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MOF-5

MOF-5, chemically denoted as Zn₄O(BDC)₃ where BDC²⁻ is 1,4-benzenedicarboxylate, is a prototypical metal-organic framework (MOF) featuring a cubic three-dimensional porous architecture composed of Zn₄O secondary building units interconnected by rigid benzene-1,4-dicarboxylate linkers.^[1] First synthesized in 1999 by Omar M. Yaghi and colleagues via a solvothermal reaction of zinc nitrate and terephthalic acid in N,N-diethylformamide, it represents a landmark in reticular chemistry for its permanent porosity upon desolvation and exceptional structural stability under vacuum. The development of MOFs, including MOF-5, was recognized by the 2025 Nobel Prize in Chemistry awarded to Yaghi, Susumu Kitagawa, and Richard Robson.^[2] This framework's design allows for tunable pore environments while maintaining crystallinity, establishing it as a foundational material in the MOF field.^[3] Key physical properties of MOF-5 include a Brunauer-Emmett-Teller (BET) surface area ranging from 2600 to 4400 m²/g, a micropore volume of 0.92–1.04 cm³/g, and pore diameters of approximately 1–2 nm, which contribute to its high capacity for guest molecule adsorption.^[3] Thermally stable up to 400°C in inert atmospheres, MOF-5 exhibits remarkable chemical robustness in non-aqueous environments but is susceptible to hydrolysis under ambient moisture, limiting its practical deployment without protective modifications such as ligand doping or composite formation.^[3] These attributes, derived from its open-framework topology, enable reversible uptake and release of gases without framework collapse, surpassing many traditional porous materials like zeolites in accessible void space.^[1] MOF-5's versatility has driven its exploration in diverse applications, including hydrogen storage with uptake capacities of ~1.3 wt% at 77 K and 1 bar, reaching up to 5.1 wt% at higher pressures (e.g., 80 bar), carbon dioxide capture for environmental remediation, and heterogeneous catalysis for reactions like CO₂ cycloaddition to epoxides.^[3] It also serves as a scaffold for sensing volatile organic compounds and nitrogen oxides, as well as photocatalysis for pollutant degradation under UV irradiation.^[3] As a pioneering MOF, its synthesis and modification strategies have inspired over two decades of research into isoreticular analogues and hybrid materials, amplifying its impact across energy, environmental, and biomedical technologies.

Discovery and History

Initial Discovery

MOF-5, also known as IRMOF-1, was first synthesized in 1999 by Omar M. Yaghi and colleagues at the University of California, Berkeley. The discovery was detailed in the seminal paper "Design and synthesis of an exceptionally stable and highly porous metal-organic framework" published in Nature by Li, H., Eddaoudi, M., O'Keeffe, M., and Yaghi, O. M.^[1], which introduced MOF-5 as a crystalline material composed of zinc oxide clusters linked by benzene-1,4-dicarboxylate (BDC) ligands, forming a three-dimensional porous framework.^[1] The initial synthesis employed a solvothermal method, reacting zinc nitrate hexahydrate and terephthalic acid in N,N-dimethylformamide (DMF) at 105°C for 24 hours.^[1] The precursor ratio of zinc to BDC was maintained at 1:1, resulting in the formation of white octahedral crystals suitable for structural analysis. This straightforward procedure highlighted the accessibility of the material, enabling rapid characterization via techniques such as X-ray diffraction, which confirmed its cubic structure and exceptional porosity. Upon its introduction, MOF-5 was recognized as the first highly porous metal-organic framework with permanent porosity, demonstrating significant potential for gas storage applications, such as hydrogen and methane adsorption. This breakthrough marked the inception of the isoreticular metal-organic framework (IRMOF) series, inspiring subsequent expansions in framework design and functionality within the broader field of porous materials.

Key Milestones

Following its initial synthesis, a pivotal advancement came in 2003 when researchers demonstrated MOF-5's potential for hydrogen storage, reporting an uptake of 1.0 wt% at room temperature and 4.5 wt% at 78 K under 20 bar pressure, which underscored its promise for gas adsorption applications.^[4] This study, conducted by Rosi, Eckert, Eddaoudi, and colleagues, marked the first systematic evaluation of MOF-5's sorption properties and spurred further investigation into its porous framework for energy-related uses.^[4] In 2007, refinements to the activation process significantly enhanced MOF-5's performance by effectively removing guest molecules such as N,N-dimethylformamide (DMF) and water through solvent exchange followed by controlled heating under vacuum, yielding a BET surface area of approximately 3000 m²/g.^[5] This optimization, building on earlier methods, ensured higher porosity and stability, enabling more reliable measurements of its intrinsic properties and facilitating broader experimental adoption.^[5] The foundational contributions to MOF-5 and reticular chemistry earned Omar Yaghi, a key figure in its development, the 2018 Wolf Prize in Chemistry, shared with Makoto Fujita, for pioneering metal-organic frameworks.^[6] This recognition highlighted MOF-5's role in establishing design principles for porous materials. Subsequently, in 2025, Yaghi shared the Nobel Prize in Chemistry with Susumu Kitagawa and Richard Robson for advancing reticular synthesis, including MOF-5, which revolutionized molecular architecture and applications in storage and separation.^[2] During the 2010s, notable progress included the synthesis of the first phase-pure interpenetrated variant of MOF-5 in 2011 by Hyunuk Kim, Sunirban Das, Min Gyu Kim, Danil N. Dybtsev, Yonghwi Kim, and Kimoon Kim, which introduced enhanced structural complexity while preserving the core topology and improving certain sorption characteristics.^[7] Additionally, in 2016, McKinstry et al. developed a scalable continuous solvothermal synthesis method for MOF-5 crystals, achieving space-time yields up to 1000 kg m⁻³ day⁻¹ and paving the way for industrial production.^[8]

