Tuning the Stacking Modes of Ultrathin Two-Dimensional Metal-Organic Framework Nanosheet Membranes for Highly Efficient Hydrogen Separation.

Two-dimensional (2D) metal-organic framework (MOF) membranes are considered potential gas separation membranes of the next generation due to their structural diversity and geometrical functionality. However, achieving a rational structure design for a 2D MOF membrane and understanding the impact of MOF nanosheet stacking modes on membrane separation performance remain challenging tasks. Here, we report a novel kind of 2D MOF membrane based on [Cu2 Br(IN)2 ]n (IN=isonicotinato) nanosheets and propose that synergetic stacking modes of nanosheets have a significant influence on gas separation performance. The stacking of the 2D MOF nanosheets is controlled by solvent droplet dynamic behaviors at different temperatures of drop coating. Our 2D MOF nanosheet membranes exhibit high gas separation performances for H2 /CH4 (selectivity >290 with H2 permeance >520 GPU) and H2 /CO2 (selectivity >190 with H2 permeance >590 GPU) surpassing the Robeson upper bounds, paving a potential way for eco-friendly H2 separation.

3-Methoxythiophene-Based Indophenine Reaction Generating an Isomeric Dynamic Equilibrium System.

A 3-methoxythiophene-based indophenine reaction with N-(2-hexyldecyl)isatin in the presence of concentrated sulfuric acid produces an indophenine cis-trans isomeric dynamic equilibrium system, which is dominated by the (Z,E,Z) configuration with a trace of the (Z,Z,Z) configuration.

Preparation of Carbon Dots from PET Waste by One-step Hydrothermal Method and its Application in Light Blocking Films and LEDs.

An environmentally friendly PET-based Carbon Dots (PET-CDs) with excellent fluorescence properties were prepared with waste PET bottle, pyromellitic acid and ammonia water as raw materials by one-step hydrothermal method. The preparation mechanism of PET-CDs was as follows: PET first underwent ammonolysis reaction to produce terephthalic acid diamide and ethylene glycol, and then dehydrated and carbonized with pyromellitic acid to form PET-CDs. The as-prepared PET-CDs exhibit excitation-independent emission properties in the range from 340 to 440 nm, and the fluorescence quantum yield is as high as 87.36%. In terms of structure, PET-CDs is a spherical structure with an average particle size of 2.0 nm, and its surface contains carboxyl and amino groups. The PET-CDs were dispersed in a PVA matrix to obtain an light blocking films(LBFs) for 250-450 nm light with excellent properties, and its transparency for 450-700 nm light is good. In addition, PET-CDs was used in the fields of LED, and it was found that the color coordinate for the LED assembled with PET-CDs and 395 nm LED chips is (0.55, 0.44) and the correlated color temperature is 2018 K.

Solvothermal preparation of nitrogen-doped carbon dots with PET waste as precursor and their application in LEDs and water detection.

Developing novel, alternative ways to recycle PET waste, which has an important influence on reduction of landfilling and CO2 emissions, has always been a research hot spot for industry and academy. In this work, PET waste was adopted as precursor for the preparation of nitrogen-doped Carbon Dots (NCDs). Firstly, PET oligomers were obtained by alcoholysis of PET waste with ethylene glycol. Then, the mixture without isolation and purification as well as pyromellitic acid dianhydride and urea were adopted as precursors for the preparation of NCDs by solvothermal method with tetrahydrofuran (THF) as solvent. The as-prepared NCDs has a spherical structure with an average particle size of 2.3 nm. What is more, NCDs exhibit excitation-independent emission properties, the largest excitation peak and emission peak of NCDs located in 360 nm and 470 nm, and the fluorescence quantum yield is 48.16 %. In term of application, NCDs are dispersed in PMMA and loaded on 365 nm and 430 nm LED chips to obtain LED devices emitting yellow light ((0.55, 0.44), 2018 K) and warm white light ((0.37, 0.31), 3783 K), respectively. In addition, NCDs could be adopted as fluorescent probe for the construction of sensor for water in organic solvents based on dynamic quenching of NCDs, and the limit of detection (LOD) is 0.00001 %.

