Metal-organic Framework Membranes Research Articles

Rational MOF Membrane Design for Gas Detection in Complex Environments.

Metal-organic frameworks (MOFs) hold significant promise in the realm of gas sensing. However, current understanding of their sensing mechanisms remains limited. Furthermore, the large-scale fabrication of MOFs is hampered by their inadequate mechanical properties. These two challenges contribute to the sluggish development of MOF-based gas-sensing materials. In this review, the selection of metal ions and organic ligands for designing MOFs is first presented, deepening the understanding of the interactions between different metal ions/organic ligands and target gases. Subsequently, the typical interfacial synthesis strategies (gas-solid, gas-liquid, solid-liquid interfaces) are provided, highlighting the potential for constructing MOF membranes on superhydrophobic and/or superhydrophilic substrates. Then, a multi-scale structure design strategies is proposed, including multi-dimensional membrane design and heterogeneous membrane design, to improve sensing performance through enhanced interfacial mass transfer and specific gas sieving. This strategy is anticipated to augment the task-specific capabilities of MOF-based materials in complex environments. Finally, several key future research directions are outlined with the aim not only to further investigate the underlying sensing principles of MOF membranes but also to achieve efficient detection of target gases amidst interfering gases and elevated moisture levels.

Direct Epitaxial Growth of Polycrystalline MOF Membranes on Cu Foils for Uniform Li Deposition in Long-life Anode-free Li Metal Batteries.

Anode-free Li-metal battery (AFLMB) is being developed as the next generation of advanced energy storage devices. However, the low plating and stripping reversibility of Li on Cu foil prevents its widespread application. A promising avenue for further improvement is to enhance the lithophilicity of Cu foils and optimise their surfaces through a metal-organic framework (MOF) functional layer. However, excessive binder usage in the current approaches obscures the active plane of the MOF, severely limiting its performance. In response to this challenge, MOF polycrystalline membrane technology has been integrated into the field of AFLMB in this work. The dense and seamless HKUST-1 polycrystalline membrane was deposited on Cu foil (HKUST-1M@Cu) via an epitaxial growth strategy. In contrast to traditional MOF functional layers, this binder-free polycrystalline membrane fully exposes lithophilic sites, effectively reducing the nucleation overpotential and optimising the deposition quality of Li. Consequently, the Li plating layer becomes denser, eliminating the effects of dendrites. When coupled with LiFePO4 cathodes, the battery based on the HKUST-1 membrane exhibits excellent rate performance and cycling stability, achieving a high reversible capacity of approximately 160 mAh g-1 and maintaining a capacity retention of 80.9% after 1100 cycles.

Anisotropic porosity and interface synergy enhanced gas permselectivity in heterolayer metal-organic framework membrane.

The pursuit of sustainable, carbon-free separation technology hinges on the efficient separation of gas mixtures with high separation factors and flow rates, i.e. high permselectivity. However, achieving this objective is arduous due to the meticulous engineering at the angstrom scale and intricate chemical manipulation required to design the pores within membranes. To address this challenge, a proof-of-concept for an anisotropic porous membrane has been devised. Employing a meticulous step-by-step methodology, two distinct porous metal-organic frameworks (MOFs) are integrated to form a monolithic anisotropic membrane. By harnessing pore anisotropy (3.4 to 6 Å) aligned with the gas permeation direction and a unique interface characterized by cross-linked pores derived from the two distinct MOFs, this membrane transcends the performance limitations inherent in the individual MOF membranes (~45% enhanced selectivity). This approach not only sheds light on the heterolayer membrane design strategy but also elucidates the intricate CO2/N2 permselectivity relationship inherent in the interface structure.

Channel construction and application of high-connectivity metal-organic framework membranes

Channel construction and application of high-connectivity metal-organic framework membranes

Investigation into the Simulation and Mechanisms of Metal-Organic Framework Membrane for Natural Gas Dehydration.

Natural gas dehydration is a critical process in natural gas extraction and transportation, and the membrane separation method is the most suitable technology for gas dehydration. In this paper, based on molecular dynamics theory, we investigate the performance of a metal-organic composite membrane (ZIF-90 membrane) in natural gas dehydration. The paper elucidates the adsorption, diffusion, permeation, and separation mechanisms of water and methane with the ZIF-90 membrane, and clarifies the influence of temperature on gas separation. The results show that (1) the diffusion energy barrier and pore size are the primary factors in achieving the separation of water and methane. The diffusion energy barriers for the two molecules (CH4 and H2O) are ΔE(CH4) = 155.5 meV and ΔE(H2O) = 50.1 meV, respectively. (2) The ZIF-90 is more selective of H2O, which is mainly due to the strong interaction between the H2O molecule and the polar functional groups (such as aldehyde groups) within the ZIF-90. (3) A higher temperature accelerates the gas separation process. The higher the temperature is, the faster the separation process is. (4) The pore radius is identified as the intrinsic mechanism enabling the separation of water and methane in ZIF-90 membranes.