Structure

Composition

MOF-5 possesses the chemical formula \mathrm{Zn_4O(BDC)_3}, where \mathrm{BDC^{2-}} represents the 1,4-benzenedicarboxylate anion, derived from the protonated form terephthalic acid (\mathrm{H_2BDC}).^[9] This composition integrates metal oxide clusters with organic dicarboxylates to form the core molecular units of the material.^[9] The secondary building unit (SBU) in MOF-5 is a tetrahedral \mathrm{Zn_4O} cluster, consisting of four zinc cations bridged by a central oxide anion, with each of the six edges of the tetrahedron capped by a carboxylate group from the \mathrm{BDC^{2-}} linkers.^[9] This \mathrm{Zn_4O(CO_2)_6} unit functions as a robust, paddlewheel-like inorganic node, enabling predictable connectivity in the framework assembly.^[9] The organic linker, \mathrm{BDC^{2-}}, serves as a linear, rigid strut that bridges adjacent SBUs, imparting structural stability and defining the spacing between metal nodes through its para-substituted benzene ring and two carboxylate termini.^[9] As synthesized, MOF-5 typically includes guest solvent molecules within its pores, such as \mathrm{Zn_4O(BDC)_3}(\mathrm{H_2O}_2) or similar formulations incorporating dimethylformamide (DMF) and water, depending on reaction conditions; variations like chlorobenzene guests have also been observed and confirmed via spectroscopic methods.^[9] The activated, porous form is achieved by removing these guests through desolvation, yielding the solvent-free \mathrm{Zn_4O(BDC)_3} while preserving crystallinity and thermal stability up to 400 °C in inert atmospheres.^[3]

Framework Topology

MOF-5 exhibits a cubic crystal structure with space group Fm-3m and a unit cell parameter of a = 25.869 Å for the fully desolvated form.^[10] This arrangement arises from the assembly of Zn₄O secondary building units (SBUs) connected by 1,4-benzenedicarboxylate (BDC) linkers, forming an extended three-dimensional lattice. The framework corresponds to a 6-connected primitive cubic net (pcu topology), where each Zn₄O node is linked to six neighboring nodes via BDC struts, resulting in a highly symmetric, non-interpenetrated architecture that maximizes void space. The pore architecture of MOF-5 consists of smaller tetrahedral pores (~11 Å diameter), larger octahedral pores (~15 Å diameter), and connecting apertures (~8 Å), forming an open channel system that permeates the framework, contributing to a total pore volume of about 1.6 cm³/g (micropore volume 0.92–1.04 cm³/g) and an accessible surface area reaching up to 3800 m²/g under optimal activation conditions.^[10]^[3] The large voids in the non-interpenetrated structure enable exceptional porosity, facilitating applications reliant on high gas accessibility. Interpenetrated variants of MOF-5, where additional frameworks weave through the primary lattice, exhibit reduced pore sizes due to the entanglement, which correspondingly increases the material's density while preserving the overall pcu topology.^[7] These modifications highlight the framework's flexibility in structural design without altering the fundamental SBU-linker connectivity.^[11]

Synthesis

Solvothermal Method

The solvothermal method represents the conventional and widely adopted approach for synthesizing MOF-5, utilizing high-temperature solvent conditions to promote the coordination between zinc ions and terephthalic acid linkers in a sealed reactor. In the standard procedure, zinc nitrate hexahydrate (Zn(NO₃)₂·6H₂O) and 1,4-benzenedicarboxylic acid (H₂BDC) are dissolved in N,N-dimethylformamide (DMF) at a molar ratio of approximately 1:1:120 (Zn:BDC:DMF), followed by heating the mixture in a Teflon-lined autoclave at 100–120 °C for 24–48 hours, which typically yields about 90% crystalline MOF-5 product.^[12]^[13] To optimize the synthesis, modulators such as triethylamine or acetic acid are frequently incorporated, which help regulate nucleation rates, enhance crystallinity, and increase overall yield by deprotonating the linker and preventing premature precipitation.^[14]^[15] Following the reaction, the crude product is subjected to post-synthetic processing, including solvent exchange with chloroform (CHCl₃) to displace residual DMF from the pores, and subsequent evacuation under vacuum at 100 °C to remove guest molecules and activate the framework for applications.^[16] Laboratory-scale syntheses achieve yields of 70–95%, but scaling to larger batches often encounters difficulties in maintaining uniform particle size and morphology due to variations in heat and mass transfer.^[13]^[8]

