Eliminating lattice defects in metal-organic framework molecular-sieving membranes.

Metal-organic framework (MOF) membranes are energy-efficient candidates for molecular separations, but it remains a considerable challenge to eliminate defects at the atomic scale. The enlargement of pores due to defects reduces the molecular-sieving performance in separations and hampers the wider application of MOF membranes, especially for liquid separations, owing to insufficient stability. Here we report the elimination of lattice defects in MOF membranes based on a high-probability theoretical coordination strategy that creates sufficient chemical potential to overcome the steric hindrance that occurs when completely connecting ligands to metal clusters. Lattice defect elimination is observed by real-space high-resolution transmission electron microscopy and studied with a mathematical model and density functional theory calculations. This leads to a family of high-connectivity MOF membranes that possess ångström-sized lattice apertures that realize high and stable separation performance for gases, water desalination and an organic solvent azeotrope. Our strategy could enable a platform for the regulation of nanoconfined molecular transport in MOF pores.

Zeolites and metal-organic frameworks for gas separation: the possibility of translating adsorbents into membranes.

Zeolites and metal-organic frameworks (MOFs) represent an attractive class of crystalline porous materials that possesses regular pore structures. The inherent porosity of these materials has led to an increasing focus on gas separation applications, encompassing adsorption and membrane separation techniques. Here, a brief overview of the critical properties and fabrication approaches for zeolites and MOFs as adsorbents and membranes is given. The separation mechanisms, based on pore sizes and the chemical properties of nanochannels, are explored in depth, considering the distinct characteristics of adsorption and membrane separation. Recommendations for judicious selection and design of zeolites and MOFs for gas separation purposes are emphasized. By examining the similarities and differences between the roles of nanoporous materials as adsorbents and membranes, the feasibility of zeolites and MOFs from adsorption separation to membrane separation is discussed. With the rapid development of zeolites and MOFs towards adsorption and membrane separation, challenges and perspectives of this cutting-edge area are also addressed.

Confined-Coordination Induced Intergrowth of Metal-Organic Frameworks into Precise Molecular Sieving Membranes.

Metal-organic framework (MOF) membranes with rich functionality and tunable pore system are promising for precise molecular separation; however, it remains a challenge to develop defect-free high-connectivity MOF membrane with high water stability owing to uncontrollable nucleation and growth rate during fabrication process. Herein, we report on a confined-coordination induced intergrowth strategy to fabricate lattice-defect-free Zr-MOF membrane towards precise molecular separation. The confined-coordination space properties (size and shape) and environment (water or DMF) were regulated to slow down the coordination reaction rate via controlling the counter-diffusion of MOF precursors (metal cluster and ligand), thereby inter-growing MOF crystals into integrated membrane. The resulting Zr-MOF membrane with angstrom-sized lattice apertures exhibits excellent separation performance both for gas separation and water desalination process. It was achieved H2 permeance of ~1200 GPU and H2/CO2 selectivity of ~67; water permeance of ~8 L ⋅ m-2 ⋅ h-1 ⋅ bar-1 and MgCl2 rejection of ~95 %, which are one to two orders of magnitude higher than those of state-of-the-art membranes. The molecular transport mechanism related to size-sieving effect and transition energy barrier differential of molecules and ions was revealed by density functional theory calculations. Our work provides a facile approach and fundamental insights towards developing precise molecular sieving membranes.

Delicate Softness in a Temperature-Responsive Porous Crystal for Accelerated Sieving of Propylene/Propane.

Soft nanoporous crystals with structural dynamics are among the most exciting recently discovered materials. However, designing or controlling a porous system with delicate softness that can recognize similar gas pairs, particularly for the promoted ability at increased temperature, remains a challenge. Here, we report a soft crystal (NTU-68) with a one-dimensional (1D) channel that expands and contracts delicately around 4 Å at elevated temperature. The completely different adsorption processes of propane (C3H8: kinetic dominance) and propylene (C3H6: thermodynamic preference) allow the crystal to show a sieving separation of this mixtures (9.9 min·g-1) at 273 K, and the performance increases more than 2-fold (20.4 min·g-1) at 298 K. This phenomenon is contrary to the general observation for adsorption separation: the higher the temperature, the lower the efficiency. Gas-loaded in situ powder X-ray analysis and modeling calculations reveal that slight pore expansion caused by the increased temperature provides plausible nanochannel for adsorption of the relatively smaller C3H6 while maintaining constriction on the larger C3H8. In addition, the separation process remains unaffected by the general impurities, demonstrating its true potential as an alternative sorbent for practical applications. Moving forward, the delicate crystal dynamics and promoted capability for molecular recognition provide a new route for the design of next-generation sieve materials.

