Synthesis Of Metal-organic Frameworks Research Articles

Successful synthesis of eco-friendly Metal-Organic framework ([Ni(BDC)]n) allows efficient extraction of multiresidues pesticides and dyes from fish samples

Contaminants such as pesticides and dyes pose substantial challenges to environmental and human health, especially when found in aquatic ecosystems and ingested through the food chain. This requires the development of methods that are efficient, safe and environmentally friendly. In this scenario, this study presents the synthesis and characterization of a metal–organic framework (MOF), specifically [Ni(BDC)]n, designed as a solid adsorbent for the determination of pesticides, including atrazine, bifenthrin, chlorpyrifos, endrin, heptachlor, flutriafol and permethrin, as well as dyes such as crystal violet (CV) and Congo red (CR) in fish samples. Using Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FT-IR), Thermogravimetric Analysis (TGA), X-ray Diffraction (XRD), and Brunauer-Emmett-Teller (BET), we verified the success of the MOF synthesis. BET analysis indicated MOF surface area and total pore volume of 2700 m2/g and 0.0136 cm3 g−1, respectively. The adsorption study revealed high affinity of the MOF for the target analytes, with qmax = 208.33 mg g−1 for pesticides and qmax = 4.18 mg g−1 for dyes. The kinetic study demonstrated that the adsorption mechanism follows a pseudo-second order model for all analytes. Furthermore, employing [Ni(BDC)]n, we have developed an efficient extraction method using Matrix-Solid Phase Dispersion (MSPD) combined with Gas Chromatography-Mass Spectrometry (GC–MS) and UV/Vis spectrophotometry for determination of pesticide and dyes, respectively, with pre-concentration factor ranging from 10 to 100 times for the studied analytes. The methods showed satisfactory linearity for both contaminants (pesticides and dyes), with recovery efficiency ranging from 81-103 % and precision < 13 % (n = 3) for the analytes. Linear ranges covering 10.0–500.0 μg L−1 (R2 > 0.995) for pesticides and 100.0–1000.0 μg L−1 (R2 > 0.988) for dyes. The limits of detection (LOD) and quantification (LOQ) ranged from 0.5-1.6 μg L−1 and 1.7–5.6 μg L−1 for pesticides, respectively, while for dyes, LOD and LOQ ranged from 2.0-12.0 μg L−1 and 7.6–39.6 μg L−1, respectively. These results highlight the potential of [Ni(BDC)]n as a promising material for efficient and selective extraction in the sustainable determination of pesticides and dyes in fish samples, with satisfactory reuse.

Synthesis and adsorption properties of new calcium metal-organic framework (Ca-MOF) ZIOC-10 based on a new carbazole linker

A carbazole-based linker 9-(carboxymethyl)carbazole-3,6-dicarboxylic acid (H3cbzac) was synthesized for the first time. Its structure was confirmed via 1H NMR and Powder X-Ray Diffraction (PXRD) methods. A novel calcium-based 2D MOF Ca(H2cbzac)2(DMF)2 (ZIOC-10) was synthesized via a solvothermal procedure. It was found that the obtained framework undergoes several structural changes upon heating, which lead to the formation of a new framework Ca(H2cbzac)2 (ZIOC-10a). Noteworthy, ZIOC-10 transforms into the permanent porous (524 m2/g) 3D framework, which can absorb methane, ethane, propane, and carbon dioxide at room temperature.

Controlled Synthesis of Preferential Facet-Exposed Fe-MOFs for Ultrasensitive Detection of Peroxides.

Exposing different facets on metal-organic frameworks (MOFs) is highly desirable to enhance the performance for various applications, however, exploiting a concise and effective approach to achieve facet-controlled synthesis of MOFs remains challenging. Here, by modulating the ratio of metal precursors to ligands, the facet-engineered iron-based MOFs (Fe-MOFs) exhibits enhanced catalytic activity for Fenton reaction are explored, and the mechanism of facet-dependent performance is revealed in detail. Fully exposed (101) and (100) facets on spindle-shaped Fe-MOFs enable rapid oxidation of colorless o-phenylenediamine (OPD) to colored products, thereby establishing a dual-mode platform for the detection of hydrogen peroxide (H2O2) and triacetone triperoxide (TATP). Thus, a detection limit as low as 2.06nm is achieved, and robust selectivity against a wide range of common substances (>16 types) is obtained, which is further improved by incorporating a deep learning architecture with an SE-VGG16 network model, enabling precise differentiation of oxidizing agents from captured images. The present strategy is expected will shine light on both the rational synthesis of nanomaterials with modulated morphologies and the exploitation of high-performance trace chemical sensors.