Alternative Approaches

While the conventional solvothermal synthesis of MOF-5 requires elevated temperatures and prolonged reaction times, alternative approaches have been developed to enhance efficiency, reduce energy consumption, and promote sustainability by minimizing solvent use or enabling room-temperature conditions. These methods include room-temperature, microwave-assisted, mechanochemical, electrochemical, and sonochemical routes, each offering distinct advantages in scalability and control over crystal morphology. Recent advances as of 2024 include continuous flow solvothermal synthesis for improved scalability and mechanistic studies using additives like formic acid to optimize nucleation and crystal growth.^[17] Room-temperature synthesis of MOF-5 was first reported in 2008, utilizing zinc acetate dihydrate and terephthalic acid (H₂BDC) in N,N-dimethylformamide (DMF) with triethylamine as a modulator at 25 °C for ~2.5 hours under rapid stirring.^[18] This approach yields crystals with comparable crystallinity to solvothermal methods but smaller sizes (typically 10-50 μm), facilitating faster nucleation and avoiding thermal decomposition risks. The method's mild conditions make it suitable for labile linkers and supports greener processing by eliminating heating energy. Microwave-assisted synthesis accelerates MOF-5 formation through rapid, uniform heating, completing the reaction in DMF at 150°C within 30 minutes—approximately five times faster than traditional solvothermal processes—while achieving a Brunauer-Emmett-Teller (BET) surface area of about 2900 m²/g. This technique promotes selective phase formation and high reproducibility due to dielectric heating effects that enhance precursor solubility and nucleation rates. Its short duration and atmospheric pressure operation reduce energy demands and solvent evaporation issues, positioning it as an efficient scale-up option for industrial applications. Mechanochemical synthesis enables solvent-free production of MOF-5 by ball-milling zinc oxide (ZnO) with H₂BDC, typically for 30-60 minutes, followed by activation to remove unreacted components. This grinding-induced reaction generates nano-sized MOF-5 particles (often <100 nm), ideal for thin-film fabrication via direct deposition on substrates without additional solvents. The approach's sustainability stems from zero solvent usage and ambient conditions, though it may yield lower crystallinity (45-70% compared to solvothermal), requiring optimization for pore accessibility. It has been applied to produce supported membranes for gas separation, highlighting its versatility in composite materials.^[19] Electrochemical methods, such as electrodeposition in ionic liquids, allow precise control over MOF-5 growth by applying a potential (e.g., 1-3 V) to zinc electrodes in H₂BDC-containing electrolytes, forming uniform films directly on conductive surfaces like indium tin oxide. This cathodic process, often at room temperature, enables morphology tuning—yielding spherical or dendritic structures—and avoids bulk precipitation for targeted thin-layer applications. Sonochemical synthesis complements this by using ultrasound irradiation (20-40 kHz) in solvent media to induce cavitation, rapidly nucleating MOF-5 crystals (5-25 μm) in 1-2 hours at ambient conditions, which enhances mass transfer and results in high-quality, monodisperse particles with BET areas exceeding 3000 m²/g. Both techniques promote sustainability through low energy input and morphological control, though electrochemical routes excel in substrate integration while sonochemical methods suit bulk powder production.^[20]^[21]

Properties

Physical Characteristics

MOF-5 is characterized by its high porosity, with a BET surface area typically ranging from 2600 to 4400 m²/g depending on the synthesis and activation conditions.^[3] The Langmuir surface area can reach as high as approximately 4570 m²/g in optimally activated samples.^[22] Pore volumes vary from 0.8 to 1.3 cm³/g, with micropore volumes commonly measured at 0.92–1.04 cm³/g, contributing to its exceptional internal void space.^[3] Activation to achieve these porosity metrics generally requires evacuation under vacuum at temperatures between 150 and 250°C to remove guest solvents from the pores.^[23] The crystal density of MOF-5 is approximately 0.83 g/cm³, while the skeletal density of the framework material is around 1.15 g/cm³, highlighting the significant porosity that dominates its bulk properties. Thermogravimetric analysis (TGA) indicates thermal stability up to 400°C in an inert atmosphere, beyond which decomposition occurs, with onset temperatures observed around 489°C in some preparations.^[24] A glass transition is noted near 350°C, preceding framework collapse under heating.^[23] Mechanically, MOF-5 is brittle with low tensile strength and a Young's modulus of approximately 2 GPa, as determined by nanoindentation studies, making it susceptible to deformation under stress despite its structural rigidity at low loads.^[25] In solvothermal synthesis, particle sizes typically range from 10 to 100 μm, influencing handling and packing density in practical applications.^[8]