Polycrystalline Metal-Organic Framework Membranes for Separation of Light Hydrocarbons.

Due to facile designability and versatile nanospace, metal-organic frameworks (MOFs) have been considered as promising membrane materials. Compared to the mixed matrix membranes that incorporated with MOF particles, the polycrystalline MOF membranes demonstrates significant advantages in maximum utilizing the crystalline nanospace, and thus yielding a fruitful of achievements in the last twenty years. Although some reviews have summarized the development of MOF-based membranes, the theoretical framework for oriented design and preparation of polycrystalline MOF membranes for highly efficient separation of light hydrocarbons remains in infancy. Herein, in this review, the fabrication strategies of polycrystalline MOF membranes and the corresponding performance in the separation of light hydrocarbons were classified and summarized. Particularly, the MOF membranes with global and local dynamics have been proposed as an interesting topic promoted performance.

Ion sieving in graphene oxide membranes via cationic control of interlayer spacing.

Graphene oxide membranes-partially oxidized, stacked sheets of graphene-can provide ultrathin, high-flux and energy-efficient membranes for precise ionic and molecular sieving in aqueous solution. These materials have shown potential in a variety of applications, including water desalination and purification, gas and ion separation, biosensors, proton conductors, lithium-based batteries and super-capacitors. Unlike the pores of carbon nanotube membranes, which have fixed sizes, the pores of graphene oxide membranes-that is, the interlayer spacing between graphene oxide sheets (a sheet is a single flake inside the membrane)-are of variable size. Furthermore, it is difficult to reduce the interlayer spacing sufficiently to exclude small ions and to maintain this spacing against the tendency of graphene oxide membranes to swell when immersed in aqueous solution. These challenges hinder the potential ion filtration applications of graphene oxide membranes. Here we demonstrate cationic control of the interlayer spacing of graphene oxide membranes with ångström precision using K+, Na+, Ca2+, Li+ or Mg2+ ions. Moreover, membrane spacings controlled by one type of cation can efficiently and selectively exclude other cations that have larger hydrated volumes. First-principles calculations and ultraviolet absorption spectroscopy reveal that the location of the most stable cation adsorption is where oxide groups and aromatic rings coexist. Previous density functional theory computations show that other cations (Fe2+, Co2+, Cu2+, Cd2+, Cr2+ and Pb2+) should have a much stronger cation-π interaction with the graphene sheet than Na+ has, suggesting that other ions could be used to produce a wider range of interlayer spacings.

Nanomaterial-based electrochemical enzymatic biosensors for recognizing phenolic compounds in aqueous effluents.

With the rapid development of industrial society, phenolic pollutants already identified in water are severe threats to human health. Traditional detection techniques like chromatography are poor in the ability of cost-effectiveness and on-site detection. In recent years, electrochemical enzymatic biosensors have attracted increasing attention for use in the recognition of phenolic compounds, which is considered an effective strategy for the product transfer of portable analytical devices. Although electrochemical enzymatic biosensors provide a fast, accurate on-site detection technique, the difficulties of enzyme deactivation, poor stability and low sensitivity remain to be solved. Thus, effective immobilization methods of enzymes and nanomaterials with excellent properties have been extensively researched to obtain a high-sensitivity and high-stability biosensing platform. Simultaneous detection of multiple phenols may become the focus of further research. In this review, we provide an overview of recent progress toward electrochemical enzymatic biosensors for the detection of phenolic compounds, including enzyme immobilization approaches and advanced nanomaterials, especially nanocomposites with attractive properties such as good conductivity, high specific surface area, and porous structure. We will comprehensively discuss the features and mechanisms of the main enzymes adopted in the construction of different phenolic biosensors, as well as traditional methods (e.g., adsorption, covalent bonding, entrapment, encapsulation, cross-linking) of enzyme immobilization. The most effective method is based on the properties of enzymes, supports and application objective because there is no one-size-fits-all method of enzymatic immobilization. The emphasis will be given to various advanced nanomaterials, including their special nanostructures, preparation methods and performance. Finally, the main challenges in future research on electrochemical phenolic biosensors will be discussed to provide further perspectives for practical applications in dynamic and on-site monitoring. We believe this review will deliver an important inspiration for the construction of novel and high-performance electrochemical biosensors from enzyme selection to nanomaterial design for the detection of various hazardous materials. We believe this review will deliver an important inspiration on the construction of novel and high-performance electrochemical biosensors from the enzyme selection to the nanomaterial design for detections of various hazardous materials.