Facile Layer Diffusion Technique for Synthesis of Terbium-Based Metal Organic Framework for Fluorometric Sensing of Hydroquinone.

A photoluminescent terbium (III)-based Metal Organic Framework (MOF) was synthesized at room temperature by layer diffusion method utilizing mixed carboxylate linkers (4,4'-oxybis(benzoic acid) and benzene-1,3,5 tricarboxylic acid). Synthesized MOF has crystalline nature and rod-shaped morphology and is thermally stable up to 455°C. The fluorescence emission spectra and theoretical results revealed that carboxylate linkers functioned as sensitizers for Tb(III) photoluminescence which resulted in four distinct emission peaks at 495, 547, 584, and 621nm corresponding to the transitions 5D4 → 7F6, 5D4 → 7F5, 5D4 → 7F4, and 5D4 → 7F3. Using synthesized MOF as fluorescent probe, hydroquinone was detected in aqueous medium with a detection limit of 0.048μM, remarkable recovery (95.6-101.1%), and relative standard deviation less than 2.25%. The quenching phenomenon may be ascribed to electron transfer from synthesized probe to oxidized hydroquinone via carboxylic groups on thesurface of MOF, which is further supported by photo-induced electron transfer mechanism. This study introduces a cheaper, faster, and more accurate method for hydroquinone detection.

Synthesis and application of metal-organic frameworks

Metal-organic frameworks (MOFs) are an intriguing class of materials that undergoes self-assembly, originating from polydentate organic ligands. These ligands are primarily composed of aromatic polynucleic acids and polybases, along with transition metal ions. The advancements in MOFs have diversified, employing ligands based on carboxylates or nitrogen-containing heterocyclic organic neutral ligands, resulting in materials characterized by their increased porosity and remarkable chemical stability. The research provides a comprehensive review of conventional and alternative synthesis methods, highlighting recent techniques such as microwave-assisted, electrochemical, mechanochemical, and sonochemical synthesis. The synthesis methods are discussed in detail, to provide a comprehensive understanding of the various techniques available. The versatile properties of MOFs find applications in various fields such as gas adsorption, chemical sensing, catalysis, and drug delivery. The analysis not only deepens the understanding of MOFs' present state but also inspires future innovations in their synthesis and applications. The research also highlights the potential of MOFs in drug delivery, where they can be used as carriers for the delivery of drugs or other therapeutic agents. The comprehensiveness of this research provides a valuable resource for understanding the current state of MOFs research and identifies future directions for innovation in their synthesis and applications.

Recent advances on metal-organic frameworks (MOFs) and their applications in energy conversion devices: Comprehensive review

Metal-organic frameworks (MOFs) have enticed huge interest over the years in a wide range of applications, including electrochemical energy storage/conversion devices, due to their controllable porous structure, tuneable composition, excellent thermal/chemical stabilities, and facile synthesis. However, conductivity enhancement and synthesis of redox-active MOFs are two key challenges hindering their large-scale applications in electrochemistry. Redox-active MOFs can be prepared using redox-active ligands and metal ions, which in turn leads to an additional benefit of π-stacking interactions. Conductivity improvements through favourable overlap of energy and orientation of both metal and ligand, π-π stacking, and the incorporation of a guest molecule to induce free charge carriers and reduce band gaps are key strategies. This review provides a detailed assessment of various synthesis techniques followed by post-production treatments to improve MOF's conductivity. Advancements in computational methods & machine learning for MOFs as well as the econmics of MOF's production are introduced. The use of MOFs and MOF-based nanomaterials in batteries, supercapacitors, and fuel cells, as well as the progress in using MOF and MOF-based catalysts for CO2 reduction and as a photocatalyst for hydrogen production, have been scrutinized by highlighting their benefits and shortcomings. Finally, the challenges MOFs and MOF-based materials face and their prospects when adopted as active materials in energy storage/conversion devices, as well as CO2 reduction and green hydrogen production, have also been elaborated.

Mechanochemical Synthesis and Three-Dimensional Electron Diffraction Structure Solution of a Novel Cu-Based Protocatechuate Metal-Organic Framework.

