Intercrystalline Channels at Subnanometer Scale for Precise Molecular Nanofiltration.

Membrane-based technologies can provide cost-effective and energy-efficient methods for various separation processes. The key goal is to develop materials with uniform, tunable, and well-defined subnanometer-scale channels. Suitable membrane materials should have high selectivity and permeance and can be manufactured in a robust and scalable fashion. Here, we report the construction of sub-1 nm intercrystalline channels with such characteristics and elucidate their transport properties. These channels are formed by assembling 3D aluminum formate crystals during the amorphous-to-crystalline transformation process. By controlling the transformation time, the channel size can be tuned from the macroscopic scale to nanometer scale. The resulting membranes exhibit tailored selectivity and permeance, with molecular weight cutoffs ranging from around 300 Da to approximately 650 Da, and ethanol permeance ranging from 0.8 to 22.0 L m-2 h-1 bar-1. We further show that liquid flow through these channels changes from viscosity-dominated continuum flow to subcontinuum flow, which can be described by a modified Hagen-Poiseuille model. Our strategy provides a new scalable platform for applications that commonly exploit nanoscale mass transport.

Multivariate Polycrystalline Metal-Organic Framework Membranes for CO2/CH4 Separation.

Membrane technology is attractive for natural gas separation (removing CO2, H2O, and hydrocarbons from CH4) because of membranes' low energy consumption and small environmental footprint. Compared to polymeric membranes, microporous inorganic membranes such as silicoaluminophosphate-34 (SAPO-34) membrane can retain their separation performance under conditions close to industrial requirements. However, moisture and hydrocarbons in natural gas can be strongly adsorbed in the pores of those membranes, thereby reducing the membrane separation performance. Herein, we report the fabrication of a polycrystalline MIL-160 membrane on an Al2O3 substrate by in situ hydrothermal synthesis. The MIL-160 membrane with a thickness of ca. 3 µm shows a remarkable molecular sieving effect in gas separation. Besides, the pore size and environment of the MIL-160 membrane can be precisely controlled using reticular chemistry by regulating the size and functionality of the ligand. Interestingly, the more polar fluorine-functionalized multivariate MIL-160/CAU-10-F membrane exhibits a 10.7% increase in selectivity for CO2/CH4 separation and a 31.2% increase in CO2 permeance compared to those of the MIL-160 membrane. In addition, hydrophobic MIL-160 membranes and MIL-160/CAU-10-F membranes are more resistant to water vapor and hydrocarbons than the hydrophilic SAPO-34 membranes.

Pressure-Responsive Two-Dimensional Metal-Organic Framework Composite Membranes for CO2 Separation.

The regulation of permeance and selectivity in membrane systems may allow effective relief of conventional energy-intensive separations. Here, pressure-responsive ultrathin membranes (≈100 nm) fabricated by compositing flexible two-dimensional metal-organic framework nanosheets (MONs) with graphene oxide nanosheets for CO2 separation are reported. By controlling the gas permeation direction to leverage the pressure-responsive phase transition of the MONs, CO2 -induced gate opening and closing behaviors are observed in the resultant membranes, which are accompanied with the sharp increase of CO2 permeance (from 173.8 to 1144 gas permeation units) as well as CO2 /N2 and CO2 /CH4 selectivities (from 4.1 to 22.8 and from 4 to 19.6, respectively). The flexible behaviors and separation mechanism are further elucidated by molecular dynamics simulations. This work establishes the relevance of structural transformation-based framework dynamics chemistry in smart membrane systems.

Ultrathin Two-Dimensional Membranes Assembled by Ionic Covalent Organic Nanosheets with Reduced Apertures for Gas Separation.

