framework Materials for Water Remediation under Visible-Light Irradiation

Access to clean drinking water is a basic requirement, and eliminating pollutants from wastewater is important for saving water ecosystems. The porous structure and surface characteristics of metal–organic frameworks (MOFs) can function as a perfect scaffold for removing toxic compounds from wastewater. Porphyrins are promising building blocks for constructing MOFs. Porphyrin-based metal–organic frameworks (P-MOFs) have been fabricated using porphyrin ligands, metal clusters, or ions. These materials can harvest light from a wide region of the solar spectrum, and their framework morphology and physicochemical properties can be controlled by changing their peripheral subunits or metal ions. These porous crystalline materials have generated interest because of their distinctive characteristics, including large permanent porosity, interesting surface morphology, broad conformational diversity, high photostability, and semiconducting nature. This article discusses the recent progress and usefulness of P-MOFs. The fabrication procedures of P-MOFs are discussed, followed by the adsorptive and photocatalytic removal of contaminants from wastewater. The relationships between the geometries of P-MOFs and their light-harvesting and charge-transfer mechanisms for the photocatalytic degradation of pollutants are highlighted. Finally, some future perspectives and obstacles in the photodegradation usage of P-MOFs are discussed, along with feasible research directions to standardize efficient photocatalysts for improved photodegradation for water treatment.

Bimetallic Organic Frameworks via In Situ Solvothermal Sol-Gel-Crystal and Sol-Crystal Transformation as Durable Electrocatalysts for Oxygen Reduction Reaction.

The in situ solvothermal conversion of metal-organic gels (MOGs) to crystalline metal-organic frameworks (MOFs) represents a versatile and ingenious strategy that has been employed for the synthesis of MOF materials with specific morphologies, high yield, and improved functional properties. Herein, we have adopted an in situ solvothermal conversion of bimetallic MOGs to crystalline bimetallic MOFs with the aim of introducing a redox-active metal heterogeneity into the monometallic counterpart. The formation of bimetallic NiZn-MOF and CoZn-MOF via in situ solvothermal sol-gel-crystal and sol-crystal transformation is found to depend on the solvent systems used. The sol-to-gel-to-crystal transformation of NiZn-MOF via the formation of NiZn-MOG is found to occur through the gradual disruption of gel fibers leading to subsequent formation of microcrystals and single crystals of NiZn-MOF. These bimetallic MOFs and MOGs serve as promising electrocatalysts for oxygen reduction reaction (ORR) with an excellent methanol tolerance property, which can be attributed to the enhanced mass and charge transfer, higher oxygen vacancies, and bimetallic synergistic interactions among the heterometals. This work demonstrates a convenient strategy for producing bimetallic MOGs to MOFs through the introduction of a redox-active metal heterogeneity in the inorganic hybrid functional materials for fundamental and applied research. Our results connect MOGs and MOFs which have been regarded as having opposite physical states, that is, soft vs hard, and provide promising structural correlation between MOGs and MOFs at the molecular level.

Bottom-Up Construction of Rhombic Lamellar CoNi-MOFs for the Electrochemical Sensing of H2S.

Lamellar metal-organic frameworks (MOFs) have attracted significant attention in the field of electrochemical sensing due to their abundant open active sites and specific electron conductivity. Herein, by employing a bottom-up synthesis strategy, rhombic lamellar heterometallic CoNi-MOFs with varying thicknesses are constructed. This is achieved by using 4-methylpyridine as a capping agent based on the (4,6)-linked Co2(azpy)2(bptc) (azpy = 4,4'-azopyridine, bptc = 3,3',5,5'-biphenyltetracarboxylic acid) structure with a fsc topology and by introducing Ni species simultaneously. To mitigate sulfur deposition on electrodes, the triple pulse amperometry (TPA) method is employed. Among the synthesized lamellar CoNi-MOFs, lamellar CoNi-MOF-3 with the minimum thickness exhibits an optimal electrochemical sensing performance toward hydrogen sulfide, with a sensitivity of 119.3 μA·mM-1·cm-2 in the linear range of 2-2000 μM. This study pioneers a new approach to the controlled construction and electrochemical activity modification of lamellar MOF materials.