Mechanochemical synthesis is a powerful approach to obtain new materials, limiting costs, and times. However, defected and submicrometrical-sized crystal products make critical their characterization through classical single-crystal X-ray diffraction. A valid alternative is represented by three-dimensional (3D) electron diffraction, in which a transmission electron microscope is used, like a diffractometer. This work matches a green water-based mechanochemical synthesis and 3D electron diffraction to obtain and characterize a Cu-based protocatechuate metal-organic framework (PC-MOF). Its structure has been fully refined through dynamical diffraction theory, and free water molecules could be detected in the channels of the framework. Thermal characterization, focused on the dehydration profile determination, leads to the formation of a novel high-temperature 2D coordination polymer, fully solved with 3D electron diffraction data. At last, the strong activity of the PC-MOF against cationic dyes like methylene blue has been reported.

Metal‐Organic Framework‐Based Composites for Rapid and Sensitive Virus Detection: Current Status and Future Prospective

AbstractThe current spread of various viruses has negatively affected human life and health. Developing enhanced virus diagnostic techniques to mitigate future outbreaks is becoming vital. Metal‐organic frameworks (MOFs) have gained significant attention for their potential applications in virus detection because of their outstanding features, including high surface area, tunable properties, and adjustable pore size. Integrating nanomaterials with MOFs can also further enhance these properties, creating a new class of materials referred to as MOF‐based nanocomposites. This review paper provides an overview of the MOF‐based nanocomposites' status and future prospects for enhanced virus detection. The recent advances in the synthesis and functionalization of MOF and MOF‐based nanocomposites for virus detection are discussed. The paper describes the different types of detection platforms, including nucleic acid and immunological detection, as well as the mechanisms of MOF‐based sensors and the techniques used to synthesize MOFs and MOF‐based nanocomposites for virus detection. Additionally, the review paper explores the potential of integrating MOFs into real sensing devices and their prospects in real‐life applications. Finally, the paper examines the current challenges of these biosensing platforms. Overall, the review paper highlights the capability of MOFs and MOF‐based nanocomposites as versatile and practical platforms for virus detection and provides a comprehensive overview of the latest advancements in this area of research.

Metal-organic skeleton derived RuCoMoCuOx/C porous nanosheet as an efficient dual-function electrocatalyst for superior water decomposition

Polymetallic composites can significantly affect the structure and active sites of materials. In this study, we prepared polymetallic organic structures using a metal-organic framework (MOF) synthesis strategy and a hydrothermal method. We controlled and adjusted the ratio of metals to create precursors, which were then calcined to produce targeted polymetallic oxides. The polymetallic oxides prepared (RuCoMoCuOx/C) demonstrated excellent properties for both HER and OER in 1.0 M KOH, with an overpotential of 136 mV @ 10 mA cm−2 for HER and 296 mV @ 10 mA cm−2 for OER. The efficient catalytic performance of dual hydrolysis is attributed to the lamellar porous structure of RuCoMoCuOx/C and the synergistic effect of each metal element in the polymetallic catalyst. DFT theoretical calculations show that when H2O molecules adsorb around Ru, Co, and Mo sites, OH* adsorbs at electron-deficient centers, while H+ is more readily adsorbed by electron-rich Cu sites. This unique configuration is more conducive to water dissociation.

Synthesis and evaluation of mixed 3d transition metal organic frameworks for energy application

Mixed metal-organic frameworks (MOFs) have generated considerable interest in the field of energy storage and conversion, attributed to their synergistic effects and exceptional electro chemical performance. In this work, a series of bimetallic-MOFs were synthesized utilizing same organic component i.e. benzene-1, 4-dicarboxylic acid (BDC) and changing the metal ions viz. Cu/Fe, Cu/Co, Cu/Ni and Cu/Zn, envisaging synergistic catalysing performance by various metal ions. All the synthesized MOFs were characterized, and the parameters were optimized. Under optimal experimental conditions, among the various MOFs examined, Cu/Co-BDC MOF exhibited the highest specific capacitance of 1892 Fg−1 at a scan rate of 1 mVs−1 with the energy density of 95.78 Whkg−1 and power density of 1915 Wkg−1. This material displayed exceptional supercapacitance performance, characterized by a superior capacitive retention of 85.5% even after 5000 cycles. These finding highlight its potential suitability for super capacitor applications.

Rapid, Massive, and Green Synthesis of Polyoxometalate-Based Metal-Organic Frameworks to Fabricate POMOF/PAN Nanofiber Membranes for Selective Filtration of Cationic Dyes.