Ultrathin and Ultrastrong Kevlar Aramid Nanofiber Membranes for Highly Stable Osmotic Energy Conversion.

An ion-selective membrane can directly convert the osmotic energy to electricity through reverse electrodialysis. However, developing an advanced membrane that simultaneously possesses high power density, excellent mechanical strength, and convenient large-scale production for practical osmotic energy conversion, remains challenging. Here, the fabrication of ultrathin and ultrastrong Kevlar aramid nanofiber (KANF) membranes with interconnected three-dimensional (3D) nanofluidic channels via a simple blade coating method is reported. The negatively charged 3D nanochannels show typical surface-charge-governed nanofluidic ion transport and exhibit excellent cation selectivity. When applied to osmotic energy conversion, the power density of the KANF membrane-based generator reaches 4.8 W m-2 (seawater/river water) and can be further increased to 13.8 W m-2 at 328 K, which are higher than most of the state-of-the-art membranes. Importantly, a 4-µm-thickness KANF membrane shows ultrahigh tensile strength (565 MPa) and Young's modulus (25 GPa). This generator also exhibits ultralong stability over 120 days, showing great potential in practical energy conversions.

A Lamellar MXene (Ti3 C2 Tx )/PSS Composite Membrane for Fast and Selective Lithium-Ion Separation.

A two-dimensional (2D) laminar membrane with Li+ selective transport channels is obtained by stacking MXene nanosheets with the introduction of poly(sodium 4-styrene sulfonate) (PSS) with active sulfonate sites, which exhibits excellent Li+ selectivity from ionic mixture solutions of Na+ , K+ , and Mg2+ . The Li+ permeation rate through the MXene@PSS composite membrane is as high as 0.08 mol m-2 h-1 , while the Li+ /Mg2+ , Li+ /Na+ , and Li+ /K+ selectivities are 28, 15.5, and 12.7, respectively. Combining the simulation and experimental results, we further confirm that the highly selective rapid transport of partially dehydrated Li+ within subnanochannels can be attributed to the precisely controlled interlayer spacing and the relatively weaker ion-terminal (-SO3 - ) interaction. This study deepens the understanding of ion-selective permeation in confined channels and provides a general membrane design concept.

Supported MXene/GO Composite Membranes with Suppressed Swelling for Metal Ion Sieving.

Novel two-dimensional (2D) membranes have been utilized in water purification or seawater desalination due to their highly designable structure. However, they usually suffer from swelling problems when immersed in solution, which limits their further applications. In this study, 2D cross-linked MXene/GO composite membranes supported on porous polyamide substrates are proposed to improve the antiswelling property and enhance the ion-sieving performance. Transition-metal carbide (MXene) nanosheets were intercalated into GO nanosheets, where the carboxyl groups of GO combined the neighboring hydroxyl terminal groups of MXene with the formation of -COO- bonds between GO and MXene nanosheets via the cross-linking reaction (-OH + -COOH = -COO- + H2O) after heat treatment. The permeation rates of the metal ions (Li+, Na+, K+, Al3+) through the cross-linked MXene/GO composite membrane were 7-40 times lower than those through the pristine MXene/GO membrane. In addition, the cross-linked MXene/GO composite membrane showed excellent Na+ rejection performance (99.3%), which was significantly higher than that through pristine MXene/GO composite membranes (80.8%), showing improved ion exclusion performance. Such a strategy represents a new avenue to develop 2D material-derived high-performance membranes for water purification.

Flexible Polypropylene-Supported ZIF-8 Membranes for Highly Efficient Propene/Propane Separation.