Enhanced absorption capacity and fundamental mechanism of electrospun MIL-101(Cr)-NH2/PAN nanofibrous membranes for Mo(VI) removal

Amidst the escalating global concern over heavy metal discharge from industrial effluents, Mo(VI), as a potentially toxic trace element, poses significant risks to human and environmental health. Traditional treatment methods such as biodegradation and ion exchange have low removal efficiency, hence, the efficient removal of Mo (VI) ions from industrial wastewater assumes paramount importance. Emerging materials, Metal-Organic Frameworks (MOFs), have garnered extensive attention in water treatment due to their strong adsorption properties, and MOFs membrane materials are hailed as the most promising adsorbents. Therefore, this study aims to prepare a novel membrane material with high efficiency for the removal of Mo (VI) by loading MOFs into nanofibers. Given the water stability of MIL-101, MIL-101-R(-H, -NH2, -NO2) with different functional groups were prepared and subsequently loaded into PAN nanofibrous for the adsorption of Mo(VI). Adsorption kinetics and isotherm studies revealed PAN/MIL-101(Cr)-NH2 to exhibit superior adsorption performance, achieving a maximum adsorption capacity of 171.81 mg g-1. Density functional theory (DFT) calculations and molecular dynamics simulations elucidated the adsorption mechanism, highlighting the role of amino modification in facilitating Mo(VI) adsorption through electrostatic attraction and high reactivity. This work not only offers novel materials and approaches for Mo(VI) wastewater treatment but also advances the industrial application of MOF materials in the domain of heavy metal wastewater treatment.

Crystal orientation control in angstrom-scale channel membranes for significantly enhanced blue energy harvesting

Achieving high-performance blue energy harvesting from the interface between seawater and river water remains challenging, because the current ion-selective membrane suffers from a trade-off between ion permeability and selectivity. Here, we tackle this issue by manipulating the crystal orientations within metal–organic framework (MOF) MIL-178 membranes, including one with the a-axis perpendicular to the substrate, and the other with the b-axis similarly configured. We show that the MIL-178-a-oriented membrane exhibited over one order of magnitude faster ion transport than the MIL-178-b-oriented membrane, and one-dimensional angstrom-scale (∼3.2 Å) channels endow the former with ultrahigh ion selectivity. Consequently, the MIL-178-a-oriented membrane achieves an ultrahigh power density of ∼9.64 W/m2, with an unprecedented energy conversion efficiency of ∼38.5 % approaching the theoretical upper limit of 50 %, when simulated seawater and river water are mixed, surpassing all the reported non-oriented MOF-based membranes. This study presents a method for finely tuning preferred orientations within polycrystalline MOF membranes, enabling precise engineering of ultrahigh-performance osmotic energy conversion.

Electric field-driven assembly of (110) oriented metal–organic framework ZIF-8 monolayer with high hydrogen selectivity

Metal-organic framework (MOF) membranes have showed great potential in gas separation. To date, it is still a great challenge to precisely control the optimal orientation of MOF membranes with an enhanced gas separation performance. Herein, we prepared a compact and (110) oriented ZIF-8 membrane with a thickness of about 265 nm on graphite substrate within 1 h at room temperature via electric-field-driven strategy. Since the membrane is an intergrown one-crystal layer, grain boundary retardation of the flux is eliminated. Furthermore, due to the reduction of the transport pathways through the oriented structure, the (110) oriented ZIF-8 membrane exhibits a high gas separation performance. At 100 °C and 1 bar for the separation of equimolar binary gas mixtures H2/CO2, H2/CH4 and H2/C3H8, separation factors of 49.5, 90.9 and 121.8 can be obtained, with H2 permeance of about 1.7 × 10-7 mol·m−2·s−1·Pa−1. The developed strategy exhibits excellent reproducibility and scalability, and a large area ZIF-8 membrane can be consistently prepared on the graphite substrate, thus facilitating the preparation and application of the ZIF-8 membrane on a large scale. Further, the electric-field-driven strategy is also helpful for the preparation oriented ZIF-67 and ZIF-L membranes, confirming its versatility for the preparation of oriented MOF membranes.

