Separation of hydrogen from carbon dioxide for sustainable H₂ production and CO₂ capture still faces great challenges due to the smaller size of H₂ and higher condensability of CO₂. Herein, a high-performance benzimidazole-linked polymer (BILP) membrane for hydrogen separation was directly prepared on α-Al₂O₃ substrate through a facile interfacial polymerization approach at room temperature. The separation performance of the BILP membrane were regulated by controlling the reaction time and the microstructure was systematically characterized. Molecular simulations were performed to deep understand the separation mechanism in the BILP membrane. The best performance membrane displays an extraordinary mixed gas selectivity of 40 for H₂/CO₂ together with outstanding H₂ permeance of 250 gas permeation units (GPU) at 473 K, far exceeding the Robeson's upper bound. Besides, the membrane can withstand high temperature and pressure, and also shows good H₂/N₂ and H₂/CH₄ selectivity. The excellent separation performance, coupled with high temperature and pressure resistance and easy preparation, render BILP membranes great potential for economic H₂ purification, H₂ recovery, and natural gas treatment.

Metal–organic frameworks (MOFs) are superior sorbents for water adsorption-based applications. The unique step-like water isotherm at a MOF-specific relative pressure allows easy loading and regeneration over a small range of temperature and pressure conditions. With good hydrothermal stability and cyclic durability, it stands out over classical sorbents used in applications for humidity control, water harvesting, and adsorption-based heating and cooling. These are easily regenerated at moderate temperatures using “waste” heat or solar heating. The isotherm thermodynamics and adsorption mechanisms are described, and the presence of MOFs in the water–air system is explained. Based on six selection criteria ≈40 reported MOFs and one COF are identified for potential application. Trends and approaches in further synthesis optimization and production scale-up are highlighted. No-MOF-fits-all, each MOF has its own specific step location matching only with a certain application type. Most applications are technically feasible and demonstrated on the bench-scale or small pilot. Their maturity is benchmarked by their technology readiness level. Retrofitting existing applications with MOFs replacing classical desiccants may lead to rapid demonstration. Studies on techno-economic analysis and life cycle analysis are required for a rational evaluation of the feasibility of promising applications.

New membrane materials with excellent water permeability and high ion rejection are needed. Metal-organic frameworks (MOFs) are promising candidates by virtue of their diversity in chemistry and topology. In this work, continuous aluminum MOF-303 membranes were prepared on α-Al2O3 substrates via an in situ hydrothermal synthesis method. The membranes exhibit satisfying rejection of divalent ions (e.g., 93.5% for MgCl2 and 96.0% for Na2SO4) on the basis of a size-sieving and electrostatic-repulsion mechanism and unprecedented permeability (3.0 L·m-2·h-1·bar-1·μm). The water permeability outperforms typical zirconium MOF, zeolite, and commercial polymeric reverse osmosis and nanofiltration membranes. Additionally, the membrane material exhibits good stability and low production costs. These merits recommend MOF-303 as a next-generation membrane material for water softening.

High performance and commercially attractive mixed-matrix membranes were developed for H₂/CO₂ separation via a scalable hollow fiber spinning process. Thin (~300 nm) and defect-free selective layers were successfully created with a uniform distribution of the nanosized (~60 nm) zeolitic-imidazole framework (ZIF-8) filler within the polymer (polybenzimidazole, PBI) matrix. These membranes were able to operate at high temperature (150 °C) and pressure (up to 30 bar) process conditions required in treatment of pre-combustion and syngas process gas streams. Compared with neat PBI hollow fibers, filler incorporation into the polymer matrix leads to a strong increase in H₂ permeance from 65 GPU to 107 GPU at 150 °C and 7 bar, while the ideal H₂/CO₂ selectivity remained constant at 18. For mixed gas permeation, there is competition between H₂ and CO₂ transport inside ZIF-8 structure. Adsorption of CO₂ in the nanocavities of the filler suppresses the transport of the faster permeating H₂ and consequently decreases the H₂ permeance with total feed pressure down to values equal to the pure PBI hollow fibers for the end pressure of 30 bar. Therefore, the improvement of fiber performance for gas separation with filler addition is compromised at high operating feed pressures, which emphasizes the importance of membrane evaluation under relevant process conditions.

Metal-organic frameworks (MOFs) have emerged as a class of promising membrane materials. UiO-66 is a prototypical and stable MOF material with a number of analogues. In this article, we review five approaches for fabricating UiO-66 polycrystalline membranes including in situ synthesis, secondary synthesis, biphase synthesis, gas-phase deposition and electrochemical deposition, as well as their applications in gas separation, pervaporation, nanofiltration and ion separation. On this basis, we propose possible methods for scalable synthesis of UiO-66 membranes and their potential separation applications in the future. [Figure not available: see fulltext.]