Metal-organic framework (MOF) membranes have enormous potential in separation applications. There are several MOF membranes grown on polymer substrates aimed for scale-up, but their brittleness hampers any industrial application. Herein, intergrown continuous polypropylene (PP)-supported ZIF-8 membranes have been successfully synthesized via fast current-driven synthesis (FCDS) within 1 h. The PP-supported ZIF-8 membranes exhibit a promising separation factor of 122 ± 13 for binary C3H6-C3H8 mixtures combined with excellent flexibility behavior. The C3H6/C3H8 separation performance of the PP-supported ZIF-8 membrane was found to be constant after bending the supported ZIF-8 film with a curvature of 92 m-1. This outstanding mechanical property is crucial for practical applications. Moreover, we further synthesized ZIF-8 membranes on various polymer substrates and even polymer hollow fibers to demonstrate the production scalability.

Balancing the Grain Boundary Structure and the Framework Flexibility through Bimetallic Metal-Organic Framework (MOF) Membranes for Gas Separation.

Separation is one of the most energy-intensive processes in the chemical industry, and membrane-based separation technology helps to reduce the energy consumption dramatically. Supported metal-organic framework (MOF) layers hold great promise as a molecular sieve membrane, yet only a few MOF membranes showed the expected separation performance. The main reasons include e.g. nonselective grain boundary transport or the flexible MOF framework, especially the inevitable linker rotation. Here, we propose a crystal engineering strategy that balances the grain boundary structure and framework flexibility in Co-Zn bimetallic zeolitic imidazolate framework (ZIF) membranes and exploit their contributions to the improvement of membrane quality and separation performance. It reveals that a good balance between the two trade-off factors enabled a "sweet spot" that offers the best C3H6/C3H8 separation factor up to 200.

Antibiotics Separation with MXene Membranes Based on Regularly Stacked High-Aspect-Ratio Nanosheets.

The uncontrolled release of antibiotics and pharmaceuticals into the environment is a worldwide increasing problem. Thus, highly efficient treatment technologies for wastewater are urgently needed. In this work, seven kinds of typical antibiotics (including water and alcohol soluble ones) are successfully separated from the corresponding aqueous and ethanolic solutions using highly regular laminated membranes. Our membranes are assembled with 2-4 µm titanium carbide nanosheets. The solvent permeance through such titanium carbide membrane is one order of magnitude higher than that through most polymeric nanofiltration membranes with similar antibiotics rejection. This high flux is due to the regular two-dimensional (2D) structure resulting from the large aspect ratio of titanium carbide nanosheets. Moreover, the electrostatic interaction between the surface terminations and the antibiotics also affects the rejection and enhances the antifouling property. Such 2D titanium carbide membranes further broaden the application scope of laminated materials for separation and purification of high value added drugs in academia and industry.

Oppositely Charged Ti3 C2 Tx MXene Membranes with 2D Nanofluidic Channels for Osmotic Energy Harvesting.

Membrane-based reverse electrodialysis (RED) is considered as the most promising technique to harvest osmotic energy. However, the traditional membranes are limited by high internal resistance and low efficiency, resulting in undesirable power densities. Herein, we report the combination of oppositely charged Ti3 C2 Tx MXene membranes (MXMs) with confined 2D nanofluidic channels as high-performance osmotic power generators. The negatively or positively charged 2D MXene nanochannels exhibit typical surface-charge-governed ion transport and show excellent cation or anion selectivity. By mixing the artificial sea water (0.5 m NaCl) and river water (0.01 m NaCl), we obtain a maximum power density of ca. 4.6 Wm-2 , higher than most of the state-of-the-art membrane-based osmotic power generators, and very close to the commercialization benchmark (5 Wm-2 ). Through connecting ten tandem MXM-RED stacks, the output voltage can reach up 1.66 V, which can directly power the electronic devices.

Self-Crosslinked MXene (Ti3C2Tx) Membranes with Good Antiswelling Property for Monovalent Metal Ion Exclusion.