Chemical Behavior

MOF-5 demonstrates notable chemical instability in aqueous environments, primarily due to the susceptibility of its zinc-carboxylate bonds to hydrolysis. Water molecules adsorb onto the coordinatively unsaturated Zn²⁺ sites within the Zn₄O clusters, leading to dissociation of the Zn–O bonds and progressive framework degradation. This process begins with water coordination lengthening the Zn–O bond from approximately 2.0 Å to 2.12 Å, weakening the coordination and ultimately causing structural collapse even at low water concentrations.^[26]^[27] In contrast, the framework maintains integrity in dry organic solvents, such as N,N-dimethylformamide (DMF) and ethanol, where no such hydrolytic attack occurs, allowing for stable storage and handling under anhydrous conditions.^[28] The reactivity of MOF-5 is largely governed by its open metal sites, which emerge upon thermal or solvent-based activation to evacuate guest molecules from the pores. These coordinatively unsaturated Zn²⁺ centers act as Lewis acid sites, capable of coordinating with electron-donating species and facilitating interactions with substrates.^[3] Additionally, the synthesis of MOF-5 is highly sensitive to pH, with optimal framework formation occurring under neutral to mildly basic conditions that promote deprotonation of the terephthalic acid linker and coordination to zinc ions; acidic environments hinder nucleation and lead to amorphous products.^[29] Regarding oxidation and reduction behavior, MOF-5 remains air-stable under ambient conditions, showing no significant reactivity with oxygen at room temperature. However, exposure to high temperatures induces oxidative decomposition, with the framework beginning to degrade above 400°C.^[23] The material exhibits no inherent electrical conductivity, behaving as an electrical insulator in its pristine form. Degradation pathways involve thermal breakdown of the organic linker, where terephthalate decomposition releases CO₂ and benzoic acid as primary products, accompanied by collapse of the metal clusters.^[23] In interpenetrated variants of MOF-5, the catenated frameworks reduce chemical accessibility by narrowing effective pore channels, limiting diffusion of reactive species into the interior.^[8]

Applications

Gas Storage

MOF-5 has been extensively studied for its potential in gas storage due to its high porosity and large surface area, which enable physisorption of various gases within its microporous structure.^[30] The material's ability to adsorb gases is primarily governed by weak van der Waals interactions with the pore walls, with additional enhancement from coordinatively unsaturated zinc sites in the secondary building units.^[30] For hydrogen storage, MOF-5 exhibits an excess uptake of 7.1 wt% at 77 K and 40 bar, achieved through optimized activation procedures to ensure defect-free crystals. At ambient conditions, the capacity is lower, reaching 1.3 wt% at 298 K and 20 bar, highlighting the temperature dependence of physisorption in this framework. These values position MOF-5 as an early benchmark for reversible hydrogen storage in porous materials, though enhancements via doping or composites are often explored for practical applications. Recent hybrids, such as 5 wt% expanded graphite-MOF-5, achieve 5.3 wt% at 77 K and 40 bar as of 2025.^[31] In CO₂ capture, MOF-5 demonstrates an adsorption capacity of 2.5 mmol/g at 298 K and 1 bar, attributed to favorable quadrupole interactions between the CO₂ molecule and the open Zn²⁺ sites.^[32] The material also shows selectivity for CO₂ over N₂ of 18-22:1 under similar conditions, making it suitable for post-combustion flue gas separation where kinetic and equilibrium selectivities favor CO₂ binding.^[32] MOF-5's methane storage capacity is 2.4 wt% at 298 K and 35 bar, aligning with early U.S. Department of Energy targets for vehicular natural gas storage by providing a balance of gravimetric and volumetric uptake.^[30] This performance stems from the framework's ability to accommodate methane molecules in its 0.8 nm pores via dispersion forces, though it falls short of later DOE goals without modifications. Adsorption isotherms for these gases in MOF-5 follow Type I behavior characteristic of microporous materials, indicating monolayer adsorption saturation at low relative pressures, as measured by volumetric or gravimetric techniques.^[30] The isosteric heat of adsorption for H₂ is typically 5–8 kJ/mol, confirming physisorptive binding without strong chemisorption.^[30] This low heat facilitates reversible storage cycles, leveraging the permanent porosity detailed in the material's physical characteristics.