Membranes for the life sciences and their future roles in medicine.

Since the global outbreak of COVID-19, membrane technology for clinical treatments, including extracorporeal membrane oxygenation (ECMO) and protective masks and clothing, has attracted intense research attention for its irreplaceable abilities. Membrane research and applications are now playing an increasingly important role in various fields of life science. In addition to intrinsic properties such as size sieving, dissolution and diffusion, membranes are often endowed with additional functions as cell scaffolds, catalysts or sensors to satisfy the specific requirements of different clinical applications. In this review, we will introduce and discuss state-of-the-art membranes and their respective functions in four typical areas of life science: artificial organs, tissue engineering, in vitro blood diagnosis and medical support. Emphasis will be given to the description of certain specific functions required of membranes in each field to provide guidance for the selection and fabrication of the membrane material. The advantages and disadvantages of these membranes have been compared to indicate further development directions for different clinical applications. Finally, we propose challenges and outlooks for future development.

PDMS with Tunable Side Group Mobility and Its Highly Permeable Membrane for Removal of Aromatic Compounds.

Polydimethylsiloxane (PDMS), as the benchmark of organophilic membrane materials, still faces challenges for removal of aromatic compounds due to the undesirable transport channels. In this work, we propose to reconstruct the PDMS conformation with tunable side group mobility by introducing phenyl as rigid molecular spacer to relieve steric hindrance of large-sized aromatic molecules; meanwhile, polymer segments are loosely stacked to provide additional degrees of freedom as increasing the permeant size. Moreover, the reconstructed PDMS is engineered into the composite membrane with prevention of condensation of aromatic compounds in the substrate pores. The resulting thin-film composite membrane achieved one order of magnitude higher flux (11.8 kg m-2 h-1 ) with an equivalent separation factor (12.3) compared with the state-of-the-art membranes for aromatic removal. The permeant-customized membrane molecular and microstructure designing strategy opens a new avenue to develop membranes for specific separation targets.

Electrostatic-Induced Crystal-Rearrangement of Porous Organic Cage Membrane for CO2 Capture.

Porous Organic Cages (POCs) with tunable tailoring chemistry properties and polymer-like processing conditions are of great potential for molecular selective membranes, but it remains challenging in the assembly of high crystalline POCs with regular nanochannels for effective molecular sieving. Here we report an electrostatic-induced crystal-rearrangement strategy for the design of a POC membrane with heterostructure. Due to electrostatic attraction, ionic liquid molecules induced cage molecules to rearrange into a sub-10 nm uniform and defect-free crystal layer, which displayed competitive CO2 separation performance. The optimized hetero-structured membrane exhibited an attractive CO2 /N2 separation selectivity of over 130, which was superior to the state-of-the-art membranes, accompanied with excellent long-term and thermal shock stability. This strategy provides a new inspiration for the preparation of crystal-rearranged membranes with regular channels for gas molecule sieving.

Janus Nanocages of Platinum-Group Metals and Their Use as Effective Dual-Electrocatalysts.

Janus nanocages with distinctive platinum-group metals on the outer and inner surfaces can naturally catalyze at least two different reactions. Here we report a general method based on successive deposition and then selective etching for the facile synthesis of such nanocages. We have fabricated 11 different types of Janus nanocages characterized by a uniform size and well-defined {100} facets, together with porous, ultrathin, asymmetric walls up to 1.6 nm thick. When tested as dual-electrocatalysts toward oxygen reduction and evolution reactions, the Janus nanocages based on Pt and Ir exhibited superior activities depending on the thickness and relative position of the metal layer. Density functional theory studies suggest that the alloy composition and surface structure of the nanocages both play important roles in enhancing the electrocatalytic activities by modulating the stability of key reaction intermediates.