A 2D membrane-based separation technique has been increasingly applied to solve the problem of fresh water shortage via ion rejection. However, these 2D membranes often suffer from a notorious swelling problem when immersed in solution, resulting in poor rejection for the monovalent metal ion. The design of the antiswelling 2D lamellar membranes has been proved to be a big challenge for highly efficient desalination. Here a kind of self-crosslinked MXene membrane is proposed for ion rejection with an obviously suppressed swelling property, which takes advantage of the hydroxyl terminal groups on the MXene nanosheets by forming Ti-O-Ti bonds between the neighboring nanosheets via the self-crosslinking reaction (-OH + -OH = -O- + H2O) through a facile thermal treatment. The permeation rates of the monovalent metal ions through the self-crosslinked MXene membrane are about two orders of magnitude lower than those through the pristine MXene membrane, which indicates the obviously improved performance of the ion exclusion by self-crosslinking between the MXene lamellae. Moreover, the excellent stability of the self-crosslinked MXene membrane during the 70 h long-term ion separation also demonstrates its promising antiswelling property. Such a facile and efficient self-crosslinking strategy gives the MXene membrane a good antiswelling property for metal ion rejection, which is also suitable for many other 2D materials with tunable surface functional groups during membrane assembly.

Ultra-Tuning of the Aperture Size in Stiffened ZIF-8_Cm Frameworks with Mixed-Linker Strategy for Enhanced CO2 /CH4 Separation.

ZIF-8 membrane has the potential for CO2 /CH4 separation based on size exclusion. But if traditionally prepared by solvothermal methods, it shows only negligible selectivity due to the linker mobility. Here, ≈500 nm-thin hybrid ZIF-7x -8 membranes with suppressed linker mobility and narrowed window aperture are prepared by a fast current-driven synthesis (FCDS) within 20 min. The in situ electric field during FCDS allows the formation of stiffened ZIF-8_Cm as parent skeleton and the mixed-linker strategy is applied to narrow the aperture size simultaneously. The ZIF-722 -8 membrane shows significantly sharpened molecular sieving for CO2 /CH4 with a separation factor above 25, which soared tenfold compared with other unmodified ZIF-8 membranes. Additionally, the membrane shows exceptional separation performance for H2 /CH4 and CO2 /N2 , with separation factors of 71 and 20, respectively. After 180 h temperature swing operation, it still maintains the excellent separation performance.

Paralyzed membrane: Current-driven synthesis of a metal-organic framework with sharpened propene/propane separation.

Metal-organic framework (MOF) membranes show great promise for propene/propane separation, yet a sharp molecular sieving has not been achieved due to their inherent linker mobility. Here, zeolitic imidazolate framework ZIF-8-type membranes with suppressed linker mobility are prepared by a fast current-driven synthesis (FCDS) strategy within 20 min, showing sharpened molecular sieving for propene/propane separation with a separation factor above 300. During membrane synthesis, the direct current promotes the metal ions and ligands to assemble into inborn-distorted and stiffer frameworks with ZIF-8_Cm (a newly discovered polymorph of ZIF-8) accounting for 60 to 70% of the membrane composition. Molecular dynamics simulations further verify that ZIF-8_Cm is superior to ZIF-8_I 4 ¯ 3 m (the common cubic phase) for propene/propane separation. FCDS holds great potential to produce high-quality, ultrathin MOF membranes on a large scale.

MXene molecular sieving membranes for highly efficient gas separation.

Molecular sieving membranes with sufficient and uniform nanochannels that break the permeability-selectivity trade-off are desirable for energy-efficient gas separation, and the arising two-dimensional (2D) materials provide new routes for membrane development. However, for 2D lamellar membranes, disordered interlayer nanochannels for mass transport are usually formed between randomly stacked neighboring nanosheets, which is obstructive for highly efficient separation. Therefore, manufacturing lamellar membranes with highly ordered nanochannel structures for fast and precise molecular sieving is still challenging. Here, we report on lamellar stacked MXene membranes with aligned and regular subnanometer channels, taking advantage of the abundant surface-terminating groups on the MXene nanosheets, which exhibit excellent gas separation performance with H2 permeability >2200 Barrer and H2/CO2 selectivity >160, superior to the state-of-the-art membranes. The results of molecular dynamics simulations quantitatively support the experiments, confirming the subnanometer interlayer spacing between the neighboring MXene nanosheets as molecular sieving channels for gas separation.