Polydopamine-assisted minute fabrication of vertically aligned ZIF-L membranes for CO2/N2 separations

Metal-organic framework (MOF) membranes demonstrate significant potential for industrial gas separations, yet fabricating vertically aligned two-dimensional (2D) MOF membranes on polymer substrates remains a considerable challenge due to the weak adhesion and difficulty in achieving precise alignment. This study presents a one-step method for the rapid synthesis of vertically aligned ZIF-L membranes, using a polydopamine (PDA)-assisted approach. This method enables the rapid formation of homogenous, thin but defect-free membranes on polymer substrates within 5 min, drastically reducing the preparation time by over 200 times. The vertically aligned ZIF-L membranes, characterized by the interlayer galleries facing the gas mixtures, exhibit an excellent CO2 permeance exceeding 1200 GPU and a CO2/N2 selectivity of 14.5. The versatility of this approach allows for its application on various flat-sheet or even hollow fiber supports. Our findings highlight the potential of PDA-assisted synthesis for efficient, scalable preparation of high-performance MOF membranes for industrial gas separations.

Fabrication of polyacrylonitrile based metal-organic frameworks membranes with super adsorption performance for potential kidney dialysis

One popular technique to remove extra metabolic waste from the blood during renal replacement therapy is blood refining. Enough removal of these toxins from the blood can reduce complications and lengthen survival in dialysis patients. The current blood purification materials are not ideal, there is a need for novel materials with better biocompatibility, less toxicity, and, in particular, more effective toxin uptake rates and cheaper production costs. This requirement has been satisfied in metal-organic frameworks (MOFs). Here, polyacrylonitrile membranes containing MOFs based in different metal sources (Ce, Ca, and Fe) were produced and characterized using PXRD, FTIR, SEM and EDX. The prepared MOFs worked really well at getting rid of a lot of dangerous toxins, such creatinine and p-cresyl sulphate. The adsorption capacities of p-cresyl sulphate onto PAN, Ca-BTC/PAN, Cu-BTC/PAN, Ce-BTC/PAN, and Fe-BTC/PAN were 101.15, 122.70, 270.52, 358.15 and 449.25 mg g−1, respectively; while in the case of creatinine the adsorption capacities were 62.68, 105.9, 225.83, 311.48 and 422.27 mg g−1, respectively. Moreover, the developed membranes showed excellent selectivity and best recyclability of about 6 times.

Low-crystallinity ZIF-8/dcIm membranes for CO2 sieving

Metal-organic framework membranes have shown great potential for efficient separation applications. However, unavoidable grain boundary defects and the inconstant pore size due to framework flexibility hinder the application of MOF membranes for gas separation. Herein, low-crystallinity ZIF-8/dcIm-x membranes are synthesized via fast current-driven synthesis. The competitive coordination of 4,5-dichloroimidazole (dcIm) linker leads to the formation of a low-crystallinity MOF with reduced grain boundary defects for better gas separation performance. Meanwhile, the in-situ substitution of the mIm linker by dcIm narrows the pore size and transforms the ZIF-8 structure in the stiffened Cm polymorph, allowing precise CO2 sieving. Consequently, the low-crystallinity ZIF-8/dcIm-14 membrane exhibits a promising CO2/CH4 selectivity of 32.4 with a CO2 permeance of 1.73 × 10−8 mol m−2 s−1 Pa−1, which surpasses other membranes. Furthermore, the membrane presents a remarkable pressure resistance up to 3 bar and stable temperature-swing operation between room temperature and 125 °C over 120 h.

Hierarchical and defect-free metal-organic framework membranes deep-rooted within flexible nanofiber substrate

Defect-free MOFs membrane on flexible substrate is challenging and promising for industrial applications. In this work, electrospun nanofiber substrates were employed to construct deep-rooted and defect-free ZIF-8 membranes by a symbiotic layer composed of interpenetrated nanofibers and ZIF-8. Nanofibers provide sufficient nucleation sites to construct an interpenetrated “symbiotic layer”, which further supports ZIF-8 growing to be defect-free. Importantly, benefiting from this symbiotic layer, the rigidity difference between substrate and ZIF-8 is well balanced, resulting in ZIF-8 membrane deep-rooted within the support. Furthermore, tannic acid (TA), was combined to modulate the surface chemistry and inter-crystalline defects of ZIF-8 membranes. Finally, a hierarchical ZIF-8 membrane with nanofibers as flexible substrates were obtained. The prepared PAN/TA2-NZIF-80.25 membrane exhibits H2 permeance of 2408 GPU and H2/CO2 selectivity of 21.80. Specifically, compared with the reported MOFs membrane for H2 separation, the H2 permeance of this work locates in a very high region, while proper H2/CO2 separation factor is still remained, exceeding the 2008 upper bound of H2/CO2 separation. Importantly, this membrane presents stable microstructures and separation performance after twisting. The proposed deep-rooted and defect-free ZIF-8 membrane on flexible substrate is competitive to achieve industrial application.

