Molecular Sieve Research Articles

Non‐selective Defect Minimization towards Highly Efficient Metal‐Organic Framework Membranes for Gas Separation

The persistence of defects in polycrystalline membranes poses a substantial obstacle to reaching the theoretical molecular sieving separation and scaling up production. The low membrane selectivity in most reported literature is largely due to the unavoidable non‐selective defects during synthesis, leading to a mismatch between the well‐defined pore structure of polycrystalline molecular sieve materials. This paper presents a novel approach for minimizing non‐selective defects in metal‐organic framework (MOF) membranes by a constricted crystal growth strategy in a confined environment. The in‐situ ZIF formation using the densely packed seeding array between the substrate and the pre‐grown top ZIF layer yields a confined membrane interlayer, which is highly uniform with a tightly packed crystalline structure. Unlike uncontrolled crystal growth, we purposely regulate the interlayer membrane growth in the direction parallel to the substrate. A notable 99% decrease in defects in the confined interlayer was achieved compared to the random‐grown top layer, leading to a ~353% increment in H2/N2 selectivity over the non‐confined reference MOF membrane. The performance of this new membrane sits in the optimal range above the Robeson upper bound. The membrane boasts a balanced high H2 permeability (>5000 Barrer) and selectivity (>50), significantly surpassing peer ZIF membranes.

Non‐selective Defect Minimization towards Highly Efficient Metal‐Organic Framework Membranes for Gas Separation

The persistence of defects in polycrystalline membranes poses a substantial obstacle to reaching the theoretical molecular sieving separation and scaling up production. The low membrane selectivity in most reported literature is largely due to the unavoidable non‐selective defects during synthesis, leading to a mismatch between the well‐defined pore structure of polycrystalline molecular sieve materials. This paper presents a novel approach for minimizing non‐selective defects in metal‐organic framework (MOF) membranes by a constricted crystal growth strategy in a confined environment. The in‐situ ZIF formation using the densely packed seeding array between the substrate and the pre‐grown top ZIF layer yields a confined membrane interlayer, which is highly uniform with a tightly packed crystalline structure. Unlike uncontrolled crystal growth, we purposely regulate the interlayer membrane growth in the direction parallel to the substrate. A notable 99% decrease in defects in the confined interlayer was achieved compared to the random‐grown top layer, leading to a ~353% increment in H2/N2 selectivity over the non‐confined reference MOF membrane. The performance of this new membrane sits in the optimal range above the Robeson upper bound. The membrane boasts a balanced high H2 permeability (>5000 Barrer) and selectivity (>50), significantly surpassing peer ZIF membranes.

Asymmetric Pore Windows in Pillar-Layered Metal-Organic Framework Membranes for H2/CO2 Separation.

In this study, a novel ultramicroporous pillar-layered Ni-LAP-NH2 [Ni2(l-asp)2(Pz-NH2)] (l-asp = l-aspartic acid, Pz-NH2 = aminopyrazine) membranes on porous α-Al2O3 tubes with high performance and good thermal stability was first fabricated using isostructural Ni-LAP[Ni2(l-asp)2(Pz)] (Pz = pyrazine) crystals as seeds. Utilizing the principle of reticular chemistry, here, we introduced the active amino side group into the Ni-LAP frameworks by replacing the pillar-layered ligand Pz with Pz -NH2 while maintaining the original Ni-LAP small pore size, and the amino side group induced a "steric hindrance" effect and the physical adsorption affinity, which synergistically delayed CO2 penetration. It was found that the preferential (111) orientation Ni-LAP-NH2 membrane (Z10) exhibited a high H2/CO2 separation performance with a separation factor of 41.7 and H2 permeance of 9.08 × 10-8 mol·m-2·s-1·Pa-1 under optimal conditions. These MOF materials demonstrated potential for industrial H2 purification due to their tunable pore structure and remarkable stability. Moreover, this strategy offers an effective approach to tailoring pillar-layered MOF membranes with targeted molecular sieving ability.

