Scalable weaving of resilient membranes with on-demand superwettability for high-performance nanoemulsion separations.

This study leverages the ancient craft of weaving to prepare membranes that can effectively treat oil/water mixtures, specifically challenging nanoemulsions. Drawing inspiration from the core-shell architecture of spider silk, we have engineered fibers, the fundamental building blocks for weaving membranes, that feature a mechanically robust core for tight weaving, coupled with a CO2-responsive shell that allows for on-demand wettability adjustments. Tightly weaving these fibers produces membranes with ideal pores, achieving over 99.6% separation efficiency for nanoemulsions with droplets as small as 20 nm. They offer high flux rates, on-demand self-cleaning, and can switch between sieving oil and water nanodroplets through simple CO2/N2 stimulation. Moreover, weaving can produce sufficiently large membranes (4800 cm2) to assemble a module that exhibits long-term stability and performance, surpassing state-of-the-art technologies for nanoemulsion separations, thus making industrial application a practical reality.

Tuning Pore Size in Graphene in the Angstrom Regime for Highly Selective Ion-Ion Separation.

Zero-dimensional pores spanning only a few angstroms in size in two-dimensional materials such as graphene are some of the most promising systems for designing ion-ion selective membranes. However, the key challenge in the field is that so far a crack-free macroscopic graphene membrane for ion-ion separation has not been realized. Further, methods to tune the pores in the Å-regime to achieve a large ion-ion selectivity from the graphene pore have not been realized. Herein, we report an Å-scale pore size tuning tool for single layer graphene, which incorporates a high density of ion-ion selective pores between 3.5 and 8.5 Å while minimizing the nonselective pores above 10 Å. These pores impose a strong confinement for ions, which results in extremely high selectivity from centimeter-scale porous graphene between monovalent and bivalent ions and near complete blockage of ions with the hydration diameter, DH, greater than 9.0 Å. The ion diffusion study reveals the presence of an energy barrier corresponding to partial dehydration of ions with the barrier increasing with DH. We observe a reversal of K+/Li+ selectivity at elevated temperature and attribute this to the relative size of the dehydrated ions. These results underscore the promise of porous two-dimensional materials for solute-solute separation when Å-scale pores can be incorporated in a precise manner.

Unit-cell-thick zeolitic imidazolate framework films for membrane application.

Zeolitic imidazolate frameworks (ZIFs) are a subset of metal-organic frameworks with more than 200 characterized crystalline and amorphous networks made of divalent transition metal centres (for example, Zn2+ and Co2+) linked by imidazolate linkers. ZIF thin films have been intensively pursued, motivated by the desire to prepare membranes for selective gas and liquid separations. To achieve membranes with high throughput, as in ångström-scale biological channels with nanometre-scale path lengths, ZIF films with the minimum possible thickness-down to just one unit cell-are highly desired. However, the state-of-the-art methods yield membranes where ZIF films have thickness exceeding 50 nm. Here we report a crystallization method from ultradilute precursor mixtures, which exploits registry with the underlying crystalline substrate, yielding (within minutes) crystalline ZIF films with thickness down to that of a single structural building unit (2 nm). The film crystallized on graphene has a rigid aperture made of a six-membered zinc imidazolate coordination ring, enabling high-permselective H2 separation performance. The method reported here will probably accelerate the development of two-dimensional metal-organic framework films for efficient membrane separation.

Microstructure optimization of bioderived polyester nanofilms for antibiotic desalination via nanofiltration.

The successful implementation of thin-film composite membranes (TFCM) for challenging solute-solute separations in the pharmaceutical industry requires a fine control over the microstructure (size, distribution, and connectivity of the free-volume elements) and thickness of the selective layer. For example, desalinating antibiotic streams requires highly interconnected free-volume elements of the right size to block antibiotics but allow the passage of salt ions and water. Here, we introduce stevioside, a plant-derived contorted glycoside, as a promising aqueous phase monomer for optimizing the microstructure of TFCM made via interfacial polymerization. The low diffusion rate and moderate reactivity of stevioside, together with its nonplanar and distorted conformation, produced thin selective layers with an ideal microporosity for antibiotic desalination. For example, an optimized 18-nm membrane exhibited an unprecedented combination of high water permeance (81.2 liter m-2 hour-1 bar-1), antibiotic desalination efficiency (NaCl/tetracycline separation factor of 11.4), antifouling performance, and chlorine resistance.

Gas Separation Membranes with Atom-Thick Nanopores: The Potential of Nanoporous Single-Layer Graphene.