In the present study, triplicate rings of 360° pipe surfaces of an operational drinking water distribution pipe were swabbed. Each ring was equally divided into 16 parts for swabbing. The collected swabs were grouped into 3 sections and compared with the biofilm samples sampled by sonication of specimens from the same pipe. The results showed that the biofilm is unevenly distributed over the 16 parts and the 3 sections of the pipe surface. Both the active biomass and the number of observed OTUs increased as the measurements proceeded from the top to the bottom of the pipe. The bacterial community was dominated in all sections by Proteobacteria. At the genus level, Nitrospira spp., Terrimonas spp., and Hyphomicrobium spp. were dominant in all sections. Gaiella spp. and Vicinamibacter spp. dominated in S-I, Blastopirellula spp. and Pirellula spp. dominated in S-II, while Holophaga spp. and Phaeodactylibacter spp. dominated in S-III. When swabbing and pipe specimen sonication were compared, the results showed that the sampling strategy significantly influences the obtained biofilm bacterial community. A consistent multisectional swabbing strategy is proposed for future biofilm sampling; it involves collecting swabs from all sections and comparing the swabs from the same position/section across locations.

The steep stepwise uptake of water vapor and easy release at low relative pressures and moderate temperatures together with high working capacities make metal-organic frameworks (MOFs) attractive, promising materials for energy efficient applications in adsorption devices for humidity control (evaporation and condensation processes) and heat reallocation (heating and cooling) by utilizing water as benign sorptive and low-grade renewable or waste heat. Emerging MOF-based process applications covered are desiccation, heat pumps/chillers, water harvesting, air conditioning, and desalination. Governing parameters of the intrinsic sorption properties and stability under humid conditions and cyclic operation are identified. Transport of mass and heat in MOF structures, at least as important, is still an underexposed topic. Essential engineering elements of operation and implementation are presented. An update on stability of MOFs in water vapor and liquid systems is provided, and a suite of 18 MOFs are identified for selective use in heat pumps and chillers, while several can be used for air conditioning, water harvesting, and desalination. Most applications with MOFs are still in an exploratory state. An outlook is given for further R&D to realize these applications, providing essential kinetic parameters, performing smart engineering in the design of systems, and conceptual process designs to benchmark them against existing technologies. A concerted effort bridging chemistry, materials science, and engineering is required. ©

Membranes with high selectivity and permeance are needed to reduce energy consumption in hydrogen purification and pre-combustion CO ₂ capture. Polybenzimidazole (PBI) is one of the leading membrane materials for this separation. In this study, we present superior novel supported PBI (poly(p-phenylene benzobisimidazole), PBDI) membranes prepared by a facile interfacial polymerization (IP) method. The effect of IP reaction duration, operating temperature and pressure on membrane separation performance was systematically investigated. The best performance was achieved for membranes prepared in a 2 h reaction time. The resulting membranes display an ultrahigh mixed-gas H ₂ /CO ₂ selectivity of 23 at 423 K together with an excellent H ₂ permeance of 241 GPU, surpassing the membrane performance of conventional polymers (the 2008 Robeson upper bound). These separation results, together with the facile manufacture, pressure resistance, long-term thermostability (>200 h) and economic analysis, recommend the PBDI membranes for industrial use in H ₂ purification and pre-combustion CO ₂ capture. Besides, PBDI membranes possess high selectivities towards H ₂ /N ₂ (up to 60) and H ₂ /CH ₄ (up to 48) mixtures, indicating their potential applications in ammonia synthesis and syngas production.

Increasing helium use in research and production processes necessitates separation techniques to secure sufficient supply of this noble gas. Energy-efficient helium production from natural gas is still a big challenge. Membrane gas separation technology could play an important role. Herein, a novel poly(p-phenylene benzobisimidazole) (PBDI) polymeric membrane for helium extraction from natural gas with low He abundance is reported. The membranes were fabricated by a facile interfacial polymerization at room temperature. The thin and defect-free membrane structure was manipulated by the confined polymerization of monomers diffusing through the interface between two immiscible liquids. Both He/CH₄ selectivity and He permeance are competitive over those of other commercial perfluoropolymers. Even at low He content of 1%, separation performance of the PBDI membrane transcended the current upper bound. The unprecedented selectivity (>1000) together with the excellent stability (∼360 h) endows PBDI membranes with a great potential for energy-efficient industrial recovery and production of this precious He resources from reservoirs with low abundance.

Preparation methods are presented of thin dual layer membranes (DLM's) and mixed matrix membranes (MMM's) based on nanosheets of the Cu-BDC metal-organic framework (MOF, lateral size range 1–5 µm, thickness 15 nm) and commercially available poly(ethylene oxide)–poly(butylene terephthalate) (PEO–PBT) copolymer (Polyactive™) and their performances are compared in CO₂/N₂ separation. The MMMs and DLMs represent two extremes, on the one hand with well-mixed components and on the other hand completely segregated layers. Compared to the free-standing membranes, the thin PAN- and zirconia-alumina-supported MMMs showed significant enhancement in both permeance and selectivity. The support properties affect the obtained selective layer thickness and its resistance impacts the CO₂/N₂ selectivity. The permeance of thin DLM's is among the highest reported literature data of MOF based thin MMMs, but have a modest selectivity. Addition of the nanosheets in the thin MMMs improves the CO₂/N₂ selectivity of the already selective polymer further to 77. The nanosheets in the thin MMMs make a gutter layer on the PAN support superfluous. The small pore support ZrO₂-alumina does not need a gutter layer. XRD analysis reveals that the spatial distribution of MOF nanosheets and polymer chains packing were responsible for differences in the permeation performance of the free-standing, thin dual layer and mixed matrix membranes.