Pore configuration control in hybrid azolate ultra-microporous frameworks for sieving propylene from propane.

Developing porous adsorbents for the complete sieving of propylene/propane mixtures represents an alternative method to energy-intensive cryogenic distillation processes. However, the similar physical properties of these molecules and the inherent trade-off among adsorption capacity, selectivity, diffusion kinetic and host-guest binding interactions in molecular sieving adsorbents makes their separation challenging. Here we report the separation of propylene/propane mixtures through a crystalline porous material (HAF-1) that features channels and shrinkage throats-the latter defined as narrower channels that connect the main channels and a molecular pocket-where the throat aperture is between the kinetic diameters of propylene and propane. Single-crystal X-ray diffraction and computational simulation reveal that the shrinkage channels and hanging molecular pockets are key to ensure high sieving efficiency and high propylene adsorption capacity. Dynamic breakthrough experiments show that HAF-1 enables the achievement of high-purity (≥99.7%) propylene with a productivity of 33.9 l kg-1 by just one adsorption-desorption circle from propylene/propane mixtures.

Carbon Molecular Sieve Membranes from Poly(oxo-biphenylene-isatin) with Increasingly Bulky Fluorine Substitution: Characterization and Gas Transport Properties

Carbon Molecular Sieve Membranes from Poly(oxo-biphenylene-isatin) with Increasingly Bulky Fluorine Substitution: Characterization and Gas Transport Properties

Functional Immunoaffinity 3D Magnetic Core-Shell Nanometallic Structure for High-Efficiency Separation and Label-Free SERS Detection of Exosomes.

Tumor exosomes, known as maternal cell messengers, play an important role in cancer occurrence, proliferation, metastasis, immune escape, drug resistance, and other processes and are an entry point for cancer research. However, there is still a lack of an efficient detection technology for exosomes. In this study, the ultrahigh sensitivity SERS nanoprobe with a three dimensional (3D) magnetic core/Au nanocolumn/Au nanoparticles shell strongly coupling multistage structure (Fe3O4@NR-NPs) was constructed by crystal growth of nanocrystals in the confined space of a central radiating single particle mesoporous molecular sieve channel and strong coupling secondary growth of gold particles. The exosomes were confined onto the "hot spot" of plasmonic nanoparticles and rapidly enriched by CD63 antibody functional-Fe3O4@NR-NPs to achieve high sensitivity detection, with the limit of detection of 1 × 103 particles/mL (S/N = 3). The spectral data set of different exosomes is applied to train for multivariate classification of cell types and to estimate how the normal exosome data resemble cancer cell exosomes by principal component analysis (PCA). Finally, this detection method has also been successfully employed for the detection of exosomes in complex samples; this proves that the proposed SERS-based method is a promising tool for clinical cancer screening.

Research on the modification technology of beta molecular sieve

The influence of temperature and time of the acid washing and hydrothermal treatment on Beta zeolite properties was examined in detail, the results revealed that acid washing at 2h and 80℃and 2h hydrothermal treatment at 650℃are the best modification operating conditions. The different SiO2/Al2O3ratio of Beta zeolite are systematically modified using optimized modification operating conditions. Beta zeolite modified from higher SiO2/Al2O3ratio of the starting Beta also has higher SiO2/Al2O3 ratio. Crystallinity of starting Beta zeolite has less effect on the modified Beta zeolite. As the SiO2/Al2O3 ratio of starting Beta increased, total acid amount of modified Beta decreased. When the SiO2/Al2O3 ratio of starting Beta is bigger, the surface area and pore volume is higher.