Ultrafast Water Transport in Two-Dimensional Channels Enabled by Spherical Polyelectrolyte Brushes with Controllable Flexibility.

Fast water transport channels are crucial for water-related membrane separation processes. However, overcoming the trade-off between flux and selectivity is still a major challenge. To address this, we constructed spherical polyelectrolyte brush (SPB) structures with a highly hydrophilic polyelectrolyte brush layer, and introduced them into GO laminates, which increased both the flux and the separation factor. At 70 °C, the flux reached 5.23 kg m-2 h-1 , and the separation factor of butanol/water increased to ≈8000, which places it among the most selective separation membranes reported to date. Interestingly, further studies demonstrated that the enhancement of water transport was not only dependent on the hydrophilicity of the polyelectrolyte chains, but also influenced by their flexibility in the solvent. Quartz crystal microbalance with dissipation and molecular dynamics simulations revealed the structure-performance correlations between water molecule migration and the flexibility of the ordered polymer chains in the 2D confined space.

Molecular insights on NaCl crystal formation approaching PVDF membranes functionalized with graphene.

Membrane-assisted crystallization is an emerging technology where microporous hydrophobic membranes are used not as selective barriers but to promote the water vapor transfer between phases inducing supersaturation in solution. This has been successfully tested in the crystallization of ionic salts, low molecular weight organic acids and proteins. In this work, molecular dynamics simulations were used to study the crystal nucleation and growth of sodium chloride in contact with hydrophobic polymer surfaces at a supersaturated concentration of salt. A pristine polyvinylidene fluoride (PVDF) surface and PVDF containing different concentrations of graphene platelets were studied. Membrane crystallization tests were performed in parallel, in order to compare the experimental results with the computational ones. Here, with an integrated experimental-computational approach, we demonstrate that graphene-containing membranes assisted the crystal growth of NaCl, speeding up crystal nucleation in comparison with the pristine PVDF membranes. The computational results agreed with the experimental data, allowing the possibility of exploring the behavior of nanomaterials in membrane processes at a microscopic level.

Molecular Bridges Stabilize Graphene Oxide Membranes in Water.

Recent innovations highlight the great potential of two-dimensional graphene oxide (GO) films in water-related applications. However, undesirable water-induced effects, such as the redispersion and peeling of stacked GO laminates, greatly limit their performance and impact their practical application. It remains a great challenge to stabilize GO membranes in water. A molecular bridge strategy is reported in which an interlaminar short-chain molecular bridge generates a robust GO laminate that resists the tendency to swell. Furthermore, an interfacial long-chain molecular bridge adheres the GO laminate to a porous substrate to increase the mechanical strength of the membrane. By rationally creating and tuning the molecular bridges, the stabilized GO membranes can exhibit outstanding durability in harsh operating conditions, such as cross-flow, high-pressure, and long-term filtration. This general and scalable stabilizing approach for GO membranes provides new opportunities for reliable two-dimensional laminar films used in aqueous environments.

A Separation-Sensing Membrane Performing Precise Real-Time Serum Analysis During Blood Drawing.

Dynamic and on-site analysis of serum from human blood is crucial, however, state-of-the-art blood-assay methods can only collect single or discrete data of physiological analytes; thus, the online reports of the dynamic fluctuation of key analytes remains a great challenge. Here, we propose a novel separation-sensing membrane by constructing a heterogeneous-nanostructured architecture, wherein a surface nanoporous layer continuously extracts serum, while the biosensing nanochannels underneath dynamically recognise biotargets, thereby achieving a continuous testing of vital clinical indices as blood is drawn. By precisely controlling the pore structure and nanoshape of biosensing crystals, this membrane achieved accurate and online glucose and lactate monitoring in patients with a variety of medical conditions within 1 min, which is one order of magnitude faster than state-of-the-art techniques. Moreover, various kinds of bio-recognisers can be introduced into this membrane to accurately detect glutamate, transaminase, and cancer biomarkers.

Tuning Gate-Opening of a Flexible Metal-Organic Framework for Ternary Gas Sieving Separation.