Developing high-efficiency membrane materials for the rapid removal of organic dyes is crucial but remains a challenge. Polyoxometalates (POMs) clusters with anionic structures are promising candidates for the removal of cationic dyes via electrostatic interactions. However, their shortcomings, such as their solubility and inability to be mass-produced, hinder their application in water pollution treatment. Here, we propose a simple and green strategy utilizing the room temperature stirring method to mass produce nanoscale polyoxometalate-based metal-organic frameworks (POMOFs) with porous rhomboid-shaped dodecahedral and hexagonal prism structures. The products were labeled as POMOF1 (POMOF-PW12) and POMOF2 (POMOF-PMo12). Subsequently, a series of x wt% POMOF1/PAN (x = 0, 3, 5, and 10) nanofiber membranes (NFMs) were prepared using electrospinning technology, where polyacrylonitrile (PAN) acts as a "glue" molecule facilitating the bonding of POMOF1 nanoparticles. The as-prepared samples were comprehensively characterized and exhibited obvious water stability, as well as rapid selective adsorption filtration performance towards cationic dyes. The 5 wt% POMOF1/PAN NFM possessed the highest removal efficiency of 96.7% for RhB, 95.8% for MB, and 86.4% for CV dyes, which realized the selective separation over 95% of positively charged dyes from the mixed solution. The adsorption mechanism was explained using FT-IR, SEM, Zeta potential, and adsorption kinetics model, which proved that separation was determined via electrostatic interaction, hydrogen bonding, and π-π interactions. Moreover, the POMOF1/PAN membrane presented an outstanding recoverable and stable removal rate after four cycles. This study provides a new direction for the systematic design and manufacture of membrane separation materials with outstanding properties for contaminant removal.

Study of process parameters that enable direct spray drying synthesis of UiO-66-NH2

This study explores the direct spray drying synthesis of UiO-66-NH2, a zirconium-based metal-organic framework (MOF). Focusing on the impact of process parameters on yield and purity, this research employs a solvent-free approach, integrating continuous manufacturing principles for a more sustainable and efficient production process. The influence of gas flow rate, inlet temperature, feed flow rate, and precursor solutions solid loading (SL) were systematically investigated. The prepared samples, mainly at two different precursor solid loadings; labelled as 3%SL-UiO-66-NH2 and 6%SL-UiO-66-NH2, were fully characterised and benchmarked against the solvothermal prepared sample. X-Ray diffraction (XRD) analysis indicated the ability to prepare a totally crystalline UiO-66-NH2 at 150 °C inlet temperature at 3% and 6% SL, without any preheating/mixing steps, and regardless of the other process conditions. Thermogravimetric analysis (TGA) indicated the presence of a higher degree of structural defects within the 3%SL-UiO-66-NH2 sample. The CO2 adsorption capacity was consistent with the decreasing order of surface area and defects as 3%SL-UiO-66-NH2 > STH-UiO-66-NH2 > 6%SL-UiO-66-NH2. This work provides insight into green synthesis and process optimization for MOF synthesis which is beneficial for industrial applications.

Facile synthesis of Co-Cu metal organic framework as efficient non-noble bifunctional electrocatalysts for overall water splitting

The rapid development of superior, highly stable, alkaline-medium-compatible, and nonprecious earth-abundant bifunctional electrocatalysts has garnered significant research interest. This interest aims to replace the costliest noble metals (Pt, Ir/IrO2, and Ru/RuO2) in renewable and green energy technologies for overall water splitting. However, there are still important limitations, such as lower stability and higher energy consumption. In this work, we report the synthesis of Cu-Co metal-organic frameworks (MOFs) as a bifunctional electrocatalyst using a simple chemical precipitation technique. Especially, when 11.5 mM of Co is combined with Cu MOF, it exhibits excellent bifunctional activity for overall water splitting with a lower overpotential of 0.21 V (OER) and -0.71 V (HER) at a current density of 10 mA cm−2, which exhibits nearly several times more enhancement than that of pristine Cu and Co MOFs in a 1 M KOH electrolyte solution. The Tafel slope value of 130 mV/dec and the lower charge transfer resistance, along with relatively high stability for up to 12 h at the onset potential of OER and HER, are observed for the 11.5 mM Cu-Co MOF electrocatalyst. The present results open an alternative pathway for developing a novel design of highly efficient and scalable bifunctional electrocatalysts for overall water splitting.