Solvent‐free synthesis of medium chain triacylglycerols by esterification of capric, caprylic acids with 1, 3‐specific and non‐specific lipases

AbstractMedium chain triacylglycerols (MCTs) are used as a functional oil in various food and pharmaceutical formulations because of their numerous health benefits and physical properties. Enzymatic esterification of glycerol with caprylic (C8:0) and capric acids (C10:0) in a molar ratio of 1:3.5 [50% (C8:0) and 50% (C10:0)] was carried out for the solvent free synthesis of MCTs using 5% (w/w) 1,3 specific lipase, Lipozyme RM IM and non‐specific lipase, Novozym 435 in the presence of molecular sieves (10%) and low pressure conditions (50 and 150 mbar) at 50°C. Novozym 435 was more effective in the esterification reaction under 50 mbar reduced pressure, achieving ~54.74% triacylglycerol formation in 6 h, compared to Lipozyme RMIM, which achieved ~31.25% under the same conditions. Further reactions with Novozym 435 for 24 h showed that the maximum formation of MCTs occurred at 20 h (86.46 ± 3%), after which the reaction reached equilibrium. When 50 mbar was used, the formation of triacylglycerols enhanced 13 times compared with the results obtained at atmospheric pressure condition. Chemical characterization of the final MCTs confirmed the formation of four triacylglycerol species (TAG (8:0/8:0/8:0), TAG (8:0/8:0/10:0), TAG (8:0/10:0/10:0), and TAG (10:0/10:0/10:0) with LC–MS and NMR analysis. The melting and crystallization points of the synthesized oil was found to be −3.47°C and −23.48°C, respectively. Our findings contribute to developing a green process for synthesizing MCTs using two different fatty acids. The final product can be used as a nutraceutical oil or as an ingredient to enhance the food's physical properties.

Gas adsorption and separation applications of MOF materials

Abstract. Low-carbon hydrocarbons (C1-C4) are really important raw materials used in making different kinds of big molecules and stuff in industries. Before, people mostly used super cold cooling and a method where stuff gets soaked up. But these ways need big machines and use a lot of energy. So, scientists are trying to make new ways to separate things that don't use as much energy. One great idea is using how different gases stick to things to separate them. This idea could be a brilliant way to replace the old methods. The most important part of this idea is making things that can stick to the gases. There's this special material called metal-organic frameworks (MOFs) that's a mix of things from nature and chemicals. It has tiny holes and places that can do special things, and it's being studied a lot for separating gases. Traditional porous materials like activated carbon, silica gel, and molecular sieves have been widely used in industries, which has greatly contributed to industrial growth and people's living standards. MOFs have changeable structures and spots that can do special things. By changing the metal bits or the organic parts, we can control the size of the holes in MOFs, the special spots, and how much surface they have. These things make MOFs useful for storing gases, separating stuff by sticking and making reactions happen in fields like chemistry [1-3]. This paper explores the categories of MOF applications.

Organic Solvent Nanofiltration Membrane with In Situ Constructed Covalent Organic Frameworks as Separation Layer

Organic solvent nanofiltration (OSN) technology is advantageous for separating mixtures of organic solutions owing to its low energy consumption and environmental friendliness. Covalent organic frameworks (COFs) are good candidates for enhancing the efficiency of solvent transport and ensuring precise molecular sieving of OSN membranes. In this study, p-phenylenediamine (Pa) and 1,3,5-trimethoxybenzene (Tp) are used to construct, in situ, a TpPa COF skin layer via interfacial polymerization (IP) on a polyimide substrate surface. After subsequent crosslinking and activation steps, a kind of TpPa/polyimide (PI) OSN membrane is obtained. Under optimized fabrications, this OSN membrane exhibits an ethanol permeance of 58.0 LMH/MPa, a fast green FCF (FGF) rejection of 96.2%, as well as a pure n-hexane permeance of 102.0 LMH/MPa. Furthermore, the TpPa/PI OSN membrane exhibits good solvent resistance, which makes it suitable for the separation, purification, and concentration of organic solvents.