Covalent organic frameworks (COFs) are a promising category of porous materials possessing extensive chemical tunability, high porosity, ordered arrangements at a molecular level, and considerable chemical stability. Despite these advantages, the application of COFs as membrane materials for gas separation is limited by their relatively large pore apertures (typically >0.5 nm), which exceed the sieving requirements for most gases whose kinetic diameters are less than 0.4 nm. Herein, we report the fabrication of ultrathin two-dimensional (2D) membranes through layer-by-layer (LbL) assembly of two kinds of ionic covalent organic nanosheets (iCONs) with different pore sizes and opposite charges. Because of the staggered packing of iCONs with strong electrostatic interactions, the resultant membranes exhibit features of reduced aperture size, optimized stacking pattern, and compact dense structure without sacrificing thickness control, which are suitable for molecular sieving gas separation. One of the hybrid membranes, TpEBr@TpPa-SO3Na with a thickness of 41 nm, shows a H2 permeance of 2566 gas permeation units (GPUs) and a H2/CO2 separation factor of 22.6 at 423 K, surpassing the recent Robeson upper bound along with long-term hydrothermal stability. This strategy provides not only a high-performance H2 separation membrane candidate but also an inspiration for pore engineering of COF or 2D porous polymer membranes.

Highly selective adsorption and separation of aniline/phenol from aqueous solutions by microporous MIL-53(Al): a combined experimental and computational study.

Experimental measurements have been combined with molecular simulations to investigate the adsorption and separation of aniline/phenol mixtures from aqueous solutions by the aluminum terephthalate MIL-53. The results show that the framework flexibility of this material plays a crucial role in the adsorption process and thus can greatly enhance the separation of the aniline/phenol mixture from their solutions. Compared with the conventional adsorbents, MIL-53(Al) shows the best performance for such systems of interest, from the points of view of both the adsorption capacities and the selectivities for aniline. The findings obtained in this work may facilitate more investigations in connection with the application of flexible nanoporous materials for the separation of organic compounds from liquid-phase environments.

One Scalable and Stable Metal-Organic Framework for Efficient Separation of CH4/N2 Mixture.

Separating CH4 from coal bed methane is of great importance but challenging. Adsorption-based separation often suffers from low selectivity, poor stability, and difficulty to scale up. Herein, a stable and scalable metal-organic framework [MOF, CoNi(pyz-NH2)] with multiple CH4 binding sites was reported to efficiently separate the CH4/N2 mixture. Due to its suitable pore size and multiple CH4 binding sites, it exhibits excellent CH4/N2 selectivity (16.5) and CH4 uptake (35.9 cm3/g) at 273 K and 1 bar, which is comparable to that of the state-of-the-art MOFs. Theoretical calculations reveal that the high density of open metal sites and polar functional groups in the pores provide strong affinity to CH4 than to N2. Moreover, CoNi(pyz-NH2) displays excellent structural stability and can be scale-up synthesized (22.7 g). This work not only provides an excellent adsorbent but also provides important inspiration for the future design and preparation of porous adsorbents for separations.

Ultrathin Covalent Organic Framework Membranes via a Multi-Interfacial Engineering Strategy for Gas Separation.

Covalent organic frameworks (COFs) are promising membrane materials due to their high porosity, ordered arrangements, and high stability. However, the relatively large pore size and complicated membrane preparation processes of COFs limit their applications in sieving small gas molecules, even at a lab scale. Herein, a multi-interfacial engineering strategy is proposed, that is, direct layer-by-layer interfacial reaction of two COFs (TpPa-SO3 H and TpTGCl ) with different pore sizes to form narrowed apertures at the COF-COF interfaces atop a relatively large-pore COF (COF-LZU1) film. At 423 K, one fabricated 155 nm-thick ultrathin COF membrane displays H2 permeance as high as 2163 gas permeation units (GPU) and a H2 /CO2 selectivity of 26, transcending the 2008 Robeson upper bound. This strategy not only provides high-performance membrane candidates for H2 separation, but also enlightens the interfacial engineering and pore engineering manipulation for other COFs, porous polymers, and their membranes.

Hybrid MOF-808-Tb nanospheres for highly sensitive and selective detection of acetone vapor and Fe3+ in aqueous solution.

We herein present MOF-808-Tb nanospheres synthesized by a microwave-assisted approach with post-synthetic modification. The hybrid material exhibits an outstanding lanthanide-based luminescence sensing performance toward acetone vapor and Fe3+ cations in aqueous solution.

Advanced Porous Materials in Mixed Matrix Membranes.