Gas separation is one of the most important industrial processes and is poised to take a larger role in the transition to renewable energy, e.g., carbon capture and hydrogen purification. Conventional gas separation processes involving cryogenic distillation, solvents, and sorbents are energy intensive, and as a result, the energy footprint of gas separations in the chemical industry is extraordinarily high. This has motivated fundamental research toward the development of novel materials for high-performance membranes to improve the energy efficiency of gas separation. These novel materials are expected to overcome the intrinsic limitations of the conventional membrane material, i.e., polymers, where a longstanding trade-off between the separation selectivity and the permeance has motivated research into nanoporous materials as the selective layer for the membranes. In this context, atom-thick materials such as nanoporous single-layer graphene constitute the ultimate limit for the selective layer. Gas transport from atom-thick nanopores is extremely fast, dependent primarily on the energy barrier that the gas molecule experiences in translocating the nanopore. Consequently, the difference in the energy barriers for two gas molecules determines the gas pair selectivity. In this Account, we summarize the development in the field of nanoporous single-layer graphene membranes for gas separation. We start by discussing the mechanism for gas transport across atom-thick nanopores, which then yields the crucial design elements needed to achieve high-performance membranes: (i) nanopores with an adequate electron-density gap to sieve the desired gas component (e.g., smaller than 0.289, 0.33, 0.346, 0.362, and 0.38 nm for H2, CO2, O2, N2, and CH4, respectively), (ii) narrow pore size distribution to limit the nonselective effusive transport from the tail end of the distribution, and (iii) high density of selective pores. We discuss and compare the state-of-the-art bottom-up and top-down routes for the synthesis of nanoporous graphene films. Mechanistic insights and parameters controlling the size, distribution, and density of nanopores are discussed. Fundamental insights are provided into the reaction of ozone with graphene, which has been successfully used by our group to develop membranes with record-high carbon capture performance. Postsynthetic modifications, which allow the tuning of the transport by (i) tailoring the relative contributions of adsorbed-phase and gas-phase transport, (ii) competitive adsorption, and (iii) molecular cutoff adjustment, are discussed. Finally, we discuss practical aspects that are crucial in successfully preparing practical membranes using atom-thick materials as the selective layer, allowing the eventual scale-up of these membranes. Crack- and tear-free preparation of membranes is discussed using the approach of mechanical reinforcement of graphene with nanoporous carbon and polymers, which led to the first reports of millimeter- and centimeter-scale gas-sieving membranes in the year 2018 and 2021, respectively. We conclude with insights and perspectives highlighting the key scientific and technological gaps that must be addressed in the future research.

In Situ Nucleation-Decoupled and Site-Specific Incorporation of Å-Scale Pores in Graphene Via Epoxidation.

Generating pores in graphene by decoupled nucleation and expansion is desired to achieve a fine control over the porosity, and is desired to advance several applications. Herein, epoxidation is introduced, which is the formation of nanosized epoxy clusters on the graphitic lattice as nucleation sites without forming pores. In situ gasification of clusters inside a transmission electron microscope shows that pores are generated precisely at the site of the clusters by surpassing an energy barrier of 1.3 eV. Binding energy predictions using ab initio calculations combined with the cluster nucleation theory reveal the structure of the epoxy clusters and indicate that the critical cluster is an epoxy dimer. Finally, it is shown that the cluster gasification can be manipulated to form Å-scale pores which then effectively sieve gas molecules based on their size. This decoupled cluster nucleation and pore formation will likely pave the way for an independent control of pore size and density.

Enhanced Water Evaporation from Å-Scale Graphene Nanopores.

Enhancing the kinetics of liquid-vapor transition from nanoscale confinements is an attractive strategy for developing evaporation and separation applications. The ultimate limit of confinement for evaporation is an atom thick interface hosting angstrom-scale nanopores. Herein, using a combined experimental/computational approach, we report highly enhanced water evaporation rates when angstrom sized oxygen-functionalized graphene nanopores are placed at the liquid-vapor interface. The evaporation flux increases for the smaller nanopores with an enhancement up to 35-fold with respect to the bare liquid-vapor interface. Molecular dynamics simulations reveal that oxygen-functionalized nanopores render rapid rotational and translational dynamics to the water molecules due to a reduced and short-lived water-water hydrogen bonding. The potential of mean force (PMF) reveals that the free energy barrier for water evaporation decreases in the presence of nanopores at the atomically thin interface, which further explains the enhancement in evaporation flux. These findings can enable the development of energy-efficient technologies relying on water evaporation.

Unblocking Ion-occluded Pore Channels in Poly(triazine imide) Framework for Proton Conduction.

