Realizing membranes of atomic thickness functioning reliably constitutes a giant leap forward for a plethora of applications where the efficient separation of fluid constituents at the molecular level is critical. Here, by employing density functional theory, we explore the energy landscape of typical gas molecules attempting permeation through graphene nanopores and determine the minimum energy permeation pathways, based on the precise knowledge of the related molecular level interactions. With this approach we investigate two basic permeation routes: direct permeation and surface-based transport. We find that for subnanometer pores, the diffusion barrier of direct and surface transport depends on the pore chemical functionalization, while the molecule pore permeation barrier is independent of the gas-pore approach due to the overlap of surface and direct diffusion paths over the pore center. The overall minimum energy permeation pathway of He, H2, CO2, and CH4 molecules, across nanopores of different dimensions and chemical functionalization, defines the pore diameter (∼1.2 nm) below which effusion theory is inaccurate, as well as the critical pore diameter (∼0.8 nm) required to achieve positive permeation barriers driving molecular sieving. We determine that achieving positive permeation barriers required for high selectivity gas separation is inseparably combined with postpermeation desorption barriers due to attractive van der Waals interactions. The discovered permeation energetics are pore-molecule-specific and are incorporated into an analytical model extending existing theory. Our results provide a scientific background for rational pore design in graphene membranes, which can lead to gas separation at a commercially relevant performance level.

Adsorptive separation by porous solids provides an energy-efficient alternative for the purification of important chemical species compared to energy-intensive distillations. Particularly, the separation of linear hexane isomers from its branched counterparts is crucial to produce premium grade gasoline with high research octane number (RON). Herein, we report the synthesis of a new, flexible zinc-based metal-organic framework, [Zn5(μ3-OH)2(adtb)2(H2O)5·5 DMA] (Zn-adtb), constructed from a butterfly shaped carboxylate linker with underlying (4,8)-connected scu topology capable of separating the C6 isomers nHEX, 3MP, and 23DMB. The sorbate-sorbent interactions and separation mechanisms were investigated and analyzed through in situ FTIR, solid state NMR measurements and computational modeling. These studies reveal that Zn-adtb discriminates the nHEX/3MP isomer pair through a kinetic separation mechanism and the nHEX/23DMB isomer pair through a molecular sieving mechanism. Column breakthrough measurements further demonstrate the efficient separation of linear nHEX from the mono- and dibranched isomers.

Coordination polymer (CP) glasses offer a way to tackle the fabrication challenges encountered by inorganic porous membranes and show great potentials for size-exclusive gas separation. However, their processability and performance still cannot simultaneously meet the requirements for high-performance membrane separation. Herein, we have developed a series of CP glasses (M-P-dmbIm, M=Zn, Cd, Cu, and Mn), which possess low vitrification temperature as well as low viscosity (η) and lave capability above the transition temperatures. The derived glass (ag M-P-dmbIm) membranes show outstanding performances for H2 /CO2 , H2 /N2 , and H2 /CH4 separation, which all far surpass the Robeson upper bound and even rival against the best of the state-of-the-art gas separation membranes. The low viscosities not only allow us to hot-cast or hot-press the CP glasses into thin membranes within 5 min without sacrificing their selectivity and permeability, but also endow the resulted glass membranes with healing ability.

Monomolecular arrays of protein subunits forming surface layers (S-layers) are the most common outermost cell envelope components of prokaryotic organisms (bacteria and archaea). Since S-layers are periodic structures, they exhibit identical physicochemical properties for each constituent molecular unit down to the sub-nanometer level. Pores passing through S-layers show identical size and morphology and are in the range of ultrafiltration membranes. The functional groups on the surface and in the pores of the S-layer protein lattice are accessible for chemical modifications and for binding functional molecules in very precise fashion. S-layer ultrafiltration membranes (SUMs) can be produced by depositing S-layer fragments as a coherent (multi)layer on microfiltration membranes. After inter- and intramolecular crosslinking of the composite structure, the chemical and thermal resistance of these membranes was shown to be comparable to polyamide membranes. Chemical modification and/or specific binding of differently sized molecules allow the tuning of the surface properties and molecular sieving characteristics of SUMs. SUMs can be utilized as matrices for the controlled immobilization of functional biomolecules (e.g., ligands, enzymes, antibodies, and antigens) as required for many applications (e.g., biosensors, diagnostics, enzyme- and affinity-membranes). Finally, SUM represent unique supporting structures for stabilizing functional lipid membranes at meso- and macroscopic scale.

Rigid molecular sieving materials are the ideal candidates for gas separation (e. g., C2 H2 /C2 H4 ) due to their ultrahigh adsorption selectivity and the absence of gas co-adsorption. However, the absolute molecular sieving effect for C2 H2 /C2 H4 separation has rarely been realized because of their similar physicochemical properties. Herein, we demonstrate the absolute molecular sieving of C2 H2 from C2 H4 by a rigid ultra-microporous metal-organic framework (F-PYMO-Cu) with 1D regular channels (pore size of ca. 3.4 Å). F-PYMO-Cu exhibited moderate acetylene uptake (35.5 cm3 /cm3 ), but very low ethylene uptake (0.55 cm3 /cm3 ) at 298 K and 1 bar, yielding the second highest C2 H2 /C2 H4 uptake ratio of 63.6 up to now. One-step C2 H4 production from a binary mixture of C2 H2 /C2 H4 and a ternary mixture of C2 H2 /CO2 /C2 H4 at 298 K was achieved and verified by dynamic breakthrough experiments. Coupled with excellent thermal and water stability, F-PYMO-Cu could be a promising candidate for industrial C2 separation tasks.