Locally controlled MOF growth on functionalized carbon nanotubes

Metal-organic frameworks (MOFs) are highly versatile materials because of their tunable properties. However, the typically poor electrical conductivity of MOFs presents challenges for their integration into electrical devices. By adding carbon nanotubes to MOF synthesis, a highly intergrown material with increased conductivity and chemiresistive sensing properties can be obtained. Here, we present a patterning technique to control MOF growth on predefined areas of one particular carbon nanotube. We found that electron beam pretreatment of -COOH functionalized multi-walled carbon nanotubes inhibits the growth of UiO-66 MOF on these multi-walled carbon nanotubes. By irradiating individual multi-walled carbon nanotubes, we show that MOF growth can be inhibited in predefined tube areas, creating MOF-free spaces on the nanotube. In this way, our method shows a possibility to pattern MOF growth on individual nanotubes.

Renewal of electrical energy by green hydrogen using a metal organic framework with Fe3O4 cluster

Recently, metal-–organic frameworks (MOFs) with high porosity have drawn extensive attention in water splitting. The present study reports the synthesis of a porous Fe-based MOF by a modified precursor made of magnetite (Fe3O4). Subsequently, a series of undoped and lanthanide -doped (MOFs) are prepared using the solvothermal method. The synthesis provided a high surface area with a high specific surface and pore volume. The synthesized electrocatalyst with a high surface area is demonstrated as an excellent electrocatalyst for the hydrogen evolution reaction(HER) investigated in acidic media. The electrochemical results demonstrated low Tafel slopes (81 and 166 mV dec–−1), high exchange current, high ssurface area (Cdl) (148.29 and 150.57 mV), and high stability for Au/MIL-53 (Fe)/Gd-Fe3O4 and glassy carbon electrode GCE/MIL-53 (Fe)/La-Fe3O4. The high activity is attributed to the large surface area of the synthesized Fe/ Fe3O4-based MOF, which is porous and magnetic. The effect of base metal on catalyst performance was discussed. Through the unification of two catalytically active metals as lanthanide, a new opportunity opens up for the development of synergistic systems in multiple applications.

Metal Organic Frameworks Synthesis: The Versatility of Triethylamine.

Metal Organic Frameworks (MOFs) are organic-inorganic hybrid materials with exceptionally customizable composition and properties. MOFs intrinsically possess open metal sites, tunable pore size/shape and an ultra-large specific surface area, and have obtained significant attention over the past 30 years. Furthermore, through the integration of functional moieties such as, molecules, functional groups, noble metal clusters and nanocrystals or nanoparticles into MOFs, the resulting composites have greatly enriched the physical and chemical properties of pure MOFs, enabling their application in a wider range of fields. Triethylamine (TEA) as an organic base has consistently played a fundamental role in the development of MOFs. In this Concept, the versatility of triethylamine when involved in the synthesis of MOFs is discussed. Four sections are used to elaborate on the role of TEA including: (1) Single crystal synthesis; (2) Size and morphology control; (3) Counterion of MOFs; (4) MOFs composites synthesis. In the last part, we highlight the potential of TEA for further developments.

Controlled growth-dependent electrochemical behavior of cobalt and 1,3,5 benzene-tricarboxylic acid-based MOFs for efficient supercapacitor applications

This study investigates the synthesis and electrochemical performance of cobalt-BTC acid-based metal-organic frameworks (Co-MOFs) under different hydrothermal conditions. The crystal growth was controlled by varying the concentration of NaOH during synthesis, resulting in three Co-BTC MOF varieties (labeled as COMOFDW-0mM, COMOFDW-3mM, and COMOFDW-6mM). Exhaustive structural-microstructural characterizations, including X-ray diffraction (XRD), scanning electron microscopy (SEM), and N2 adsorption-desorption isotherms, elucidate the structural and morphological variation among these Co-BTC MOF varieties. The crystal structures of COMOFDW-0mM and COMOFDW-3mM exhibit similar laminar configurations, while COMOFDW-6mM shows major variations, such as changes in the coordination modes between BTC and cobalt complexes and differences in BTC plane directions in MOF crystal faces. SEM images reveal distinctive needle-like morphologies, and the as-synthesized crystals exhibit varying aspect ratios. Nitrogen adsorption-desorption isotherms indicate variations in the presence of micropores and mesoporosities, revealing microstructural differences. Electrochemical evaluations in a three-electrode system reveal superior performance for COMOFDW-6mM, with a maximum specific capacitance of 261.27 F/g, an energy density of 7.34 Wh/kg, and a maximum power density of 1325.2 W/kg under 2 M KOH electrolyte. Two-electrode coin cell measurements further validate its potential, maintaining competitive capacitance values. This systematic exploration of Co-MOFs not only elucidates the impact of growth conditions on crystal structures but also underscores the potential for tailoring electrochemical properties. Moreover, the findings present opportunities for further enhancements through composite strategies, opening new avenues for advancing MOFs in energy storage applications.