Adipic acid-mediated hydrogen bonding network allocation for efficient proton conduction in water-stabilized lamellar MOF membranes

The poor water-stability and cross-layer proton transfer property pose a challenge to the lamellar metal–organic frameworks (MOFs) membrane when acting as a promising proton exchange membrane. Herein, we report an adipic acid-mediated strategy to improve the water-stability and the cross-layer proton conductivity of CuTCPP lamellar MOF membrane, which achieves a maximum power density and current density of 112.6 mW cm−2 and 424.4 mA cm−2, respectively. Adipic acid with extra functional groups (–PO3H2, –COOH) stably bridges the adjacent crystal layers via the terminal carboxylic acid anchoring Cu sites. In particular, the extra functional groups introduced into the adipic acid regulate the allocation of hydrogen bonding networks in an umbrella-shape around adipic acid with copper-porphyrin structures as external margin, enriching the coherence of hydrogen bonding network on the proton transport path. Benefiting from the regular pore structure of MOF, the optimized hydrogen bonding networks in adjacent crystal layers construct a more abundant through-plane transfer pathway. The resultant through-plane proton conductivities of CuTCPP-PO3H2/–COOH membranes are up to 108/89 mS cm−1 at 80 °C and 100 % RH, which is ∼ 6-fold higher than that of the pristine CuTCPP membrane (13 mS cm−1), with a conductivity attenuation of < 5 % during a humidity cycling test for 12 times.

Desalination Performance Evaluation of hBN@UiO‐66 MOF Incorporated Hollow Fiber Membrane using Membrane Distillation

AbstractIn the present study, the polyvinylidene fluoride (PVDF) modified hollow fiber (HF) membranes have been synthesized by dry‐jet wet phase inversion technique for desalination via direct contact membrane distillation (DCMD). UiO‐66 metal‐Organic framework (MOF) and surface‐modified UiO‐66 with h‐BN nanomaterial have been incorporated with PVDF‐HF membrane. The various analytical methods like FE‐SEM, FTIR, PXRD, TGA, tensile strength, were used to characterize prepared MOF and HF membranes. It was observed from DCMD results that the h‐BN@UiO‐66/PVDF (M3) HF membrane gives higher flux than UiO‐66/PVDF (M2) and pure PVDF (M1) membrane. In the present investigation, response surface methodology (RSM) by box‐behnken design (BBD) was used to optimize the DCMD system and evaluate the behavior of operating parameters such as feed temperature, feed concentration, and feed flow rate. The optimum operating values of feed temperature, feed flow rate, and feed concentration were found as 65 °C, 1 LPM, and 1.5 wt.%, respectively. Under optimum conditions, the M3 HF membrane gives the highest flux of 26.78 L/m2 ⋅ h compared to M2 and M1 membranes. During DCMD, salt rejection is almost greater than 99.8 % for all prepared membranes. Other salts like potassium chloride (KCl), Magnisium Sulphate (MgSO4), and calcium sulphate (CaSO4) are also used to check salt rejection of all membranes at optimum operating conditions. Moreover, the M3 membrane exhibits stable permeate flux and high salt rejection (&gt;99.9 %) at optimized process parameters over 80 h running. Overall, the present study provides the positive effects of h‐BN nanoparticles and UiO‐66 MOF on HF membrane to improve performance in DCMD.

Fabrication Methods of Continuous Pure Metal-Organic Framework Membranes and Films: A Review.

Metal-organic frameworks (MOFs) have drawn intensive attention as a class of highly porous, crystalline materials with significant potential in various applications due to their tunable porosity, large internal surface areas, and high crystallinity. This paper comprehensively reviews the fabrication methods of pure MOF membranes and films, including in situ solvothermal synthesis, secondary growth, electrochemical deposition, counter diffusion growth, liquid phase epitaxy and solvent-free synthesis in the category of different MOF families with specific metal species, including Zn-based, Cu-based, Zr-based, Al-based, Ni-based, and Ti-based MOFs.