Catalysis and Separation

MOF-5's coordinatively unsaturated zinc sites serve as Lewis acid centers, facilitating heterogeneous catalysis in various organic transformations. These sites activate carbonyl groups in substrates, promoting reactions such as Knoevenagel condensation. For instance, MOF-5 catalyzes the condensation of benzaldehyde with ethyl cyanoacetate at 333 K, achieving notable conversion rates attributed to acidic defects or occluded zinc oxide species within the framework.^[33] In a nanosheet variant of MOF-5 synthesized with 2-methylimidazole, the Knoevenagel condensation of benzaldehyde and malononitrile proceeds with enhanced activity due to increased exposure of catalytic sites, yielding up to 99% product in optimized conditions.^[34] Additionally, MOF-5 supports oxidation reactions; nickel-substituted MOF-5 demonstrates high efficiency in the aerobic oxidation of ethylbenzene to acetophenone, with 56% conversion and 90% selectivity under mild conditions.^[3] Catalysts based on MOF-5 exhibit good recyclability, maintaining activity over at least five cycles with minimal metal leaching (<5%) after separation and reactivation.^[34] In gas separation applications, MOF-5 demonstrates moderate selectivity for CO₂ over CH₄, with ideal adsorbed solution theory (IAST) values around 2.8–8.3 for equimolar mixtures at ambient conditions, driven primarily by equilibrium adsorption differences rather than pronounced kinetic sieving effects.^[35] The framework's uniform pores (approximately 0.8 nm) contribute to size-based discrimination, though diffusion rates for CO₂ and CH₄ are comparable. MOF-5 has also been fabricated into mixed-matrix membranes for post-combustion CO₂ capture from flue gas (CO₂/N₂ mixtures), achieving separation factors >60 with permeances suitable for industrial scaling at high CO₂ feed (88%).^[36] The open zinc sites in MOF-5, which provide coordinative binding, enhance affinity for quadrupolar CO₂ molecules. For liquid-phase separations, MOF-5 effectively adsorbs cationic pollutants through coordination to zinc nodes. It removes dyes such as methylene blue from aqueous solutions, with adsorption capacities reaching up to 194 mg/g in phosphomolybdic acid-modified variants, following Langmuir isotherm models indicative of monolayer binding.^[37] Similarly, for heavy metal ions like Pb²⁺, MOF-5 achieves capacities of 450–750 mg/g at pH 4–6, via electrostatic attraction and chelation at unsaturated Zn sites, outperforming many traditional sorbents.^[38] These processes are reversible, allowing regeneration with dilute acids. The separation mechanisms in MOF-5 involve physisorptive interactions modulated by framework characteristics. Site-specific binding energies for CO₂ range from 20–30 kJ/mol, reflecting weak van der Waals and electrostatic forces that favor selective uptake without strong chemisorption.^[39] While MOF-5 is largely rigid, subtle flexibility at high loadings can induce minor gate-opening effects, potentially aiding dynamic separations by adjusting pore accessibility during adsorption cycles.^[23]

Modifications

Post-Synthetic Changes

Post-synthetic modifications (PSM) of MOF-5 involve targeted alterations to its zinc-based secondary building units (SBUs) or benzene-1,4-dicarboxylate (BDC) linkers after initial synthesis, enabling property tuning while preserving the cubic framework topology. These changes, typically performed via immersion in solvent solutions, allow for the introduction of functional groups or ions without resynthesizing the material, addressing limitations such as limited hydrophilicity or catalytic inactivity in the pristine structure. PSM strategies for MOF-5 are particularly effective due to the lability of Zn-O bonds in the SBUs and the accessibility of linker sites, facilitating partial exchanges that often result in core-shell morphologies where the core remains unmodified and the shell incorporates new components. Ligand exchange represents a key PSM approach for MOF-5, involving the partial substitution of BDC linkers with functionalized analogs, such as 2-aminoterephthalate (amino-BDC), through immersion in dimethylformamide (DMF) solutions at elevated temperatures. This process, driven by diffusion-limited linker ingress, yields core-shell crystals where the outer layer exhibits altered surface chemistry, enhancing hydrophilicity for applications like selective adsorption. For instance, partial linker replacement has been achieved without framework collapse, demonstrating the method's control over functional gradient distribution. Such modifications tune interactions with polar molecules, as seen in increased affinity for water or specific gases compared to the hydrophobic pristine MOF-5. Metal ion exchange in MOF-5 replaces a portion of the Zn²⁺ ions in the Zn₄O SBUs with transition metals like Mn²⁺, Cu²⁺, or Co²⁺, often via soaking in ethanolic metal salt solutions, to impart catalytic properties. This substitution enhances redox activity at the nodes; for example, Mn²⁺-exchanged MOF-5 catalyzes olefin epoxidation with t-BuSO₂PhIO as oxidant, achieving >99% selectivity for epoxide formation from cyclic alkenes through a proposed Mnᴵᵛ-oxo intermediate.^[40] Similarly, Cu²⁺ exchange boosts CO₂ adsorption capacity to 4.6 mmol/g at 274 K and 0–1 bar, a ~31% improvement over unmodified MOF-5, attributed to stronger Lewis acid-base interactions at the mixed-metal nodes.^[41] These exchanges maintain over 90% of the original porosity while introducing site-specific reactivity. Covalent grafting extends PSM capabilities by attaching organic moieties, such as amines, directly to BDC linkers post-exchange to introduce amino groups, followed by reaction with acyl chlorides or anhydrides to form amides or other derivatives. This has been applied to amino-functionalized MOF-5 variants like IRMOF-3, improving water stability by shielding Zn sites; Ni²⁺-exchanged MOF-5, for instance, retains structural integrity in humid environments compared to rapid degradation of pristine MOF-5.^[3] Amine grafting also enhances CO₂ affinity through chemisorption, with examples showing uptake increases from baseline values to enhanced capacities under low-pressure conditions. Additionally, fluorescent tagging via PSM, such as incorporating rhodamine derivatives onto modified linkers, enables sensing applications by quenching or enhancement upon analyte binding, preserving much of the framework's porosity.^[3]

