Ultrathin Metal-organic Framework Research Articles

Preparation of a Nanosheeted Uranyl-Organic Framework for Enhanced Photocatalytic Oxidation of Toluene.

Preparation of ultrathin metal-organic framework (MOF) nanosheets is an effective way to improve the catalytic efficiency of MOF photocatalysts owing to their superiority in reducing the recombination rate of photogenerated electrons and holes and enhancing charge transfer. Herein, a light-sensitive two-dimensional uranyl-organic framework named HNU-68 was synthesized. Due to its interlayer stacking structure, the corresponding ultrathin nanosheets with a thickness of 4.4 nm (HNU-68-N) can be obtained through ultrasonic exfoliation. HNU-68-N exhibited an enhanced ability to selectively oxidize toluene to benzaldehyde, with the value of turnover frequency being approximately three times higher than that of the bulk HNU-68. This enhancement is attributed to the smaller size and interface resistance of the layered HNU-68-N nanosheets, which facilitate more thorough substrate contact and faster charge transfer, leading to an improvement in the photocatalytic efficiency. This work provides a potential candidate for the application of ultrathin uranyl-based nanosheets.

Asymmetric ionogel electrolyte with an ultrathin metal–organic framework layer for lithium dendrite inhibition in solid-state lithium-metal batteries

Solid-state electrolytes (SSEs) are used to prevent internal short circuits caused by the growth of lithium dendrites in solid-state lithium-metal batteries (SSLMBs). Ionogel electrolytes are new polymeric SSEs with outstanding processability, excellent flexibility, and superior ionic conductivity. Lithium-ion transport in ionogel electrolytes depends on ionic liquid (IL) content; however, increasing the IL content improves ionic conductivity but sharply decreases mechanical properties, thus limiting the ability to resist lithium dendrites. Thus, ionogel electrolytes must strike a balance between ionic conductivity and mechanical properties. Herein, we adopt a new strategy to suppress the growth of lithium dendrites by in situ polymerizing an ultrathin metal–organic framework (MOF) layer (9.8 μm) onto a highly ionic conductive ionogel electrolyte. The ionogel electrolyte provides an asymmetric SSE (ASSE) with a remarkable ionic conductivity of 4.8 × 10−4 S cm−1 (30 °C), whereas the ultrathin MOF layer regulates uniform dissolution/deposition of lithium and inhibits lithium dendrite growth, thereby increasing critical current density of the ASSE to 0.65 mA cm−2. An SSLMB assembled with the ASSE and LiFePO4 exhibits excellent performance and cycling stability, maintaining a specific capacity of 125.4 mAh g−1 after 500 cycles at 0.3C.

Large‐Area Ultrathin Metal–Organic Framework Membranes Fabricated on Flexible Polymer Supports for Gas Separations

AbstractUltrathin continuous metal–organic framework (MOF) membranes have the potential to achieve high gas permeance and selectivity simultaneously for otherwise difficult gas separations, but with few exceptions for zeolitic‐imidazolate frameworks (ZIF) membranes, current methods cannot conveniently realize practical large‐area fabrication. Here, we propose a ligand back diffusion‐assisted bipolymer‐directed metal ion distribution strategy for preparing large‐area ultrathin MOF membranes on flexible polymeric support layers. The bipolymer directs metal ions to form a cross‐linked two‐dimensional (2D) network with a uniform distribution of metal ions on support layers. Ligand back diffusion controls the feed of ligand molecules available for nuclei formation, resulting in the continuous growth of large‐area ultrathin MOF membranes. We report the practical fabrication of three representative defect‐free MOF membranes with areas larger than 2,400 cm2 and ultrathin selective layers (50–130 nm), including ZIFs and carboxylate‐linker MOFs. Among these, the ZIF‐8 membrane displays high gas permeance of 3,979 GPU for C3H6, with good mixed gas selectivity (43.88 for C3H6/C3H8). To illustrate its scale‐up practicality, MOF membranes were prepared and incorporated into spiral‐wound membrane modules with an active area of 4,800 cm2. The ZIF‐8 membrane module presents high gas permeance (3,930 GPU for C3H6) with acceptable ideal gas selectivity (37.45 for C3H6/C3H8).

Large-Area Ultrathin Metal-Organic Framework Membranes Fabricated on Flexible Polymer Supports for Gas Separations.