Water Transport with Ultralow Friction through Partially Exfoliated g-C3 N4 Nanosheet Membranes with Self-Supporting Spacers.

Two-dimensional (2D) graphitic carbon nitride (g-C3 N4 ) nanosheets show brilliant application potential in numerous fields. Herein, a membrane with artificial nanopores and self-supporting spacers was fabricated by assembly of 2D g-C3 N4 nanosheets in a stack with elaborate structures. In water purification the g-C3 N4 membrane shows a better separation performance than commercial membranes. The g-C3 N4 membrane has a water permeance of 29 L m-2 h-1 bar-1 and a rejection rate of 87 % for 3 nm molecules with a membrane thickness of 160 nm. The artificial nanopores in the g-C3 N4 nanosheets and the spacers between the partially exfoliated g-C3 N4 nanosheets provide nanochannels for water transport while bigger molecules are retained. The self-supported nanochannels in the g-C3 N4 membrane are very stable and rigid enough to resist environmental challenges, such as changes to pH and pressure conditions. Permeation experiments and molecular dynamics simulations indicate that a novel nanofluidics phenomenon takes place, whereby water transport through the g-C3 N4 nanosheet membrane occurs with ultralow friction. The findings provide new understanding of fluidics in nanochannels and illuminate a fabrication method by which rigid nanochannels may be obtained for applications in complex or harsh environments.

A Two-Dimensional Lamellar Membrane: MXene Nanosheet Stacks.

Two-dimensional (2D) materials are promising candidates for advanced water purification membranes. A new kind of lamellar membrane is based on a stack of 2D MXene nanosheets. Starting from compact Ti3 AlC2 , delaminated nanosheets of the composition Ti3 C2 Tx with the functional groups T (O, OH, and/or F) can be produced by etching and ultrasonication and stapled on a porous support by vacuum filtration. The MXene membrane supported on anodic aluminum oxide (AAO) substrate shows excellent water permeance (more than 1000 L m-2 h-1 bar-1 ) and favorable rejection rate (over 90 %) for molecules with sizes larger than 2.5 nm. The water permeance through the MXene membrane is much higher than that of the most membranes with similar rejections. Long-time operation also reveals the outstanding stability of the MXene membrane for water purification.

A Dual-Phase Ceramic Membrane with Extremely High H2 Permeation Flux Prepared by Autoseparation of a Ceramic Precursor.

A novel concept for the preparation of multiphase composite ceramics based on demixing of a single ceramic precursor has been developed and used for the synthesis of a dual-phase H2 -permeable ceramic membrane. The precursor BaCe0.5 Fe0.5 O3-δ decomposes on calcination at 1370 °C for 10 h into two thermodynamically stable oxides with perovskite structures: the cerium-rich oxide BaCe0.85 Fe0.15 O3-δ (BCF8515) and the iron-rich oxide BaCe0.15 Fe0.85 O3-δ (BCF1585), 50 mol % each. In the resulting dual-phase material, the orthorhombic perovskite BCF8515 acts as the main proton conductor and the cubic perovskite BCF1585 as the main electron conductor. The dual-phase membrane shows an extremely high H2 permeation flux of 0.76 mL min(-1)  cm(-2) at 950 °C with 1.0 mm thickness. This auto-demixing concept should be applicable to the synthesis of other ionic-electronic conducting ceramics.

Enhanced stability of Zr-doped Ba(CeTb)O(3-δ)-Ni cermet membrane for hydrogen separation.

A mixed protonic and electronic conductor material BaCe(0.85)Tb(0.05)Zr(0.1)O(3-δ) (BCTZ) is prepared and a Ni-BCTZ cermet membrane is synthesized for hydrogen separation. Stable hydrogen permeation fluxes can be obtained for over 100 h through the Ni-BCTZ membrane in both dry and humid conditions, which exhibits an excellent stability compared with Ni-BaCe(0.95)Tb(0.05)O(3-δ) membrane due to the Zr doping.