Efficient removal of per- and polyfluoroalkyl substances by a metal-organic framework membrane with high selectivity and stability

Per- and polyfluoroalkyl substances (PFAS) in water requires sufficient removal due to their extreme chemical stability and potential health risk. Membrane separation can be a promising strategy, while membranes with conventional structures used for PFAS removal often face challenges such as limited efficiency and stability. In this study, a novel metal-organic framework (MOF) membrane with local modification of polyamide (PA) was developed by introducing interfacial polymerization process during the construction of lamellar membranes with MOF nanosheets. Benefiting from the dense structure and strong negative surface charge, the PA-modified MOF membrane could effectively remove 11 types of PFAS (five short-chain and six long-chain ones with molecular weights ranging from 214.0 to 514.1 Da), especially displaying high rejections for short-chain PFAS (over 84%), along with a remarkable water permeance of 21.4 L·m⁻²·h⁻¹·bar⁻1. The membrane removal characteristics for PFAS were deeply analyzed by elucidating various rejection mechanisms, with particularly distinguishing the rejection and adsorption capacity. Moreover, the membrane stability was significantly enhanced, demonstrated by the structural integrity after 10 min of ultrasonic treatment and stable separation efficiency over 120 h of continuous filtration. With enhanced surface hydrophilicity and negative charge as well as dense membrane pores, the novel membrane also exhibited more superior anti-fouling performance compared to conventional lamellar and PA membranes, further manifesting advantages for practical applications. This work provides a promising solution for developing high-performance membranes tailored specifically for efficient PFAS removal, addressing a critical need in water treatment.

The Key to MOF Membrane Fabrication and Application: the Trade-off between Crystallization and Film Formation.

Metal-organic frameworks (MOFs), owing the merits of ordered and tailored channel structures in the burgeoning crystalline porous materials, have demonstrated significant promise in construction of high-performance separation membranes. However, precisely because this crystal structure with strong molecular interaction in their lattice provides robust structural integrity and resistance to chemical and thermal degradation, crystalline MOFs typically exhibit insolubility, infusibility, stiffness and brittleness, and therefore their membrane-processing properties are far inferior to the flexible amorphous polymers and hinder their subsequent storage, transportation, and utilization. Hence, focusing on film-formation and crystallization is the foundation for exploring the fabrication and application of MOF membranes. In this review, the film-forming properties of crystalline MOFs are fundamentally analyzed from their inherent characteristics and compared with those of amorphous polymers, influencing factors of polycrystalline MOF membrane formation are summarized, the trade-off relationship between crystallization and membrane formation is discussed, and the strategy solving the film formation of crystalline MOFs in recent years are systematically reviewed, in anticipation of realizing the goal of preparing crystalline membranes with optimized processability and excellent performance.

Oriented growth of large-area metal-organic framework ZIF-8 membrane for hydrogen separation

Optimal orientation is the key factor to optimize the gas separation performance of metal-organic framework (MOF) membranes. However, it is still greatly challenging to prepare large-area oriented MOF membranes for industrial applications. Herein, we prepared compact and (100) oriented zeolitic-imidazolate framework-8 (ZIF-8) membranes with membrane area up to 500 cm2 on the graphite substrate via support-induced strategy within 2 h. With membrane thickness of only 620 nm, the (100) oriented ZIF-8 membranes exhibit high gas separation performances due to the reduction of inter-crystalline defects and permeation resistance. At 100 °C and 1 bar, the separation factors of H2/CO2, H2/CH4 and H2/C3H8 are 18.5, 58.2 and 101.6, respectively, with H2 permeance of about 160 x 10−9 mol m−2 s−1·Pa−1. The different positions of the 500 cm2 ZIF-8 membrane show complete consistency in orientation and separation performance, recommending this membrane suitable for future industrial applications. Further, also oriented ZIF-67 and MOF-303 membranes can be consistently prepared by this strategy, confirming its versatility for the preparation of large-area MOF membranes.

Adaptive healing of stress-induced dynamic cracks in a metal-organic framework membrane using nanoparticles.

Dewatering of aqueous azeotropes is crucial and pervasive in raw chemical refineries and solvent recovery in the chemical industry but is recognized as one of the most energy-intensive processes. Pervaporation using crystalline molecular sieve membranes provides an energy-efficient solution, but stress loads stemming from thermal and mechanical risks of pervaporation are most likely to cause membrane cracks, which greatly reduces reliability of membranes in real-world applications. Here, we propose adaptive healing of stress-induced dynamic cracks (AHSDC) in the membrane in a risk-responding manner before separation by using in situ-formed nanoparticles in the same chemical environment. These nanoparticles naturally filled in fissure gaps once cracks formed in the membrane, forming adaptive healing zones. Without loss of dewatering capacity, the separation durability of the membrane after AHSDC was improved by at least two orders of magnitude. The membrane also exhibited tolerance to industrial-grade azeotropes that epitomize industrial multisource nature and complexity.

Selective liquid-phase molecular sieving via thin metal–organic framework membranes with topological defects

Selective liquid-phase molecular sieving via thin metal–organic framework membranes with topological defects