Ultrathin continuous metal-organic framework (MOF) membranes have the potential to achieve high gas permeance and selectivity simultaneously for otherwise difficult gas separations, but with few exceptions for zeolitic-imidazolate frameworks (ZIF) membranes, current methods cannot conveniently realize practical large-area fabrication. Here, we propose a ligand back diffusion-assisted bipolymer-directed metal ion distribution strategy for preparing large-area ultrathin MOF membranes on flexible polymeric support layers. The bipolymer directs metal ions to form a cross-linked two-dimensional (2D) network with a uniform distribution of metal ions on support layers. Ligand back diffusion controls the feed of ligand molecules available for nuclei formation, resulting in the continuous growth of large-area ultrathin MOF membranes. We report the practical fabrication of three representative defect-free MOF membranes with areas larger than 2,400 cm2 and ultrathin selective layers (50‒130 nm), including ZIFs and carboxylate-linker MOFs. Among these, the ZIF-8 membrane displays high gas permeance of 3,979 GPU for C3H6, with good mixed gas selectivity (43.88 for C3H6/C3H8). To illustrate its scale-up practicality, MOF membranes were prepared and incorporated into spiral-wound membrane modules with an active area of 4,800 cm2. The ZIF-8 membrane module presents high gas permeance (3,930 GPU for C3H6) with acceptable ideal gas selectivity (37.45 for C3H6/C3H8).

Exfoliation of Metal–Organic Frameworks to Give 2D MOF Nanosheets for the Electrocatalytic Oxygen Evolution Reaction

AbstractThe structure and properties of materials are determined by a diverse range of chemical bond formation and breaking mechanisms, which greatly motivates the development of selectively controlling the chemical bonds in order to achieve materials with specific characteristics. Here, an orientational intervening bond‐breaking strategy is demonstrated for synthesizing ultrathin metal–organic framework (MOF) nanosheets through balancing the process of thermal decomposition and liquid nitrogen exfoliation. In such approach, proper thermal treatment can weaken the interlayer bond while maintaining the stability of the intralayer bond in the layered MOFs. And the following liquid nitrogen treatment results in significant deformation and stress in the layered MOFs’ structure due to the instant temperature drop and drastic expansion of liquid N2, leading to the curling, detachment, and separation of the MOF layers. The produced MOF nanosheets with five cycles of treatment are primarily composed of nanosheets that are less than 10 nm in thickness. The MOF nanosheets exhibit enhanced catalytic performance in oxygen evolution reactions owing to the ultrathin thickness without capping agents which provide improved charge transfer efficiency and dense exposed active sites. This strategy underscores the significance of orientational intervention in chemical bonds to engineer innovative materials.

Exfoliation of Metal-Organic Frameworks to Give 2D MOF Nanosheets for the Electrocatalytic Oxygen Evolution Reaction.

The structure and properties of materials are determined by a diverse range of chemical bond formation and breaking mechanisms, which greatly motivates the development of selectively controlling the chemical bonds in order to achieve materials with specific characteristics. Here, an orientational intervening bond-breaking strategy is demonstrated for synthesizing ultrathin metal-organic framework (MOF) nanosheets through balancing the process of thermal decomposition and liquid nitrogen exfoliation. In such approach, proper thermal treatment can weaken the interlayer bond while maintaining the stability of the intralayer bond in the layered MOFs. And the following liquid nitrogen treatment results in significant deformation and stress in the layered MOFs' structure due to the instant temperature drop and drastic expansion of liquid N2, leading to the curling, detachment, and separation of the MOF layers. The produced MOF nanosheets with five cycles of treatment are primarily composed of nanosheets that are less than 10 nm in thickness. The MOF nanosheets exhibit enhanced catalytic performance in oxygen evolution reactions owing to the ultrathin thickness without capping agents which provide improved charge transfer efficiency and dense exposed active sites. This strategy underscores the significance of orientational intervention in chemical bonds to engineer innovative materials.

Two-Dimensional Sulfonate-Functionalized Metal-Organic Framework Membranes for Efficient Lithium-Ion Sieving.

Two-dimensional (2D) membranes have shown promising potential for ion-selective separation but often suffer from the trade-off between permeability and selectivity. Herein, we report an ultrathin 2D sulfonate-functionalized metal-organic framework (MOF) membrane for efficient lithium-ion sieving. The narrow pores with angstrom precision in the MOF assist hydrated ions to partially remove the hydration shell, according to different hydration energies. The abundant sulfonate groups in the MOF channels serve as hopping sites for fast lithium-ion transport, contributing to a high Li-ion permeability. Then, the difference in affinity of the Li+, Na+, K+, and Mg2+ ions to the terminal sulfonate groups further enhances the Li-ion selectivity. The reported ultrathin MOF membrane overcomes the trade-off between permeability and selectivity and opens up a new avenue for highly permselective membranes.