Poly(triazine imide) or PTI is an ordered graphitic carbon nitride hosting Å-scale pores attractive for selective molecular transport. AA'-stacked PTI layers are synthesized by ionothermal route during which ions occupy the framework and occlude the pores. Synthesis of ion-free PTI hosting AB-stacked layers has been reported, however, pores in this configuration are blocked by the neighboring layer. The unavailability of open pore limits application of PTI in molecular transport. Herein, we demonstrate acid treatment for ion depletion which maintains AA' stacking and results in open pore structure. We provide first direct evidence of ion-depleted open pores by imaging with the atomic resolution using integrated differential phase-contrast scanning transmission electron microscopy. Depending on the extent of ion-exchange, AA' stacking with open channels and AB stacking with closed channels are obtained and imaged for the first time. The accessibility of open channels is demonstrated by enhanced proton transport through ion depleted PTI.

Demonstrating and Unraveling a Controlled Nanometer-Scale Expansion of the Vacancy Defects in Graphene by CO2.

A controlled manipulation of graphene edges and vacancies is desired for molecular separation, sensing and electronics applications. Unfortunately, available etching methods always lead to vacancy nucleation making it challenging to control etching. Herein, we report CO2 -led controlled etching down to 2-3 Šper minute while completely avoiding vacancy nucleation. This makes CO2 a unique etchant for decoupling pore nucleation and expansion. We show that CO2 expands the steric-hindrance-free edges with an activation energy of 2.71 eV, corresponding to the energy barrier for the dissociative chemisorption of CO2 . We demonstrate the presence of an additional configurational energy barrier for nanometer-sized vacancies resulting in a significantly slower rate of expansion. Finally, CO2 etching is applied to map the location of the intrinsic vacancies in the polycrystalline graphene film where we show that the intrinsic vacancy defects manifest mainly as grain boundary defects where intragrain defects from oxidative etching constitute a minor population.

Bottom-up synthesis of graphene films hosting atom-thick molecular-sieving apertures.

Incorporation of a high density of molecular-sieving nanopores in the graphene lattice by the bottom-up synthesis is highly attractive for high-performance membranes. Herein, we achieve this by a controlled synthesis of nanocrystalline graphene where incomplete growth of a few nanometer-sized, misoriented grains generates molecular-sized pores in the lattice. The density of pores is comparable to that obtained by the state-of-the-art postsynthetic etching (1012 cm-2) and is up to two orders of magnitude higher than that of molecular-sieving intrinsic vacancy defects in single-layer graphene (SLG) prepared by chemical vapor deposition. The porous nanocrystalline graphene (PNG) films are synthesized by precipitation of C dissolved in the Ni matrix where the C concentration is regulated by controlled pyrolysis of precursors (polymers and/or sugar). The PNG film is made of few-layered graphene except near the grain edge where the grains taper down to a single layer and eventually terminate into vacancy defects at a node where three or more grains meet. This unique nanostructure is highly attractive for the membranes because the layered domains improve the mechanical robustness of the film while the atom-thick molecular-sized apertures allow the realization of large gas transport. The combination of gas permeance and gas pair selectivity is comparable to that from the nanoporous SLG membranes prepared by state-of-the-art postsynthetic lattice etching. Overall, the method reported here improves the scale-up potential of graphene membranes by cutting down the processing steps.

Multipulsed Millisecond Ozone Gasification for Predictable Tuning of Nucleation and Nucleation-Decoupled Nanopore Expansion in Graphene for Carbon Capture.

Predictable and tunable etching of angstrom-scale nanopores in single-layer graphene (SLG) can allow one to realize high-performance gas separation even from similar-sized molecules. We advance toward this goal by developing two etching regimes for SLG where the incorporation of angstrom-scale vacancy defects can be controlled. We screen several exposure profiles for the etchant, controlled by a multipulse millisecond treatment, using a mathematical model predicting the nucleation and pore expansion rates. The screened profiles yield a narrow pore-size-distribution (PSD) with a majority of defects smaller than missing 16 carbon atoms, suitable for CO2/N2 separation, attributing to the reduced pore expansion rate at a high pore density. Resulting nanoporous SLG (N-SLG) membranes yield attractive CO2 permeance of 4400 ± 2070 GPU and CO2/N2 selectivity of 33.4 ± 7.9. In the second etching regime, by limiting the supply of the etchant, the nanopores are allowed to expand while suppressing the nucleation events. Extremely attractive carbon capture performance marked with CO2 permeance of 8730 GPU, and CO2/N2 selectivity of 33.4 is obtained when CO2-selective polymeric chains are functionalized on the expanded nanopores. We show that the etching strategy is uniform and scalable by successfully fabricating high-performance centimeter-scale membrane.