Membrane technology has gained great interest in industrial separation processing over the past few decades owing to its high energy efficiency, small capital investment, environmentally benign characteristics, and the continuous operation process. Among various types of membranes, mixed matrix membranes (MMMs) combining the merits of the polymer matrix and inorganic/organic fillers have been extensively investigated. With the rapid development of chemistry and materials science, recent studies have shifted toward the design and application of advanced porous materials as promising fillers to boost the separation performance of MMMs. Here, first a comprehensive overview is provided on the choices of advanced porous materials recently adopted in MMMs, including metal-organic frameworks, porous organic frameworks, and porous molecular compounds. Novel trends in MMMs induced by these advanced porous fillers are discussed in detail, followed by a summary of applying these MMMs for gas and liquid separations. Finally, a concise conclusion and current challenges toward the industrial implementation of MMMs are outlined, hoping to provide guidance for the design of high-performance membranes to meet the urgent needs of clean energy and environmental sustainability.

Enhanced Polymer Crystallinity in Mixed-Matrix Membranes Induced by Metal-Organic Framework Nanosheets for Efficient CO2 Capture.

The design and fabrication of novel mixed-matrix membranes (MMMs) with simultaneously enhanced gas permeability and selectivity are highly sought for the industrial deployment of membrane technology for large-scale CO2 capture and storage. Conventional isotropic bulky particle fillers often exhibit limited interfacial compatibility that eventually leads to significant selectivity loss in MMMs. Here, we report the incorporation of chemically stable metal-organic framework (MOF) nanosheets into a highly permeable polymer matrix to prepare defect-free MMMs. MOF nanosheets are homogeneously dispersed within the polymer matrix, owing to their high aspect ratios that improve the polymer-filler integration. The strong hydrogen bonding and π-π interactions between the two components not only enhance the interfacial compatibility but also favor the efficient polymer chain packing along the surface of MOF nanosheets, leading to enhanced polymer crystallinity as well as size-sieving capability of the membranes. The as-prepared MMMs demonstrate high CO2-selective separation performance, good antipressure, and antiaging abilities, thus offering new opportunities in developing advanced membranes for industrial gas separation applications.

High-Flux Graphene Oxide Membranes Intercalated by Metal-Organic Framework with Highly Selective Separation of Aqueous Organic Solution.

Graphene oxide (GO) membranes assembled by single-atom thick GO nanosheets have displayed huge potential application both in gas and liquid separation processes due to its facile and large-scale preparation resulting from various functional groups, such as hydroxyl, carboxyl, and epoxide groups. Taking advantage of these characters, GO membranes intercalated by superhydrophilic metal-organic frameworks (MOFs) as strengthening separation fillers were prepared on modified polyacrylonitrile (PAN) support by a novel pressure-assisted self-assembly (PASA) filtration technique instead of traditional vacuum filtration method for the first time. The synthesized MOF@GO membranes were characterized with several spectroscopic techniques including X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS), as well as scanning electron microscopy (SEM). Compared with GO membrane, these MOF@GO membranes combine the unique properties of MOF and GO and thus have significant enhancements of pervaporation (PV) permeation flux and separation factor simultaneously for ethyl acetate/water mixtures (98/2, w/w) through the PV process, which are also superior to the reported other kinds of membranes. Especially, for MOF@GO-0.3 membrane (corresponding MOF loading: 23.08 wt %), the increments are 159% and 244%, respectively, at 303 K, and the permeate water content can reach as high as 99.5 wt % (corresponding separation factor, 9751) with a high permeation flux of 2423 g m-2 h-1. Moreover, the procedures of both the synthesis of MOF and membranes preparation are environmentally friendly that only water was used as solvent. Such a nanosized MOF-intercalating approach may be also extended to other laminated membranes, providing valuable insights in designing and developing of advanced membranes for effective separation of aqueous organic solution through nanostructure manipulation of the nanomaterials.

Mixed-matrix membranes containing functionalized porous metal-organic polyhedrons for the effective separation of CO2-CH4 mixture.

To enhance dispersion and adhesion, functionalized porous metal-organic polyhedrons were incorporated into polysulfone as a filler to obtain mixed-matrix membranes, which exhibit largely improved gas permeability and separation factor simultaneously for CO2-CH4 separation.