Highly efficient and selective capture of uranium from groundwater by using an ultrathin 2D MOF nanosheet with pocket-like cavities

Highly efficient and selective removal of uranium from aqueous media is crucial for the sustained development of nuclear energy. Herein, we utilized the intrinsic advantages of two-dimensional (2D) metal–organic frameworks (MOFs) and developed an ultrathin 2D MOF nanosheet with cavity structure. The preconcentration of the pocket-like cavities on the MOF nanosheet and sufficient interactions with the adsorption sites in the cavity structure realized highly efficient removal of uranium from water. Even in the low concentration range of 0.05–1 ppm, relatively high removal ratios and fast adsorption kinetics still can be achieved. Additionally, the MOF nanosheet exhibited extremely high anti-interference capability, which can efficiently reduce uranium pollution (0.05–1 ppm) in acid groundwater to the safe level (≤30 ppb) recommended by World Health Organization, and the removal performance was comparable to that in deionized water. The adsorption mechanism was thoroughly studied by Fourier transform infrared analysis, X-ray photoelectron spectroscopy, and density functional theory calculations, which revealed that the interactions between uranyl ions and the carboxylate groups dominated uranium adsorption, and the H-bonding interactions in the pocket-like cavities played an important role in uranium extraction.

Benzothiadiazole-functionalized Zr-MOF nanosheets enable visible-light mediated photocatalytic oxidation of sulfides in water

Ultrathin metal-organic frameworks (MOFs) nanosheets incorporating photochromic units are highly efficient heterogeneous photocatalysts, thanks to their highly exposed catalytic sites, short diffusion pathways, and efficient separation of photo-generated carriers. Herein, we report on the solvothermal synthesis of photoactive benzothiadiazole (BTz) functionalized Zr-MOF nanosheets (Zr-BTDB-NS), which are constructed from Zr12 nodes linked by nine BTDB2− (BTDB = 4,4′-(benzo[c][1,2,5]thiadiazole-4,7-diyl)dibenzoate) ligands. The Zr-BTDB-NS exhibited superior photocatalytic activity towards the aerobic oxidation of a broad range of sulfides to their corresponding sulfoxides under visible light irradiation in water at room temperature, even in a gram-scale. The Zr-BTDB-NS can be efficiently recycled and reused for seven cycles without a decrease in conversion or selectivity. Detailed mechanism studies revealed that the Zr-BTDB-NS generates singlet oxygen (1O2) and superoxide radical (O2–) reactive oxygen species under visible light irradiation, which are responsible for the oxidation of sulfides into their corresponding sulfoxides. The simplicity of the synthetic approach as well as the diversity of photoactive organic units hold great promise for designing ultrathin, water-stable, and photoactive Zr-MOF nanosheets. This work will also be of added value for selective photooxidation of sulfides under green and mild conditions.

Ultrathin MOF nanosheets and their mixed-matrix membranes for ammonia and aliphatic amine sensing in water.

Ultrathin 2D metal-organic frameworks (MOFs) exhibit a myriad of unparalleled properties, rendering them extensively applicable across various fields. Despite this, developing a 2D MOF sensor for detecting hazardous amines in water remains a formidable challenge. To address this issue, we synthesized Ni-btc MOF ultrathin nanosheets with a thickness of approximately 4.15 nm for the detection of amines in water. These nanosheets demonstrated a notable "turn-on" fluorescence response in the presence of ammonia and aliphatic amines. The detection limit for aliphatic amines ranged from 297 to 424 nM, while for ammonia, it reached an impressive low limit of around 42 nM, which is an excellent value compared to other reported MOFs for ammonia sensing in water. Density functional theory calculations elucidated the mechanism underlying fluorescence enhancement. Additionally, a mixed matrix membrane based on MOF nanosheets was fabricated for real-time sensing that exhibits an immediate color change in the presence of ammonia and aliphatic amines.

Fabrication of Carboxylate-Functionalized 2D MOF Nanosheet with Caged Cavity for Efficient and Selective Extraction of Uranium from Aqueous Solution.