The preparation and the performance of mixed matrix membranes based on metal-organic polyhedra (MOPs) are reported. MOP fillers can be dispersed as discrete molecular units (average 9 nm in diameter) when low filler cargos are used. In spite of the low doping amount (1.6 wt %), a large performance enhancement in permeability, aging resistance, and selectivity can be achieved. We rationalize this effect on the basis of the large surface to volume ratio of the filler, which leads to excellent dispersion at low concentrations and thus alters polymer packing. Although membranes based only on the polymer component age quickly with time, the performance of the resulting MOP-containing membranes meets the commercial target for postcombustion CO₂ capture for more than 100 days.

To gain insight into the influence of metal-organic framework (MOF) fillers and polymers on membrane performance, eight different composites were studied by combining four MOFs and two polymers. MOF materials (NH₂-MIL-53(Al), MIL-69(Al), MIL-96(Al) and ZIF-94) with various chemical functionalities, topologies, and dimensionalities of porosity were employed as fillers, and two typical polymers with different permeability-selectivity properties (6FDA-DAM and Pebax) were selected as matrices. The best-performing MOF-polymer composites were prepared by loading 25wt% of MIL-96(Al) as filler, which improved the permeability and selectivity of 6FDA-DAM to 32 and 10%, while for Pebax they were enhanced to 25 and 18%, respectively. The observed differences in membrane performance in the separation of CO₂ from N₂ are explained on the basis of gas solubility, diffusivity properties, and compatibility between the filler and polymer phases.

The performance of mixed-matrix membranes (MMMs) based on Matrimid^® and benzimidazole-linked polymers (BILPs) have been investigated for the separation CO₂/N₂ and the dependency on the filler porosity. BILPs with two different porosities (BILP-101 and RT-BILP-101) were synthesized through controlling the initial polymerization rate and further characterized by several techniques (DRIFTs, ¹³C CP/MAS NMR, SEM, TEM, N₂ and CO₂ adsorption). To investigate the influence of porosity, the two types of fillers were incorporated into Matrimid^® to prepare MMMs at varied loadings (8, 16 and 24 wt%). SEM confirmed that both BILP-101 and RT-BILP-101 are well dispered, indicating their good compatibility with the polymeric matrix. The partial pore blockage in the membrane was verified by CO₂ adsorption isotherms on the prepared membranes. In the separation of CO₂ from a 15:85 CO₂:N₂ mixture at 308 K, the incorporation of both BILPs fillers resulted in an enhancement in gas permeability together with constant selectivity owing to the fast transport pathways introduced by the porous network. It was noteworthy that the initial porosity of the filler had a large impact in separation permeability. The best improvement was achieved by 24 wt% RT-BILP-101 MMMs, for which the CO₂ permeability increases up to 2.8-fold (from 9.6 to 27 Barrer) compared to the bare Matrimid^®.

We demonstrate that b-oriented MFI (Mobil Five) zeolite membranes can be manufactured by in situ crystallization using an intermediate amorphous SiO₂ layer. The improved in-plane growth by using a zeolite growth modifier leads to fusion of independent crystals and eliminates boundary gaps, giving good selectivity in the separation of CO₂/Xe mixtures. The fast diffusion of CO₂ dominates the overall membrane selectivity toward the CO₂/Xe mixture. Because of the straight and short [010] channels, the obtained CO₂ permeation fluxes are several orders of magnitude higher than those of carbon molecular sieving membranes and polymeric membranes, opening opportunities for Xe recovery from waste anesthetic gas.

The development of new membranes with high H₂ separation performance under industrially relevant conditions (high temperatures and pressures) is of primary importance. For instance, these membranes may facilitate the implementation of energy-efficient precombustion CO₂ capture or reduce energy intensity in other industrial processes such as ammonia synthesis. We report a facile synthetic protocol based on interfacial polymerization for the fabrication of supported benzimidazole-linked polymer membranes that display an unprecedented H₂/CO₂ selectivity (up to 40) at 423 K together with high-pressure resistance and long-term stability (>800 hours in the presence of water vapor).

Membrane separation for gas purification is an energy-efficient and environment-friendly technology. However, the development of high performance membranes is still a great challenge. In principle, mixed matrix membranes (MMMs) have the potential to overcome current materials limitations, but in practice there is no straightforward method to match the properties of fillers and polymers (the main components of MMMs) in such a way that the final membrane performance reflects the high performance of the microporous filler and the processability of the continuous polymer phase. This issue is especially important when high flux polymers are utilized. In this work, we demonstrate that the use of small amounts of a glassy polymer in combination with high performance PIM-1 allow for the preparation of metal–organic framework (MOF)-based MMMs with superior separation properties and low aging rates under humid conditions, meeting the commercial target for post-combustion CO₂ capture.