In this study, three polymer precursor conformations, dilute, semi-dilute, and concentrated, were used to fabricate carbon molecular sieving (CMS) membranes via a fixed carbonization protocol. The effects of the precursor conformation on the microstructure of the resultant CMS membranes were characterized by Raman analysis. Their ability to separate light gases, such as H2/CH4 and H2/N2, was assessed with a single-gas system. Additionally, a novel method was proposed to detect the cutoff size of the CMS membranes created in this study. The method combined high-resolution transmission electron microscopy (HR-TEM) and a focused ion beam (FIB) system. Finally, due to the semi-dilute solution\'s denser polymer chains and lack of severe polymer entanglement, highly graphited CMS membranes with excellent gas separation performance were successfully synthesized using a semi-dilute polyetherimide dope solution. Interlayer distances in the carbon matrix were visualized and measured using our novel probing tool (HR-TEM and FIB) and software. The CMS membrane fabricated with a semi-dilute dope exhibited the best gas separation performance of the tested membranes. It had the most ordered carbon sheet orientation and exhibited a superior selectivity of H2/CH4 = 293 with a hydrogen permeability of 1138.7 Barrer, far surpassing the reported permselectivity of other membranes. We believe that the high H2/CH4 selectivity presented here is unprecedented for CMS membranes reported in the literature.

The structuring of the metal-organic framework material ZIF-8 as films and membranes through the vapor-phase conversion of ZnO fractal nanoparticle networks is reported. The extrinsic porosity of the resulting materials can be tuned from 4% to 66%, and the film thickness can be controlled from 80 nm to 0.23 mm, for areas >100 cm2. Freestanding and pure metal-organic frameworks (MOF) membranes prepared this way are showcased as separators that minimize capacity fading in model Li-S batteries.

The treatment of VOCs (volatile organic compounds) in waste streams is very important. Herein, we propose to use a network microporous polyimide (PI) membrane for the molecular sieving of nitrogen over VOC molecules to control their emission. 2,6,14-triaminotriptycene (Trip) was reacted with aromatic dianhydride monomers, such as 3,3\',4,4\'-benzophenone tetracarboxylic dianhydride (BTDA), to synthesize ultramicroporous polyimides, which readily form composite membranes via solution coating. The properties of the PIs were characterized by X-ray photoelectron spectroscopy (XPS), Brunner-Emmet-Teller (BET) analysis, etc., which validated the formation of a network structure and ultramicroporosity in these polyimides. Therefore, the outstanding separation performance for the separation of nitrogen over VOCs, such as cyclohexane, by molecular sieving was obtained by using these membranes; a rejection higher than 99 % was realized with a permeability of approximately 2000∼2600 Barrer under a temperature of 25 °C and feed concentration of 30,000 ± 2000 ppm. Finally, the stability of the Trip-BTDA-PI membrane over time was studied.

Highly permselective nanostructured membranes are desirable for the energy-efficient molecular sieving on the subnanometer scale. The nanostructure construction and charge functionalization of the membranes are generally carried out step by step through the conventional layer-by-layer coating strategy, which inevitably brings about a demanding contradiction between the permselective performance and process efficiency. For the first time, we report the concurrent construction of the well-defined molecular sieving architectures and tunable surface charges of nanofiltration membranes through precisely controlled release of the nanocapsule decorated polyethyleneimine and carbon dioxide. This novel strategy not only substantially shortens the fabrication process but also leads to impressive performance (permeance up to 37.4 L m-2 h-1 bar-1 together with a rejection 98.7% for Janus Green B-511 Da) that outperforms most state-of-art nanofiltration membranes. This study unlocks new avenues to engineer next-generation molecular sieving materials simply, precisely, and cost efficiently.

Transmembrane protein channels, including ion channels and aquaporins that are responsible for fast and selective transport of water, have inspired membrane scientists to exploit and mimic their performance in membrane technologies. These biomimetic membranes comprise discrete nanochannels aligned within amphiphilic matrices on a robust support. While biological components have been used directly, extensive work has also been conducted to produce stable synthetic mimics of protein channels and lipid bilayers. However, the experimental performance of biomimetic membranes remains far below that of biological membranes. In this review, we critically assess the status and potential of biomimetic desalination membranes. We first review channel chemistries and their transport behavior, identifying key characteristics to optimize water permeability and salt rejection. We compare various channel types within an industrial context, considering transport performance, processability, and stability. Through a re-examination of previous vesicular stopped-flow studies, we demonstrate that incorrect permeability equations result in an overestimation of the water permeability of nanochannels. We find in particular that the most optimized aquaporin-bearing bilayer had a pure water permeability of 2.1 L m-2 h-1 bar-1, which is comparable to that of current state-of-the-art polymeric desalination membranes. Through a quantitative assessment of biomimetic membrane formats, we analytically show that formats incorporating intact vesicles offer minimal benefit, whereas planar biomimetic selective layers could allow for dramatically improved salt rejections. We then show that the persistence of nanoscale defects explains observed subpar performance. We conclude with a discussion on optimal strategies for minimizing these defects, which could enable breakthrough performance.