Millisecond lattice gasification for high-density CO2- and O2-sieving nanopores in single-layer graphene.

Etching single-layer graphene to incorporate a high pore density with sub-angstrom precision in molecular differentiation is critical to realize the promising high-flux separation of similar-sized gas molecules, e.g., CO2 from N2 However, rapid etching kinetics needed to achieve the high pore density is challenging to control for such precision. Here, we report a millisecond carbon gasification chemistry incorporating high density (>1012 cm-2) of functional oxygen clusters that then evolve in CO2-sieving vacancy defects under controlled and predictable gasification conditions. A statistical distribution of nanopore lattice isomers is observed, in good agreement with the theoretical solution to the isomer cataloging problem. The gasification technique is scalable, and a centimeter-scale membrane is demonstrated. Last, molecular cutoff could be adjusted by 0.1 Å by in situ expansion of the vacancy defects in an O2 atmosphere. Large CO2 and O2 permeances (>10,000 and 1000 GPU, respectively) are demonstrated accompanying attractive CO2/N2 and O2/N2 selectivities.

Gas-sieving zeolitic membranes fabricated by condensation of precursor nanosheets.

The synthesis of molecular-sieving zeolitic membranes by the assembly of building blocks, avoiding the hydrothermal treatment, is highly desired to improve reproducibility and scalability. Here we report exfoliation of the sodalite precursor RUB-15 into crystalline 0.8-nm-thick nanosheets, that host hydrogen-sieving six-membered rings (6-MRs) of SiO4 tetrahedra. Thin films, fabricated by the filtration of a suspension of exfoliated nanosheets, possess two transport pathways: 6-MR apertures and intersheet gaps. The latter were found to dominate the gas transport and yielded a molecular cutoff of 3.6 Å with a H2/N2 selectivity above 20. The gaps were successfully removed by the condensation of the terminal silanol groups of RUB-15 to yield H2/CO2 selectivities up to 100. The high selectivity was exclusively from the transport across 6-MR, which was confirmed by a good agreement between the experimentally determined apparent activation energy of H2 and that computed by ab initio calculations. The scalable fabrication and the attractive sieving performance at 250-300 °C make these membranes promising for precombustion carbon capture.

Large-scale synthesis of crystalline g-C3N4 nanosheets and high-temperature H2 sieving from assembled films.

Poly(triazine imide) (PTI), a crystalline g-C3N4, hosting two-dimensional nanoporous structure with an electron density gap of 0.34 nm, is highly promising for high-temperature hydrogen sieving because of its high chemical and thermal robustness. Currently, layered PTI is synthesized in potentially unsafe vacuum ampules in milligram quantities. Here, we demonstrate a scalable and safe ambient pressure synthesis route leading to several grams of layered PTI platelets in a single batch with 70% yield with respect to the precursor. Solvent exfoliation under anhydrous conditions led to single-layer PTI nanosheets evidenced by the observation of triangular g-C3N4 nanopores. Gas permeation studies confirm that PTI nanopores can sieve He and H2 from larger molecules. Last, high-temperature H2 sieving from PTI nanosheet-based membranes, prepared by the scalable filter coating technique, is demonstrated with H2 permeance reaching 1500 gas permeation units, with H2/CO2, H2/N2, and H2/CH4 selectivities reaching 10, 50, and 60, respectively, at 250°C.

Ultrathin Carbon Molecular Sieve Films and Room-Temperature Oxygen Functionalization for Gas-Sieving.

Inorganic membranes based on carbon molecular sieve (CMS) films hosting slit-like pores can yield high molecular selectivity with a sub-angstrom resolution in molecular differentiation and therefore are highly attractive for energy-efficient separations. However, the selective layer thickness of the state-of-the-art CMS membranes for gas separation is more than 1 µm, yielding low gas permeance. Also, there is no room-temperature functionalization route for the modification of the pore-size-distribution of CMS to increase the molecular selectivity. In this context, we report two novel fabrication routes, namely, transfer and masking techniques, leading to CMS films with thicknesses as small as 100 nm, yielding attractive gas-sieving performances with H2 permeance reaching up to 3060 gas permeation unit (GPU). Further, a rapid and highly tunable room-temperature ozone treatment-based postsynthetic modification is reported, shrinking the electron density gap in the nanopores by a fraction of an angstrom and improving gas selectivities by several folds. The optimized membranes yielded H2 permeance of 507 GPU and H2/CH4 selectivity of 50.7.