Interface Engineering of MOF-Derived Co3O4@CNT and CoS2@CNT Anodes with Long Cycle Life and High-Rate Properties in Lithium/Sodium-Ion Batteries.

Metal-organic framework materials can be converted into carbon-based nanoporous materials by pyrolysis, which have a wide range of applications in energy storage. Here, we design special interface engineering to combine the carbon skeleton and nitrogen-doped carbon nanotubes (CNTs) with the transition metal compounds (TMCs) well, which mitigates the bulk effect of the TMCs and improves the conductivity of the electrodes. Zeolitic imidazolate framework-67 is used as a precursor to form a carbon skeleton and a large number of nitrogen-doped CNTs by pyrolysis followed by the in situ formation of Co3O4 and CoS2, and finally, Co3O4@CNTs and CoS2@CNTs are synthesized. The obtained anode electrodes exhibit a long cycle life and high-rate properties. In lithium-ion batteries (LIBs), Co3O4@CNTs have a high capacity of 581 mAh g-1 at a high current of 5 A g-1, and their reversible capacity is still 1037.6 mAh g-1 after 200 cycles at 1 A g-1. In sodium-ion batteries (SIBs), CoS2@CNTs have a capacity of 859.9 mAh g-1 at 0.1 A g-1 and can be retained at 801.2 mAh g-1 after 50 cycles. The unique interface engineering and excellent electrochemical properties make them ideal anode materials for high-rate, long-life LIBs and SIBs.

Metal-organic frameworks based on ternary transition metal ions for high-performance lithium ion batteries

Metal-organic frameworks (MOFs) materials have been widely researched in energy conversion systems because of porosity and active sites. However, applying MOF as an electrode material remains challenging because of its structural instability. In this work, two novel materials are designed to promote the research of MOFs-based electrode materials for lithium-ion batteries (LIBs). Two ternary metallic ions (Mn2+, Co2+, Ni2+) constituent MOFs with two- and three-dimensional (3D) structures are synthesized by combining with benzene-1,2,3,4,5,6-hexacarboxylate (BHC) ligand via a simple hydrothermal method. The structures of MCN-1 and MCN-2 belong to monoclinic symmetry, C2/c space group. The 3D structure of MCN-2 can enhance the interfacial contact between electrode materials and electrolytes and provide more active sites for the storage of Li+. Electrochemical experiments show that the 3D structure ternary MOF delivers an ultra-high capacity of 807.3 mAh g−1 after 100 cycles at 100 mA g−1, even though a phase transition occurs during the electrochemical process. This superior performance is rationally owing to the synergetic mechanism of intercalation/deintercalation combined with capacitance behavior, which has broad application prospects as anode material.

Recent Progress on Conversion of Lignocellulosic Biomass by MOF-Immobilized Enzyme.

The enzyme catalysis conversion of lignocellulosic biomass into valuable chemicals and fuels showed a bright outlook for replacing fossil resources. However, the high cost and easy deactivation of free enzymes restrict the conversion process. Immobilization of enzymes in metal-organic frameworks (MOFs) is one of the most promising strategies due to MOF materials' tunable building units, multiple pore structures, and excellent biocompatibility. Also, MOFs are ideal support materials and could enhance the stability and reusability of enzymes. In this paper, recent progress on the conversion of cellulose, hemicellulose, and lignin by MOF-immobilized enzymes is extensively reviewed. This paper focuses on the immobilized enzyme performances and enzymatic mechanism. Finally, the challenges of the conversion of lignocellulosic biomass by MOF-immobilized enzyme are discussed.