In comparison with the fast development of binary mixture separations, ternary mixture separations are significantly more difficult and have rarely been realized by a single material. Herein, a new strategy of tuning the gate-opening pressure of flexible MOFs is developed to tackle such a challenge. As demonstrated by a flexible framework NTU-65, the gate-opening pressure of ethylene (C2 H4 ), acetylene (C2 H2 ), and carbon dioxide (CO2 ) can be regulated by temperature. Therefore, efficient sieving separation of this ternary mixture was realized. Under optimized temperature, NTU-65 adsorbed a large amount of C2 H2 and CO2 through gate-opening and only negligible amount of C2 H4 . Breakthrough experiments demonstrated that this material can simultaneously capture C2 H2 and CO2 , yielding polymer-grade (>99.99 %) C2 H4 from single breakthrough separation.

Finely Tuned Porous Coordination Polymers To Boost Methane Separation Efficiency.

Absorbents with high breakthrough efficiency and weak host-guest interaction are considered to be promising candidates for an energy-saving process in feasible pressure/volume swing adsorption (PSA/VSA). Herein, two groups of finely designed Fe- and Co-based porous coordination polymers (PCPs) are proposed and validated; these possess hourglass-shaped nanochannels, through the cooperation of T-shaped ligands with shifted methyl groups. Featuring optimal nanochannels, high static adsorption, and relatively lower binding energy, one of these polymers, named NTU-30, enables significant C2 H6 /CH4 and C2 H4 /CH4 breakthrough efficiency, with approximately 1.0 or 0.6 g CH4 (100 %) harvested from the corresponding mixtures using 1 g of sample at ambient temperature. Furthermore, the positive effect of aromatic sites within NTU-30 is detected and investigated through an in situ IR study.

Iridium-Based Cubic Nanocages with 1.1-nm-Thick Walls: A Highly Efficient and Durable Electrocatalyst for Water Oxidation in an Acidic Medium.

We report a highly active and durable water oxidation electrocatalyst based on cubic nanocages with a composition of Ir44 Pd10 , together with well-defined {100} facets and porous walls of roughly 1.1 nm in thickness. Such nanocages substantially outperform all the water oxidation electrocatalysts reported in literature, with an overpotential of only 226 mV for reaching 10 mA cm-2 geo at a loading of Ir as low as 12.5 µgIr cm-2 on the electrode in acidic media. When benchmarked against a commercial Ir/C electrocatalyst at 250 mV of overpotential, such a nanocage-based catalyst not only shows enhancements (18.1- and 26.2-fold, respectively) in terms of mass (1.99 A mg-1 Ir ) and specific (3.93 mA cm-2 Ir ) activities, but also greatly enhanced durability. The enhancements can be attributed to a combination of multiple merits, including a high utilization efficiency of Ir atoms and an open structure beneficial to the electrochemical oxidation of Ir to the active form of IrOx .

Finely Controlled Stepwise Engineering of Pore Environments and Mechanistic Elucidation of Water-Stable, Flexible 2D Porous Coordination Polymers.

Two porous coordination polymers (PCPs) with different topologies (NTU-19: sql and NTU-20: dia) underwent finely controlled, stepwise crystal conversions to yield a common water-stable, flexible 2D framework (NTU-22: kgm). The crystal conversions occurred directly at higher temperature via the 3D intermediate (NTU-21: nbo), which could be observed at lower temperature. The successful isolation of the intermediate product of NTU-21, characterization with in situ PXRD and UV/Vis spectra were combined with DFT calculations to allow an understanding of the dynamic processes at the atomic level. Remarkably, breakthrough experiments demonstrate NTU-22 with integral structural properties allowed significant CO2 /CH4 mixture separation.

Accelerating Membrane-based CO2 Separation by Soluble Nanoporous Polymer Networks Produced by Mechanochemical Oxidative Coupling.

Achieving homogeneous dispersion of nanoporous fillers within membrane architectures remains a great challenge for mixed-matrix membrane (MMMs) technology. Imparting solution processability of nanoporous materials would help advance the development of MMMs for membrane-based gas separations. A mechanochemically assisted oxidative coupling polymerization strategy was used to create a new family of soluble nanoporous polymer networks. The solid-state ball-milling method affords inherent molecular weight control over polymer growth and therefore provides unexpected solubility for the resulting nanoporous frameworks. MMM-based CO2 /CH4 separation performance was significantly accelerated by these new soluble fillers. We anticipate this facile method will facilitate new possibilities for the rational design and synthesis of soluble nanoporous polymer networks and promote their applications in membrane-based gas separations.