The efficient removal of radioactive uranium from aqueous solution is of great significance for the safe and sustainable development of nuclear power. An ultrathin 2D metal-organic framework (MOF) nanosheet with cavity structures was elaborately fabricated based on a calix[4]arene ligand. Incorporating the permanent cavity structures on MOF nanosheet can fully utilize its structural characteristics of largely exposed surface area and accessible adsorption sites in pollutant removal, achieving ultrafast adsorption kinetics, and the functionalized cavity structure would endow the MOF nanosheets with the ability to achieve preconcentration and extraction of uranium from aqueous solution, affording ultrahigh removal efficiency even in ultra-low concentrations. Thus, more than 97% uranium can be removed from the concentration range of 50-500µgL-1 within 5min. Moreover, the 2D nano-material exhibits ultra-high anti-interference ability, which can efficiently remove uranium from groundwater and seawater. The adsorption mechanism was investigated by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FT-IR) analysis, and density functional theory (DFT) calculations, which revealed that the cavity structure plays an important role in uranium capture. This study not only realizes highly efficient uranium removal from aqueous solution but also opens the door to achieving ultrathin MOF nanosheets with cavity structures, which will greatly expand the applications of MOF nanosheets.

Ultrathin Metal-Organic Framework Nanosheets for Selective Photocatalytic C2 H2 Semihydrogenation in Aqueous Solution.

The selective semihydrogenation of C2 H2 to C2 H4 in crude C2 H4 (with ~1 vol % C2 H2 contamination) is a crucial process in the manufacture of polyethylene. Comparing to conventional thermalcatalytic route with Pd as catalyst under high temperature with H2 as hydrogen source, photocatalytic C2 H2 reduction reaction with H2 O as hydrogen source can achieve high selectivity under milder conditions, but has rarely been reported. Here, we present a kind of ultrathin metal-organic framework nanosheets (Cu-Co-MNSs) that demonstrate excellent catalytic activities in the semihydrogenation of C2 H2 . Employing Ru(bpy)3 2+ as the photosensitizer, this catalyst attains a noteworthy turnover number (TON) of 2124 for C2 H4 , coupled with an impressive selectivity of 99.5 % after 12 h visible light irradiation. This performance is comparable to molecular catalysts and notably surpasses the efficiency of bulk metal-organic framework materials. Furthermore, Cu-Co-MNSs achieve a 99.95 % conversion of C2 H2 under industrial relevant conditions (1.10 % C2 H2 in C2 H4 ) with 90.3 % selectivity for C2 H4 over C2 H6 , demonstrating a great potential for polymer-grade C2 H4 production.

Step-Nucleation In Situ Self-Repair to Prepare Rollable Large-Area Ultrathin MOF Membranes.

Ultrathin membranes with ultrahigh permeance and good gas selectivity have the potential to greatly decrease separation process costs, but it requires the practical preparation of large area membranes for implementation. Metal-organic frameworks (MOFs) are very attractive for membrane gas separation applications. However, to date, the largest MOF membrane area reported in the literature is only about 100 cm2 . In the present study, a new step-nucleation in situ self-repair strategy is proposed that enables the preparation of large-area (2400 cm2 ) ultrathin and rollable MOF membranes deposited on an inexpensive flexible polymer membrane support layer for the first time, combining a polyvinyl alcohol (PVA)-metal-ion layer and a pure metal-ion layer. The main role of the pure metal-ion layer is to act as the main nucleation sites for MOF membrane growth, while the PVA-metal-ion layer acts as a slow-release metal-ion source, which supplements MOF crystal nucleation to repair any defects occurring. Membrane modules are necessary components for membrane applications, and spiral-wound modules are among the most common module formats that are widely applied in gas separation. A 4800 cm2 spiral-wound membrane modulewas successfully prepared, demonstrating the practical implementation of large-area MOF membranes.

Scalable and sustainable manufacturing of ultrathin metal–organic framework nanosheets (MONs) for solar cell applications

Metal-organic framework nanosheets (MONs) are an emerging class of 2D materials whose tunable chemistry make them ideal for a wide range of sensing, catalytic, electronics and separation applications. However, creating scalable routes to the synthesis of high quality, ultrathin nanosheets remains challenging and little consideration has been given to the economics of making these materials. Here, we demonstrate a scalable synthesis of zinc-porphyrin based nanosheets, Zn2(H2TCPP), for use in organic solar cells and conduct a techno-economic analysis of their pilot-plant scale manufacture. A thorough investigation of the process chemistry of the solvothermal synthesis enabled reduction of reaction time, increased solid content and scale-up of the reaction in batch. Significantly, the addition of triethylamine accelerated the reaction kinetics, which enabled the synthesis temperature to be dropped from > 80 °C to room temperature. Application of these new reaction conditions in a continuous stirred-tank reactor directly formed monolayer MONs at 99 % yield with a space–time yield of 16 kg m−3 day−1, an approximately 20-fold increase in yield compared to adapting the literature procedure. Techno-economic analysis showed a 94 % reduction in the production costs compared to the literature reaction conditions and indicated that the production cost was dominated by ligand price. The general applicability of the method was demonstrated through synthesis of related Cu2(H2TCPP) MONs and tunability through metalation of the porphyrin units with six different metal ions. Finally, the value of the nanosheets was demonstrated through a near doubling in the power conversion efficiency of organic photovoltaic devices when the MONs were incorporated into the active layer. Overall, this work demonstrates the first scalable and sustainable route to producing monolayer nanosheets for high value applications.