Homogeneous electrochemical ratiometric biosensor for MircoRNA detection based on UiO-66-NH2 signal probe and waste-free entropy-driven DNA machine

The construction of efficient methods for highly sensitive and rapid detection of disease markers is essential for the early diagnosis of serious diseases. In this paper, taking advantage of the UiO-66-NH2 signal molecule in combination with a waste-free entropy-driven DNA machine, a novel homogeneous electrochemical ratiometric platform is developed to detect MircoRNA (miRNA). Metal-organic framework materials (UiO-66-NH2 MOF) and ferrocene were utilized as electrochemical signal tags and reference probes, respectively. The target-initiated waste-free three-dimensional (3D) entropy-driven DNA nanomachine is activated in the presence of miRNA, resulting in DNA-labeled-UiO-66-NH2 falling off from the electrode, leading to a decrease in the signal of UiO-66-NH2 at 0.83V. Our strategy can mitigate false positive responses induced by the DNA probes immobilized on electrodes in traditional distance-dependent signal adjustment ratiometric strategies. The proposed ratiometric platform demonstrates superior sensitivity (a detection limit of 9.8 fM), simplified operation, high selectivity, and high repeatability. The ratiometric biosensor is also applied to detect miRNA content in spiked serum samples.

Metal organic frameworks as polysulfide reaction modulators for lithium sulfur batteries: advances and perspectives.

Currently, lithium sulfur (Li-S) battery with high theoretical energy density has attracted great research interest. However, the diffusion and loss process of intermediate lithium polysulfide during charge-discharge hindered the application of the Li-S batteryin modern life. To overcome this issue, metal organic frameworks (MOFs) and their composites have been regarded as effective additions to restrain the LiPS diffusion process for Li-S battery. Benefiting from the unique structure with rich active sites to adsorb LiPS and accelerate the LiPS redox, the Li-S batteries with MOFs modified exhibit superior electrochemical performance. Considering the rapid development of MOFs in Li-S battery, this review summarizes the recent researches of MOFs and their composites as the sulfur host materials, functional interlayer, separator coating layer, and separator/solid electrolyte for Li-S batteries in detail. In addition, the promising design strategies of functional MOF materials are proposed to improve the electrochemical performance of Li-S battery.

A Highly Robust and Conducting Ultramicroporous 3D Fe(II)-Based Metal-Organic Framework for Efficient Energy Storage.

Exploitation of metal-organic framework (MOF) materials as active electrodes for energy storage or conversion is reasonably challenging owing to their poor robustness against various acidic/basic conditions and conventionally low electric conductivity. Keeping this in perspective, herein, a 3D ultramicroporous triazolate Fe-MOF (abbreviated as Fe-MET) is judiciously employed using cheap and commercially available starting materials. Fe-MET possesses ultra-stability against various chemical environments (pH-1 to pH-14 with varied organic solvents) and is highly electrically conductive (σ=0.19Sm-1) in one fell swoop. By taking advantage of the properties mentioned above, Fe-MET electrodes give prominence to electrochemical capacitor (EC) performance by delivering an astounding gravimetric (304Fg-1) and areal (181mFcm-2) capacitance at 0.5Ag-1 current density with exceptionally high cycling stability. Implementation of Fe-MET as an exclusive (by not using any conductive additives) EC electrode in solid-state energy storage devices outperforms most of the reported MOF-based EC materials and even surpasses certain porous carbon and graphene materials, showcasing superior capabilities and great promise compared to various other alternatives as energy storage materials.

Progressive Insights into Metal-Organic Frameworks and Metal-Organic Framework-Membrane Composite Systems for Wastewater Management.

The sustainable management of wastewater through recycling and utilization stands as a pressing concern in the trajectory of societal advancement. Prioritizing the elimination of diverse organic contaminants is paramount in wastewater treatment, garnering significant attention from researchers worldwide. Emerging metal-organic framework materials (MOFs), bridging organic and inorganic attributes, have surfaced as novel adsorbents, showcasing pivotal potential in wastewater remediation. Nevertheless, challenges like limited water stability, elevated dissolution rates, and inadequate hydrophobicity persist in the context of wastewater treatment. To enhance the performance of MOFs, they can be modified through chemical or physical methods, and combined with membrane materials as additives to create membrane composite materials. These membrane composites, derived from MOFs, exhibit remarkable characteristics including enhanced porosity, adjustable pore dimensions, superior permeability, optimal conductivity, and robust water stability. Their ability to effectively sequester organic compounds has spurred significant research in this field. This paper introduces methods for enhancing the performance of MOFs and explores their potential applications in water treatment. It delves into the detailed design, synthesis strategies, and fabrication of composite membranes using MOFs. Furthermore, it focuses on the application prospects, challenges, and opportunities associated with MOF composite membranes in water treatment.