Fluorinated Squareimines for Molecular Sieving of Aromatic over Aliphatic Compounds

The development of more energy‐efficient separation technologies is essential. Especially the separation of cyclic aliphatic hydrocarbons from their aromatic counterparts remains a significant challenge due to azeotrope formation and similar physical properties, often requiring energy‐intensive processes. Herein, we introduce a novel class of electron‐deficient macrocycles with a unique rectangular structure to optimise π···π interactions within the pore, enabling the highly selective molecular sieving of aromatic compounds from mixtures. Utilising dynamic covalent imine chemistry, the squareimine NDI2F42‐based crystalline functional material is directly obtained from the reaction mixture in a single self‐assembly step in high yields of 84%, alongside the larger NDI2F82 congener, which can be obtained in 69% yield. In vapour sorption and diffusion experiments, NDI2F42 demonstrates rapid adsorption kinetics with selectivities of 97:3 for benzene over cyclohexane and 93:7 for toluene over methylcyclohexane, while single‐crystal and powder X‐ray diffraction studies confirm that the selectivity is primarily governed by directed π···π interactions.

Shape‐Selective Zeolites for Tandem CO2 Hydrogenation‐Carbonylation Reactions

The valorization of carbon dioxide as a C1 building block in C‐C bond forming reactions is a critical link on the road to carbon‐circular chemistry. Activation of this inert molecule through reduction with H2 to carbon monoxide in the reverse water‐gas shift (RWGS) reaction can be followed by a wide spectrum of consecutive carbonylation reactions, but the RWGS is severely equilibrium limited at the moderate temperatures of carbonylations. Here we successfully reconcile both reactions in one pot, while avoiding incompatibilities through a zeolite‐based compartmentalized approach. More specifically, Pt encapsulated in a small‐pore LTA zeolite selectively generates carbon monoxide in mild reaction conditions; an ensuing one‐pot carbonylation reaction allows to shift the equilibrium through continuous consumption of CO. Moreover, the zeolite encapsulation avoids undesired reactions like hydrogenation of the olefin reactant through a molecular sieving effect. This strategy was first studied in‐depth for Rh‐catalyzed olefin hydroformylation with CO2/H2, affording aldehydes in good yields with high regioselectivities. The methodology was then extended to a variety of carbonylations using CO2 for the synthesis of bulk and fine chemicals.

Shape-Selective Zeolites for Tandem CO2 Hydrogenation-Carbonylation Reactions.

The valorization of carbon dioxide as a C1 building block in C-C bond forming reactions is a critical link on the road to carbon-circular chemistry. Activation of this inert molecule through reduction with H2 to carbon monoxide in the reverse water-gas shift (RWGS) reaction can be followed by a wide spectrum of consecutive carbonylation reactions, but the RWGS is severely equilibrium limited at the moderate temperatures of carbonylations. Here we successfully reconcile both reactions in one pot, while avoiding incompatibilities through a zeolite-based compartmentalized approach. More specifically, Pt encapsulated in a small-pore LTA zeolite selectively generates carbon monoxide in mild reaction conditions; an ensuing one-pot carbonylation reaction allows to shift the equilibrium through continuous consumption of CO. Moreover, the zeolite encapsulation avoids undesired reactions like hydrogenation of the olefin reactant through a molecular sieving effect. This strategy was first studied in-depth for Rh-catalyzed olefin hydroformylation with CO2/H2, affording aldehydes in good yields with high regioselectivities. The methodology was then extended to a variety of carbonylations using CO2 for the synthesis of bulk and fine chemicals.

Fluorinated Squareimines for Molecular Sieving of Aromatic over Aliphatic Compounds.