Towards ultrathin metal-organic frameworks membranes for high-performance separation

Research on metal-organic frameworks (MOFs) based membranes has gained a lot of attention in the last decade thanks to the unique and highly versatile chemistry of MOFs, which allows one to synthesize a variety of structural dimensions, topologies, pore sizes, pore shapes, functional groups, and chemical environments. For membrane application, the field is rapidly progressing, with the focus shifting from the synthesis of pinhole-free polycrystalline films to the synthesis of ultrathin MOF films on scalable support to surpass the performance of polymeric membranes. In this research update, we review promising methodologies for the synthesis of ultrathin MOF membranes. We then discuss the application of these ultrathin MOF films in gas separation, ion transport and ion–ion separation, and desalination. We then provide our perspective on opportunities and challenges for the future development of ultrathin MOF membranes.

Ultrathin 2D Pd/Cu Single-Atom MOF Nanozyme to Synergistically Overcome Chemoresistance for Multienzyme Catalytic Cancer Therapy.

Single-atom nanozymes (SAzymes) have obtained increasing interest to mimic natural enzymes for efficient cancer therapy, while challenged by chemoresistance from cellular redox homeostasis and the interface of reductive species in tumor microenvironment (TME). Herein, a dual single-atomic ultrathin 2D metal organic framework (MOF) nanosheet of multienzyme (Pd/Cu SAzyme@Dzy) is prepared to synergistically overcome chemoresistance for multienzyme enhanced cancer catalytic therapy. The Pd SAzyme exhibits peroxidase (POD)-like catalytic activity for overcoming chemoresistance via disturbing cellular redox balance. This is further enhanced by cascade generation of more ∙OH via Cu+ -catalyzed POD-like reactions, initiated by in situ-reduction of Cu2+ into Cu+ upon GSH depletion. This process can also avoid the consumption of ∙OH by endogenous reductive GSH in TME, ensuring the adequate amount of ∙OH for highly efficient therapy. Besides, the DNAzyme is also delivered for gene therapy of silencing cancer-cell-targeting VEGFR2 protein to further enhance the therapy. Based on both experiments and theoretical calculations, the synergetic multienzyme-based cancer therapy is examined and the enhancement by the cascade tumor antichemoresistance is revealed.

The engineering design of single-site nanozyme based on metal-organic layers for the detection of antioxidant substances

Nanozyme is a kind of nanomaterial with enzyme activity similar to that of a natural enzyme. In order to endow nanozymes with high catalytic efficiency, reducing the dimensionality of nanomaterials, which means more active sites of nanozymes can be exposed, is an effective way. Herein, as a kind of ultra-thin metal organic framework, metal organic layers (MOLs) based on Zr4+ and 4'-(4-carboxyphenyl)-[2,2':6′,2″-terpyridine]-5,5″-dicarboxylic acid (TPY) were selected for the construction of a single-site nanozyme. To achieve higher catalytic efficiency, single-site structure, which featured with “Fe–N–C,” was designed intelligently through coordination between Fe2+ and TPY. The as-prepared nanozyme Fe–Zr–MOL with just 2.7 wt% Fe showed high peroxidase-like activity. What's more, Fe–Zr–MOL showed excellent detection ability of ascorbic acid (AA) through colorimetric method based on the redox of oxidated 3,3′,5,5′-tetramethylbenzidine. In particular, owing to the temperature-dependent mimic enzyme activity of Fe–Zr–MOL, linear discriminant analysis method could be well used to distinguish different antioxidant substances. This work not only provides a nanozyme with high catalytic efficiency by single-site engineering based on MOL, but also realizes the sensitive colorimetric detection of AA and the differentiation of different antioxidant substances.