Electrochemical Impedimetric Platform Based on Con A@MIL-101 for Glycoprotein Detection.

An electrochemical impedimetric biosensing platform with lectin as a molecular recognition element has been established for the sensitive detection of glycoproteins, a class of important biomarkers in clinical diagnosis. One of the representative metal-organic framework materials, MIL-101(Cr)-NH2, was utilized as the supporting matrix, and its amino groups served as the anchors to immobilize the lectins of concanavalin A (Con A), constituting Con A@MIL-101(Cr)-NH2 for the determination of invertase (INV) as a model glycoprotein. The Con A concentration, immobilization time, and incubation time with INV were optimized. Under the optimal conditions, the degree of impedance increase was linearly proportional to the logarithm of INV concentration between 1.0 × 10-16 and 1.0 × 10-11 M, affording a limit of detection as low as 3.98 × 10-18 M. Good specificity, stability, reproducibility, and repeatability were demonstrated for the fabricated biosensing platform. Moreover, real mouse serum samples were spiked with different concentrations of INV. Excellent recoveries were obtained, which demonstrated the biosensing platform's capability of analyzing glycoproteins within a complex matrix.

The design and preparation of NDI modified MOFs for high efficiency removal of MB and Cr(VI)

The naphthalene tetracarboxdiimide (NDI) modified NH2-UiO-66(Zr) and NH2-MIL-101(Cr) (NDI/UZr and NDI/MCr for short) metal organic frameworks (MOFs) materials with strong covalent bond O=C-N-C=O were designed and prepared by solvothermal method. The comprehensive physical and chemical properties of the materials were characterized, and the adsorption and photocatalytic properties of the materials were evaluated by using methylene blue (MB) and Cr(VI) in single and mixture system. When the initial concentration of MB was 50mg·L−1, the photocatalytic degradation rate constant of NDI/MCr(2:1) was 10.3 and 13.8 times higher than that of NH2-MIL-101(Cr) and NDI/UZr(2:1), respectively. Additionally, NDI/MCr(2:1) exhibited 1.6 times higher reaction rate constant than that of NDI/UZr(2:1) for the removal of 10mg∙L−1 Cr(VI). The enhanced adsorption and photocatalytic ability over NDI/MOFs were attributed to the MOFs larger specific surface area and wider spectral response, and NDI showed high electron affinity, superior charge carrier transport properties. Free radical and electron capture experiments indicated that h+, •O2−, and e− were the main active species in the NDI/MOFs system. Among them h+ and •O2− played an essential role in the removal of MB, while e− and •O2− contributed to the photocatalytic reduction of Cr(VI). The mechanism of the photocatalytic process was discussed in detail.

Bio-inspired MOF nanozyme-engineered biocatalytic precipitation strategy mediates electron transfer for ultrasensitive photoelectrochemical immunoassay

Enzyme-like nanomaterials (nanozyme) has been used to generate amplified response signals in biosensors instead of the bio-enzyme, on account of their higher stability and comparable catalytical activity. Especially the metal-organic framework (MOF) materials with ultra-high porosity and high specific surface area, which is more suitable for deriving superior nanozyme. In order to deal with the increasing demand of healthcare diagnostics and biomedical research, here we propose a novel approach for ultrasensitive photoelectrochemical (PEC) immunoassay. The bio-inspired MOF-derived nanozyme Hemin/BSA@ZIF-8 was introduced into the target biorecognition and sensing processes to accelerate the oxidization of substrate to produce insoluble precipitate, which will impede the electron transfer and lead to a significant reduction in photocurrent. The proposed PEC sensor exhibits a wide linear range of 0.1pgmL−1 ~ 100ngmL−1, and a low detection limit of 11.9 fg mL−1 for cardiac troponin I (cTnI) detection. This work brings a new insight of the bio-inspired MOF nanozyme-mediated PEC immunoassay designing, and offers a novel sensing strategy for accurate human biomarker analysis.