The development of more energy-efficient separation technologies is essential. Especially the separation of cyclic aliphatic hydrocarbons from their aromatic counterparts remains a significant challenge due to azeotrope formation and similar physical properties, often requiring energy-intensive processes. Herein, we introduce a novel class of electron-deficient macrocycles with a unique rectangular structure to optimise π···π interactions within the pore, enabling the highly selective molecular sieving of aromatic compounds from mixtures. Utilising dynamic covalent imine chemistry, the squareimine NDI2F42-based crystalline functional material is directly obtained from the reaction mixture in a single self-assembly step in high yields of 84%, alongside the larger NDI2F82 congener, which can be obtained in 69% yield. In vapour sorption and diffusion experiments, NDI2F42 demonstrates rapid adsorption kinetics with selectivities of 97:3 for benzene over cyclohexane and 93:7 for toluene over methylcyclohexane, while single-crystal and powder X-ray diffraction studies confirm that the selectivity is primarily governed by directed π···π interactions.

MAPO-5 molecular sieves from alkylimidazolium bromide ionic liquids

The ionic liquids diisopropylimidazolium bromide (DIPI) and diisobutylimidazolium bromide (DIBU) were used both as solvents and structure-directing agents (SDAs) to obtain AlPO4-5 and MnAPO-5 (Mn-AFI) molecular sieves. For increasing level of manganese, DIBU always yielded pure-phase Mn-AFI whereas DIPI led to amorphous product when more than 0.13 eq of Mn was added. Varying amounts of water, HF and metal led to AFI, cristobalite or tridymite phases. We also explored the use of nickel as the metal dopant, and although AFI phase were obtained under certain conditions, no framework incorporation of the metal was observed. Because of the vanishingly low vapor pressure of the ILs, the synthesis does not carry the risk of pressure build-up. The ILs were easily and fully recyclable and used for multiple syntheses. The MnAPO-5 material was characterized with powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), electron paramagnetic resonance (EPR), multinuclear solid-state nuclear magnetic resonance (SS-NMR) and X-ray absorption fine structure (XAFS). These findings provide new insight into the ionothermal synthesis of metal-doped AFI frameworks with possible implications in catalytic applications.

Physical and Chemical Dual Confinement Promotes Controllable Synthesis of Loose-Structured Azine-Linked Nanofilms for Fast Molecular Separation.

Thin-film composite (TFC) membranes, featuring nanoscale film thickness and customizable pore structures, hold promise for solute-solute separations. However, achieving on-demand molecular sieving requires fine control over the membrane microstructure. Here, the concept of physical and chemical dual confinement (PCDC) is introduced to fabricate loose-structured TFC membranes via confined interfacial polymerization (IP). This concept leverages the synergistic effects of physically restricted monomer diffusion and a chemically inhibited reaction to achieve controlled nanofilm growth. Dorsal addition of the aqueous phase to the hydrogel reduces the diamine diffusion via electrostatic and H-bonding interactions within its nanopores. The prepassivation of hydrazine using acid protonation effectively weakens its ability for nucleophilic reactivity. This confined IP between twisted TFPA and short-chain hydrazine yielded loosely structured azine-linked nanofilms, which displayed a high permeability of 53.4 LMH bar-1 and effective differentiation of binary mixtures. This PCDC concept offers a useful guideline to finely tailor polymeric nanofilms for precise separations.

Dynamics of Water, CO₂, Ethane and Their Mixtures in ZSM-22 Zeolite: The Role of Polarity and Hydrogen Bonding

Abstract Understanding the interplay between confinement effects and intermolecular interactions is essential for predicting molecular diffusion in zeolites. In this study, we investigate the diffusion behavior of ethane, CO₂, and water in ZSM-22 molecular sieves, focusing on the effects of mixing these fluids. Our results reveal that while CO₂ has minimal impact on ethane diffusion, water significantly slows ethane’s motion by forming molecular bridges across the pore structure, reducing ethane's diffusion by up to 30%. Ethane, in turn, restricts water’s mobility, and reduces the water-water coordination number from 2.22 to 0.73 depending on concentration. The diffusion of CO₂ in mixtures shows a 40% increase in pure state under confinement. The role of polarity and hydrogen bonding is crucial, with water molecules exhibiting 1.2 hydrogen bonds in the confined state—much lower than the 3.4 bonds in bulk water. Molecular rotation in ZSM-22 of all fluids occurs at two distinct time scales: the short-time fast rotation dominated by molecular inertia and the long-time rotation hindered by fluid-zeolite interactions. For water, hydrogen bonding further restricts full rotational freedom. These findings provide a comprehensive understanding of how ethane, water, and CO₂ interact and diffuse in nanoporous materials.