Composite Materials

MOF-5 composites integrate the porous framework with other materials to address inherent limitations such as mechanical fragility, low water stability, and poor electrical conductivity, enabling enhanced performance in practical applications. These hybrids leverage the high surface area of MOF-5 while incorporating polymers, carbon-based materials, or protective shells to improve durability, transport properties, and functionality. Seminal studies have demonstrated that such composites maintain much of MOF-5's porosity while adding synergistic effects from the secondary phase. MOF-5/polymer composites, particularly mixed-matrix membranes, enhance gas separation by combining the polymer's processability with MOF-5's selective adsorption. In Matrimid®-based membranes, incorporation of 30 wt% MOF-5 nanocrystals increased CO₂ permeability by 120% compared to the pure polymer, while ideal gas selectivities such as CO₂/CH₄ remained unchanged, attributed to the uniform dispersion and reduced interfacial voids. This approach overcomes scalability issues in pure MOF membranes by embedding the filler within a flexible polymer matrix like Matrimid®, facilitating large-area fabrication for industrial CO₂ capture. Similar enhancements have been observed in other polymers, underscoring the role of MOF-5 in boosting permeability without sacrificing selectivity. MOF-5/graphene oxide (GO) composites form layered structures through hydrothermal or solvothermal assembly, where GO sheets interlink MOF-5 crystals to improve mechanical strength and multifunctionality. These hybrids boost electrical conductivity due to the conductive pathways provided by reduced GO, enabling applications in electrochemical devices. For hydrogen storage, MOF/GO composites exhibit enhanced uptake at 77 K and 1 bar in simulation-guided designs, surpassing pure MOF-5 through increased surface area and binding sites from GO functionalization.^[42] Core-shell designs encapsulate MOF-5 cores with protective layers like silica or ZIF-8 to impart water resistance, mitigating hydrolysis of the Zn-oxo clusters. In silica-confined MOF-5 (MOF-5@SBA-15), synthesized via a ship-in-a-bottle method, the framework retains structural integrity after 8 hours in humid conditions, compared to complete degradation of pure MOF-5 within 15 minutes, while preserving much of the original surface area for sustained porosity.^[43] ZIF-8 shells on MOF-5 enhance moisture tolerance by leveraging ZIF-8's hydrophobic imidazolate linkers, enabling use in humid environments without pore blockage. These composites extend MOF-5's utility to biomedical and energy applications. In polymer-MOF hybrids, such as nano-MOF-5 embedded in biocompatible matrices, ibuprofen loading occurs via π-π interactions within the pores, enabling controlled release for enhanced drug delivery with reduced burst effects. For energy storage, MOF-5-derived carbon/GO composites in supercapacitors achieve specific capacitances around 300 F/g at low current densities, benefiting from the hierarchical porosity and improved conductivity for high-rate performance. Recent studies as of 2025 have explored machine learning-optimized PSM and sustainable synthesis for MOF-5 composites to further enhance scalability and environmental compatibility.^[3]