Facile Tailoring of Metal-Organic Frameworks for Förster Resonance Energy Transfer-Driven Enhancement in Perovskite Photovoltaics.

Förster resonance energy transfer (FRET) has demonstrated its potential to enhance the light energy utilization ratio of perovskite solar cells by interacting with metal-organic frameworks (MOFs) and perovskite layers. However, comprehensive investigations into how MOF design and synthesis impact FRET in perovskite systems are scarce. In this work, nanoscale HIAM-type Zr-MOF (HIAM-4023, HIAM-4024, and HIAM-4025) is meticulously tailored to evaluate FRET's existence and its influence on the perovskite photoactive layer. Through precise adjustments of amino groups and acceptor units in the organic linker, HIAM-MOFs are synthesized with the same topology, but distinct photoluminescence (PL) emission properties. Significant FRET is observed between HIAM-4023/HIAM-4024 and the perovskite, confirmed by spectral overlap, fluorescence lifetime decay, and calculated distances between HIAM-4023/HIAM-4024 and the perovskite. Conversely, the spectral overlap between the PL emission of HIAM-4025 and the perovskite's absorption spectrum is relatively minimal, impeding the energy transfer from HIAM-4025 to the perovskite. Therefore, the HIAM-4023/HIAM-4024-assisted perovskite devices exhibit enhanced EQE via FRET processes, whereas the HIAM-4025 demonstrates comparable EQE to the pristine. Ultimately, the HIAM-4023-assisted perovskite device achieves an enhanced power conversion efficiency (PCE) of 24.22% compared with pristine devices (PCE of 22.06%) and remarkable long-term stability under ambient conditions and continuous light illumination.

Enantiomeric analysis of chiral phenyl aromatic compounds by coated capillary electrochromatography based on aMOF-on-MOF stationary phase.

Chiral phenyl aromatic compounds (CPACs) are widely used in drug development, food/cosmetic production, and other organic synthesis processes, and their different enantiomers have distinct physiological activities and application differences. A double-layer metal-organic framework composite (MOF-on-MOF) was obtained by in situ synthesis of chiral metal-organic framework (CMOM-3S) on the surface of an iron-based metal-organic framework (NH2-MIL-101(Fe)). According to ourinvestigation, MOF-on-MOF composite was for the first time applied tothe stationary phase of capillary electrochromatography (CEC), and enantioseparations of eight CPACs were accomplished. Compared with single CMOM-3S, the enantioseparation performance of the coated capillary columns based on NH2-MIL-101(Fe)@CMOM-3S was improved by 34.07 ~ 720.0%. The R-/S-mandelic acid in actual sample (apricot leaves) was detected by the newly CEC system to be 0.0118mgmL-1 and 0.0523mgmL-1, respectively. The spike recoveries were 96.60 ~ 104.7%, indicating its good stability and accuracy. In addition, the selective adsorption capacity of MOF-on-MOF composites was verified by adsorption experiments.

Enhancing char formation of flame retardant epoxy composites: Onigiri-like ZIF-67 modification with carboxymethyl β-cyclodextrin crosslinking

To enhance char formation of flame retardant epoxy (EP) composites, carboxymethyl β-cyclodextrin (CM-β-CD) is employed as an etchant for or ZIF-67 derivatives. In the early stage, etching plays a dominant role. The mismatch in size between CM-β-CD opening and ZIF-67 pore leads to the stacking of carboxyl cobalt complexes on the shell. When the reaction time is prolonged, crosslinking occurs between carboxyl and hydroxyl groups. Crosslinked CM-β-CD weakens and eventually stops the etching process. Triethyl phosphate (TEP), an additive to improve flame retardancy, is also absorbed on the shell in this one-pot synthesis. Herin, the synthesis of metal-organic framework (MOF) derivatives can impart multiple functions to MOF. This novel nanohybrid significantly improved flame retardancy of EP composites with only 2.0 wt% loading. The peak heat release rate (pHRR) and total smoke production (TSP) were reduced by 54.8 and 46.9%, respectively. The integrated multi-element system resulted in an expanded and reinforced char layer. This study proposes a simple and precise method for controlling the structure of MOF-carbohydrate hybrids through competition between chemical reactions.