Fabrication of phosphorylated UiO-66 for efficient selective removal of Pb2+ from acidic wastewater

Metal-organic framework (MOF) materials have emerged as promising candidates for treating heavy metal wastewater because of their controllable pore size, high specific surface area, and abundant active sites. Nevertheless, the currently reported MOFs usually require near-neutral environments (pH = 5–6) to achieve efficient removal of Pb2+ and cannot be applied to acidic environments (pH = 2–3). In this work, the structurally stabilized zirconium-based MOF UiO-66 was chosen as the object of study. Three phosphate ester-based MOFs (UiO-66-(OPO3)X) containing different amounts and spatial positions were designed and prepared by simple chemical modification and used to remove Pb2+. Adsorption experiments showed that they could reach adsorption equilibrium in 30 min with excellent adsorption rate. Owing to the unique ionization ability of the phosphate ester group, UiO-66-(OPO3)X maintains a high removal efficiency of Pb2+ even at pH = 2 and pH = 3. In addition, selectivity and competition experiments demonstrated that UiO-66-(OPO3)X possessed excellent selectivity and anticompetitive ability towards Pb2+.The excellent regeneration performance demonstrates their value for practical application. Moreover, the adsorption mechanism was investigated in detail by experiment combined with density functional theory (DFT).

Construction of a novel Eu-MOF material based on different detection mechanisms and its application in sensing pollutants aniline, F- and Hg2+

Aniline is an organic pollutant with carcinogenicity and teratogenicity, while F- and Hg2+ are toxic ions that are easily soluble in water. When they are released to the environment, they will pose a threat to human health. Designing a material that can simultaneously detect three types of pollutants is of great significance. In this paper, a novel rare earth metal organic framework material (Eu-MOF) with three-dimensional structure based on 1-methylimidazole-4,5-dicarboxylic acid was synthesized for the first time through solvent thermal method. It has excellent luminescent performance and can be used as a multifunctional fluorescent probe to detect aniline, F-, and Hg2+ based on photoinduced electron transfer, energy competitive absorption, and ion exchange mechanisms, with detection limits of 1.79 × 10-8, 8.13 × 10-8, and 8.83 × 10-7 M, respectively. It is worth noting that Eu-MOF can detect F- and Hg2+ in real water samples, such as lake water and green tea water, with favorable recovery rates.

Engineering ZIF-67 loaded nanofibrous membrane with thermal stabilization treatment for efficient photocatalytic CO2 reduction

The photocatalytic Metal-organic frameworks (MOFs) membrane addresses challenges faced by MOF powders in practical applications such as aggregation and difficult recovery, but its current application is mainly confined to wastewater treatment. Expanding the application of MOFs membranes to CO2 reduction could unleash their greater potential in energy conversion and storage field. In this study, ZIF-67 was deposited on polyacrylonitrile (PAN) nanofiber membranes (NFMs) using an in-situ growth technique, followed by thermal stabilization to produce SZIF-67/PAN NFMs for photocatalytic CO2 reduction. ZIF-67 was uniformly and densely distributed on the NFMs, with a mass loading of up to 8 wt%. The thermal stabilization process significantly enhanced the photothermal conversion capability and solvent resistance of the NFMs, enabling SZIF-67/PAN NFMs to exhibit outstanding photocatalytic activity even under mild environmental conditions, with a remarkable CO generation rate of 39,250 μmol g−1h−1. Furthermore, the performance remained at 70 % even after five consecutive tests. This study presents a novel and effective method for preparing MOF NFMs with excellent photocatalytic CO2 reduction performance, offering valuable insights for advancing the practical application of MOF materials.