Embedding 1D Conducting Channels into 3D Isoporous Polymer Films for High-Performance Humidity Sensing.

Isoporous block copolymer (BCP) films have received exponential interest as highly selective membranes, stemming from their unique morphological features, but their applications in functional devices remain to be realized. Now single-walled carbon nanotubes (CNTs) were efficiently incorporated into isoporous block copolymer films for chemiresistive sensing at room temperature. Leveraging the efficient charge extraction ability of CNTs together with nanochannel arrays aligned perpendicular to the surface of the films, an ultrafast response time of 0.3 s was achieved for humidity detection with a sensor response of about 800 on changing humidity from 10 % to 95 %. Furthermore, the sensor also responds to various organic vapors, underscoring its promising detection capability.

Cyclodextrin Films with Fast Solvent Transport and Shape-Selective Permeability.

This study describes the molecular-level design of a new type of filtration membrane made of crosslinked cyclodextrins-inexpensive macrocycles of glucose, shaped like hollow truncated cones. The channel-like cavities of cyclodextrins spawn numerous paths of defined aperture in the separation layer that can effectively discriminate between molecules. The transport of molecules through these membranes is highly shape-sensitive. In addition, the presence of hydrophobic (cavity) and hydrophilic (ester-crosslinked outer part) domains in these films results in high permeances for both polar and nonpolar solvents.

A Metal Chelating Porous Polymeric Support: The Missing Link for a Defect-Free Metal-Organic Framework Composite Membrane.

Since the discovery of size-selective metal-organic frameworks (MOFs), researchers have tried to incorporate these materials into gas separation membranes. Impressive gas selectivities were found, but these MOF membranes were mostly made on inorganic supports, which are generally too bulky and expensive for industrial gas separation. Forming MOF layers on porous polymer supports is industrially attractive but technically challenging. Two features to overcome these problems are described: 1) a metal chelating support polymer to bind the MOF layer, and 2) control of MOF crystal growth by contra-diffusion, aiming at a very thin nanocrystalline MOF layer. Using a metal chelating poly-thiosemicarbazide (PTSC) support and adjusting the metal and organic ligand concentrations carefully, a very compact ZIF-8 (ZIF=zeolitic imidazolate framework) layer was produced that displayed interference colors because of its smooth surface and extreme thinness-within the range of visible light. High performances were measured in terms of hydrogen/propane (8350) and propylene/propane (150) selectivity.

Antibiofilm effect enhanced by modification of 1,2,3-triazole and palladium nanoparticles on polysulfone membranes.

Biofouling impedes the performance of membrane bioreactors. In this study, we investigated the antifouling effects of polysulfone membranes that were modified by 1,2,3-triazole and palladium (Pd) nanoparticles. The modified membranes were evaluated for antibacterial and antifouling efficacy in a monoculture species biofilm (i.e., drip flow biofilm reactor, DFR) and mixed species biofilm experiment (i.e., aerobic membrane reactor, AeMBR). 1,2,3-triazole and Pd nanoparticles inhibited growth of Pseudomonas aeruginosa in both aerobic and anaerobic conditions. The decrease in bacterial growth was observed along with a decrease in the amount of total polysaccharide within the monoculture species biofilm matrix. When the modified membranes were connected to AeMBR, the increase in transmembrane pressure was lower than that of the non-modified membranes. This was accompanied by a decrease in protein and polysaccharide concentrations within the mixed species biofilm matrix. Biomass amount in the biofilm layer was also lower in the presence of modified membranes, and there was no detrimental effect on the performance of the reactor as evaluated from the nutrient removal rates. 16S rRNA analysis further attributed the delay in membrane fouling to the decrease in relative abundance of selected bacterial groups. These observations collectively point to a lower fouling occurrence achieved by the modified membranes.

Polymer and Membrane Design for Low Temperature Catalytic Reactions.

Catalytically active asymmetric membranes have been developed with high loadings of palladium nanoparticles located solely in the membrane's ultrathin skin layer. The manufacturing of these membranes requires polymers with functional groups, which can form insoluble complexes with palladium ions. Three polymers have been synthesized for this purpose and a complexation/nonsolvent induced phase separation followed by a palladium reduction step is carried out to prepare such membranes. Parameters to optimize the skin layer thickness and porosity, the palladium loading in this layer, and the palladium nanoparticles size are determined. The catalytic activity of the membranes is verified with the reduction of a nitro-compound and with a liquid phase Suzuki-Miyaura coupling reaction. Very low reaction times are observed.