Curtailing the Excess eg-Orbital Filling of a Ni Atom by Enhanced Interatomic Charge Transfer within a Bimetallic 2D Metal–Organic Framework for the Oxygen Evolution Reaction

Electrochemical conversion technologies rely on the design and creation of highly efficient electrocatalysts. The oxygen evolution reaction (OER), which has applications in water splitting and metal–air batteries, is a crucial process in such conversions. Herein, a bimetallic Co, Ni-based ultrathin metal–organic framework nanoribbon (NiCo-NR) is reported for an efficient OER. It is proposed that in ultrathin MOF nanoribbons, the surface atoms (Co, Ni) are coordinatively unsaturated, due to which the interatomic electron transfer within the MOF makes more active adsorption sites on the surface. The catalyst exhibits an overpotential of 244 mV at a current density of 10 mA cm–2 with a Tafel slope value of 85 mV dec–1. For the stability experiment, the catalyst was exposed for 35 h of uninterrupted operation at a current density of 100 mA cm–2. Our findings showed that coordinatively unsaturated transition metal atoms were dominant active sites and the electrocatalytic activity can be tuned by the coupling interactions of Ni and Co metals. The excess eg-orbital filling of the Ni atom, which limits the electrocatalytic performance, can be reduced by π-donation from Ni to Co through the oxygen atom.

Multi‐assembled nanofiltration membranes with excellent separation and catalytic performance

AbstractBACKGROUNDAccording to the characteristics of various nanomaterials, assembling these nanomaterials is an effective way to control the structure and properties of nanocomposites.RESULTSIn this work, nanofiltration membranes (NM) were prepared by assembling several nanomaterials that have excellent separation and catalytic properties. SiO2 nanoparticles were employed to optimize the water nanochannels between graphene oxide (GO) nanosheets to fabricate GO/SiO2 NM, whose water flux was 73.2 L m−2 h−1 and the rejection ratio was 99.1%. The combination of high‐conductivity hydroxylated graphene (G‐OH) with flake NiCo‐BDC (BDC refers to deprotonated terephthalic acid) ultra‐thin metal organic framework (UMOF) to obtain UMOF&G‐OH could improve the catalytic performance of the UMOF by about 23.5%. In order to realize the synchronous catalysis and separation performance of nanofiltration membrane, UMOF&G‐OH was reassembled with GO and SiO2. The pure water flux of (UMOF&G‐OH)/GO/SiO2 nanofiltration membrane was 95.8 L m−2 h−1 and the rejection ratio was 99.1%. TiO2 nanoparticles were added to the membrane to regulate the distance between the flake, and the selective permeation of the composite membrane was further improved to 99.9%; the pure water flux reached 92.6 L m−2 h−1.CONCLUSIONThe introduction of G‐OH would be beneficial in improving the migration and separation efficiency of the photogenerated electron holes, and effectively improve the catalytic performance of the semiconductor catalyst. Through the assembly of a variety of nanoparticles and lamellar materials, the water nanochannel could be accurately controlled and the catalytic performance of the membrane could be given, so as to obtain a nanofiltration membrane with high water flux and high rejection ratio. © 2023 Society of Chemical Industry.

Large-Area Fabrication of Ultrathin Metal-Organic Framework Membranes.

Metal-organic framework (MOF)-based membranes, featuring potential molecular sieving effects and therefore capable of surmounting the ubiquitous trade-off between membrane selectivity and permeability, hold great promise for multitudinous chemical separations. Nevertheless, it remains highly challenging for the large-area fabrication of ultrathin MOF membranes with variable thickness, great homogeneity, and preferential orientation. Herein, this work reports the facile fabrication of ultrathin (down to 20nm) NUS-8 membranes in large-area (>200 cm2 ) yet with great homogeneity and texture along (00l) direction due to the superior solution processability of the as-synthesized NUS-8 nanosheets. The resultant NUS-8 membranes with good adhesion properties and certain flexibility exhibit excellent rejections (>98% for Mg2+ and Al3+ , and dyes with molecular weights larger than 585.5 g mol-1 ) toward aqueous separation of various metal ions and dyes at modest permeance (1-3.2 L m-2 h-1 bar-1 ) due to the well-aligned structures. Such separation performance outstands among polymetric membranes, thin-film composite membranes, mixed matrix membranes, and other MOF membranes reported in the literature. The separation mechanism is reasonably discussed based on the experimental and theoretical results. This study opens up novel perspectives for preparing ultrathin and large-area MOF membranes using the solution processability of MOFs.