References

[1]
Design and synthesis of an exceptionally stable and highly porous metal-organic framework - Nature
### Key Facts About MOF-5 from the Paper
[2]
The pioneering role of metal–organic framework-5 in ever-growing ...
May 12, 2022 · MOF-5 molecules possess a BET surface area from 260 to 4400 m2 g−1 based on a synthetic method with 0.92–1.04 cm3 g−1 micropore and thermal ...Missing: original | Show results with:original
[3]
Hydrogen Storage in Microporous Metal-Organic Frameworks
Here we report very favorable hydrogen sorption properties obtained at 78 K or ambient temperature under safe pressures (up to 20 bar) with crystalline metal- ...Missing: Eddaoudi | Show results with:Eddaoudi
[4]
Impact of Preparation and Handling on the Hydrogen Storage ...
Depending on the preparation, the N2 uptake at saturation varies from 11.8 to 34.4 mmol/g, while the maximum H2 uptake varies from 1.3 to 5.2 excess wt %.
[5]
Omar Yaghi awarded 2018 Wolf Prize | College of Chemistry
Feb 14, 2018 · The Wolf Prize in Chemistry(link is external) has been awarded to The James and Neeltje Tretter Professor of Chemistry Omar M. Yaghi, University of California, ...
[6]
Press release: Nobel Prize in Chemistry 2025 - NobelPrize.org
Oct 8, 2025 · Susumu Kitagawa, Richard Robson and Omar Yaghi are awarded the Nobel Prize in Chemistry 2025. They have developed a new form of molecular ...Missing: 2010 | Show results with:2010
[7]
Scalable continuous solvothermal synthesis of metal organic ...
Here, we show that crystals of MOF-5 can be formed in a scalable solvothermal continuous process with a maximum space time yield of nearly 1000 kg m −3 day −1.
[8]
https://www.sciencedirect.com/science/article/pii/S1385894715014205
[9]
[PDF] Design and synthesis of an exceptionally stable and highly porous ...
Yaghi, O. M., Li, G. & Li, H. Selective binding and removal of guests in a microporous metal-organic framework. Nature 378, 703±706 (1995) ...
[10]
Synthesis of Phase-Pure Interpenetrated MOF-5 and Its Gas ...
Mar 17, 2011 · For the first time, phase-pure interpenetrated MOF-5 (1) has been synthesized and its gas sorption properties have been investigated.Introduction · Results and Discussion · Conclusions · Supporting Information
[11]
Synthesis and characterization of the interpenetrated MOF-5
Mar 12, 2010 · MOF-5 is an important metal–organic framework and has been intensely studied, especially in its hydrogen storage properties.
[12]
MOF-5 Metal−Organic Framework as Sorbent for In-Field Sampling ...
The large tunability of the pore size leads to unprecedented properties and applications. They concern adsorption of species, storage and delivery and the ...
[13]
[PDF] Optimization of Reaction Conditions for Synthesis of MOF-5 using ...
Synthesis of MOF-5 with Solvothermal Method. The clear solution of (Zn(NO3)2. 6H2O) and H2BDC in DMF turned into a mixture of a white solid on the walls and ...
[14]
Continuous manufacturing and scale up of metal organic materials ...
Original studies that were conducted on MOF-5 employed modulators such as triethylamine ... Scalable continuous solvothermal synthesis of metal organic framework ...
[15]
Review on Metal–Organic Framework Classification, Synthetic ...
Due to the unique structure of MOFs, the key application is gas storage because of their large surface area and absence of dead volume. (120) This outcome could ...
[16]
[PDF] Thermal conductivity of a metal-organic framework (MOF-5)
Nov 7, 2006 · chloroform-exchange of large MOF-5 single crystals was 3 days in ... Old solvent, solvent-exchange: direct addition of chloroform liquid.Missing: CHCl3 | Show results with:CHCl3
[17]
[PDF] Room temperature synthesis of metal-organic frameworks
Jun 14, 2008 · MOF-5, originally described in 1999, consists of Zn4O units connected by linear 1,4-benzenedicarboxylate struts to form a cu- bic network.2 ...
[18]
Synthesis of Metal Organic Frameworks by Ball-Milling - MDPI
Dec 27, 2020 · Ball milling is a method of small pollution, short time-consumption, and large-scale synthesis of MOFs. In recent years, many important advances have been made.
[19]
Review—Direct Electrochemical Synthesis of Metal Organic ...
Nov 18, 2020 · In this review, we focus on the direct electrochemical synthesis of MOF with emphasis on anodic and cathodic electrodeposition.
[20]
Sonochemical synthesis of MOF-5. - Semantic Scholar
High quality MOF-5 crystals of 5-25 mum in size were prepared for the first time using a sonochemical method in substantially reduced synthesis time ...
[21]
The pioneering role of metal–organic framework-5 in ever-growing ...
MOF-5 based composites possess ample applications in modern chemistry. Huge surface area, suitable pore dimensions and scope of tunability make MOF-5 noteworthy ...