Multiple stimulus responsive of a novel naphthalenediimide-based 2D alkaline-earth metal MOF material: Hydrochromism, amine-/acid-induced chromism and ionochromism as well as visual artificial film application

Metal–organic frameworks (MOFs) with naphthalene-1,4,5,8-tetracarboxylic dianhydride (H4NDISA) chromophoric unit provide an intriguing platform for the design of multiple stimulus responsive materials. Herein, the first NDISA-based 2D MOF [Ca(H2NDISA)(DMF)3]∙H2O (Ca-NDISA) constructed from alkaline-earth metal ion was successfully synthesized. The structural analysis shown that a binuclear secondary building unit (SBU) [Ca2(COO)2(DMF)6] is extended to generate a 2D planar network structure with abundant open-activity sites, endowing Ca-NDISA with multiple stimulus responsive chromic behaviors. Ca-NDISA could undergo a color change from yellow to red in hydrochromism, rendering it with the applications in detecting the water content of organic solvents, as a humidity sensor when fabricating a PMMA@Ca-NDISA film, and a potential hydrochromic imaging material. In amine-/acid-induced chromism, Ca-NDISA respectively changed its color to red and brown when exposed to strong acid and some small size ammonia/organic amines vapors environment, which makes the PMMA@Ca-NDISA film as a visual and portable recognition detector for acids and amines. In ionochromism, Ca-NDISA is suitable for the naked-eye discrimination and detection of I− with obvious color change to black brown. Our work not only provide a facile way to obtain NDISA-based 2D MOF with multi-stimulus responsive chromic properties, but also present some convenient chromism devices, which will enrich the family of multifunctional chromic materials for practical applications.

A novel magnetic Fe, N co-doped Ce-MOFs derived carbon as a peroxymonosulfate activator for the degradation of tetracycline hydrochloride: Performance and activation mechanism

The activation of peroxymonosulfate (PMS) using metal-organic frameworks (MOFs) has garnered significant interest in the field of wastewater treatment. However, the environmental challenges associated with traditional methods for synthesizing MOFs precursors, such as the requirement for high temperatures and pressures, remain. Furthermore, the catalytic performance and stability of mono-metallic materials are areas needing enhancement. This work successfully synthesized a novel magnetic Fe-Ce bimetallic N-doped porous MOF material (Fe/Ce@5MNC). The optimized Fe/Ce@5MNC exhibited a higher specific surface area and a more extensive pore structure, as verified by various characterization techniques. Moreover, the synthesis process of the precursor is simpler, energy-saving, and relatively environmentally friendly. Notably, the synergistic effect between Fe and Ce, coupled with the presence of multiple active sites such as FeNx and graphite N, enabled Fe/Ce@5MNC to decompose 86.4 % of TCH within 30 min, marking a 31.4 % increase over Ce@NC. After four cycles, the catalyst maintained good surface stability, with the degradation efficiency remaining at 67.7 %. Quenching and electron paramagnetic resonance (EPR) experiments confirmed that the main degradation mechanisms are singlet oxygen (1O2) generation and electron transfer. This study presents a new method for synthesizing efficient Fe, N co-doped magnetic bimetallic PMS activators and designing carbon catalysts for deep oxidation.

ZIF-67C@CeO2 Composite for the Electrochemical Non-Enzymatic Determination of Nitrite in Fish Dry Samples

Nitrite is widely present in the human environment, and it is one of the most common nitrogenous compounds in nature. However, Nitrite is often used as a preservative in meat products even though it has always been considered a carcinogen. Herein, dimethylimidazole was used as a ligand to coordinate Co2+ to prepare a metal-organic framework material- ZIF67, then the ZIF67 was added to the prepared cerium hydroxide to produce ZIF67C@CeO2 composite via high-temperature calcination. Furthermore, a novel ZIF67C@CeO2 composite modified glassy carbon electrode (ZIF67C@CeO2/GCE) was constructed to detect nitrite in fish dried samples. Scanning electron microscopy and X-ray diffraction were used to characterize the microstructure of the ZIF-67C@CeO2 composite. The experimental condition, such as applied potentials, load mass of composite, and pH value of electrolyte were optimized by electrochemical tests. In the optimal conditions, the linear range of the sensor for detecting nitrite is 0.3–1150 μM, and the detection limit (DL) is 0.102 μM. Moreover, the sensor possesses a good anti-jamming capability, repeatability, and reproducibility. The constructed sensor- ZIF-67C@CeO2/GCE showed excellent electrochemical performance and enabled the detection of nitrite in fish dried foods.