Engineering Molecule‐Designed In Situ Polymerization on Al‐Doped Molecular‐Sieve Framework Enables Robust Quasi‐Solid‐State Lithium Batteries

AbstractAchieving fast Li+ transport kinetics and stable electrode/electrolyte interfaces is of paramount importance, yet extremely challenging for the practical success of solid‐state lithium metal batteries, which requires the rational design of the structure and composition of solid‐state electrolytes. Herein, a composite quasi‐solid‐state electrolyte is fabricated through in situ polymerization of a molecule‐designed polymer chain within the functionalized molecular sieve framework (Al‐MCM41). In this design, the robust Brønsted/Lewis acid–base interactions between Al‐MCM41 and TFSI− facilitate the dissociation of lithium salt, leading to a Li+ transference number as high as 0.81. Meanwhile, the well‐ordered mesopores of Al‐MCM41 act as the “reservoir” of the polymer chain, creating continuous ionic migration pathways to offer an excellent Li+ conductivity of 1.09 × 10−3 S cm−1 at 30 °C. Furthermore, the polymer with fluorinated and nitrided functional groups guarantees a dual‐reinforced anode and cathode interface. Such an integrated electrolyte with simultaneous unimpeded Li+ transport and robust interfaces delivers extraordinary capacity retention of 84.6% over 600 cycles at 5 C when coupled with LiFePO4 cathode and remarkable reversible capacity of 129.0 mAh g−1 after 200 cycles with high‐voltage NCM622 cathode. This work provides a significant avenue for enhancing the practical feasibility of solid‐state lithium metal batteries.

Bottom-Up Porous Graphene Synthesis and Its Applications.

Incorporation of regular order pores/holes/defects into semimetalic graphene sheets can tune the band gap up to 1 eV or more introducing semiconducting property and therefore exhibiting promising applications for organic electronics such as field-effect transistors (FETs), molecular sieve membranes, gas sensing, catalysis devices, etc. In this mini review, we focused on bottom-up approaches to introduce periodic homogeneous pores into graphene and nanographene and graphene nanoribbons along with their characteristics and potential applications in various fields.

A methodology for selection of solid desiccants in energy recovery ventilators

Controlling indoor humidity levels is essential for maintaining acceptable indoor air quality in buildings. The use of energy recovery ventilators (ERVs) is an energy-efficient way to regulate indoor air humidity. Fixed-bed regenerators and rotary wheels are widely used ERVs because of their high sensible and latent effectiveness. These ERVs are made of desiccant-coated substrates, which enable them to transfer moisture between the supply and exhaust air streams. However, the moisture transfer ability of ERVs depends on the physiochemical and sorption properties of desiccants. Extensive, full-scale experiments are required to determine the best desiccant material for these systems. This paper presents a simplified method of selecting suitable desiccant materials for ERVs. The methodology involves important characterization methods, literature correlations for performance prediction, and cost-effective testing methods prior to full-scale testing, and full-scale test methods are discussed in detail. Furthermore, the performance of a few newly derived materials is evaluated and compared with that of conventional desiccants such as silica gel and molecular sieves. The highest latent effectiveness was obtained for composite of super absorbent polymer (SAP) with potassium formate (SAP-HCO2K-50 %), all-polymer porous solid desiccant (APPSD) and metal organic framework (MOF)–MIL–101 (Cr), followed by activated carbon fibre felt (ACF) Silica sol-LiCl30, SAP, silica gel, MOF–303, and molecular sieve. Researchers and manufacturers would benefit from the proposed methodology and presented data in developing new desiccant materials for ERV applications.