[22]
Postsynthesis Annealing of MOF-5 Remarkably Enhances the ...
Oct 23, 2014 · We obtained samples with pore vols. ranging from 0.44 to 1.0 cm3/g and Brunauer-Emmett-Teller surface areas ranging from 1000 to 1600 m2/g, the ...
[23]
Mechanical properties of metal–organic frameworks - RSC Publishing
Oct 17, 2019 · Mattesini, Soler, and Ynduráin computed the bulk modulus and Young's modulus of MOF-5 in 2006, predicting that the material is readily ...
[24]
Probing the Water Stability Limits and Degradation Pathways of ...
Mar 4, 2020 · The Zn–carboxylate bond length, d(Zn−O), changed from 2.0 to 2.12 Å, signifying weakening of the Zn–carboxylate bond upon water coordination ( ...
[25]
Water Adsorption and Insertion in MOF-5 | ACS Omega
Aug 24, 2017 · The present study employs van der Waals-augmented density functional theory, transition-state finding techniques, and thermodynamic integration
[26]
In Situ Observation of Solvent Exchange Kinetics in a MOF with ...
Aug 8, 2023 · Solvent exchange of synthesis ... Dynamic DMF Binding in MOF-5 Enables the Formation of Metastable Cobalt-Substituted MOF-5 Analogues.Introduction · Results and Discussion · Conclusion · ReferencesMissing: CHCl3 | Show results with:CHCl3<|control11|><|separator|>
[27]
Synthesis of Phase-Pure Interpenetrated MOF-5 and Its Gas ...
For the first time, phase-pure interpenetrated MOF-5 (1) has been synthesized and its gas sorption properties have been investigated.
[28]
Hydrogen Storage in Metal–Organic Frameworks | Chemical Reviews
In 2003, the initial H2 storage data were reported for MOF-5 (4.5 wt % at 77 K ... Simulation of Hydrogen Storage in MOF-5 and Li-MOF-5 by Ring Polymer ...
[29]
Adsorption of CO2, CH4, N2O, and N2 on MOF-5, MOF-177, and Zeolite 5A
- **CO2 Adsorption Capacity for MOF-5 at 298 K and 1 bar**: 2.95 mmol/g (derived from adsorption equilibrium data at low pressure, as measured volumetrically up to 800 Torr, approximately 1 bar).
[30]
Synthesis of metal organic framework (MOF-5) with high selectivity ...
Jun 3, 2016 · More importantly, synthesized MOF-5 by the maximum C tw exhibits a high selectivity for CO2/N2 of 18-22 at 298 K and 20-130 kPa in simulated ...
[31]
An unexpected bifunctional acid base catalysis in IRMOF-3 for ...
Jul 15, 2012 · ▻ IRMOF-3 is a highly active catalyst for the Knoevenagel condensation. ▻ MOF-5, lacking the amino groups of IRMOF-3, is also active for this ...
[32]
2-Methylimidazole-assisted synthesis of a two-dimensional MOF-5 ...
2-Methylimidazole-assisted synthesis of a two-dimensional MOF-5 catalyst with enhanced catalytic activity for the Knoevenagel condensation reaction†.
[33]
Thermodynamics and kinetics of CH 4 /CO 2 binary mixture ...
Separation of CH4/CO2 by MOF-5 is driven by equilibrium selectivity with no significant contribution from kinetic factors. Abstract. We combine the isotope ...
[34]
Gas Separation Properties of Metal Organic Framework (MOF-5 ...
Aug 5, 2025 · The MOF-5 membranes exhibit a separation factor for CO2/H2 of close to 5 with a feed CO2 composition of 82% and a separation factor for CO2/N2 ...
[35]
[PDF] Achieving Adsorption of Cationic Dyes by the Composites Based on H
The quite efficient adsorption of methylene blue dye in aqueous solution on H3PMo12O40/MOF-5 was studied. The maximum adsorption capacity was. 194.93 mg/g, and ...<|control11|><|separator|>
[36]
Highly Efficient Adsorption of Aqueous Pb(II) with Mesoporous Metal ...
MOF-5 showed relatively high removal capacities at pH 4 and 6, 750, and 660 mg/g, respectively, but a low value at pH 5 (450 mg/g, without pH adjustment). This ...
[37]
CO2 Capture by Metal–Organic Frameworks with van der Waals ...
The vdW-DFs explored here yield a large spread in CO2–MOF binding energies, about 50% (around 20 kJ/mol), depending on the choice of exchange functional, which ...
[38]
Enhanced CO2 adsorption in Cux-MOF-5: Optimal doping and ...
The maximum CO2 adsorption capacity of Cux-MOF-5 material was 4.6052 mmol/g, which was nearly 31 % higher than that of MOF-5 without Cu2+ doping. Even after ...
[39]
Upgrading the Hydrogen Storage of MOF-5 by Post-Synthetic ... - MDPI
Dec 9, 2021 · The highest Brunauer–Emmett–Teller (BET) surface area reported for MOF-5 under optimized synthesis conditions is about 3800 m2/g [23]. The ...
[40]
Synthesis of MOF-5 and IRMOF-3 and post-synthetic introduction of ...
This module focused on the synthesis and characterization of MOF-5 and IRMOF-3 ( Figure 1). The latter of these is subjected to a post-synthetic- modification ...
[41]
https://www.sciencedirect.com/science/article/pii/S2589234725001101
[42]
https://doi.org/10.1016/j.ijhydene.2022.09.199