Pore Aperture Research Articles

Doubly Interpenetrated Metal-Organic Framework of pcu Topology for Selective Separation of Propylene from Propane.

Adsorptive separation is an appealing alternative technology to reduce the high energy and capital cost of the distillation separation of propylene/propane; however, it is very challenging to realize. A new flexible metal-organic framework (MOF) material [Zn2(BDC-Cl)2(Py2TTz)] with a doubly interpenetrated pillared paddle wheel structure of pcu (primitive cubic) topology has been realized for this difficult separation for the first time. Through a judicious choice of linkers, the framework has small pore apertures that lead to much more propylene adsorption than propane. The selective adsorption relies on the sieving effect of the flexible framework. The column breakthrough experiment further demonstrated that efficient separation can be achieved under dynamic conditions.

Intensification of water/ethanol separation by PVA hybrid membrane with different functional ligand UiO-66-X nanochannels in pervaporation process

In order to investigate the effects of MOFs by altering ligands with various functional groups on separation selection in pervaporation dehydration, three hydrophilic UiO-66-X nanoparticles were respectively synthesized and blended into poly (vinyl alcohol) matrix to fabricate water-selective membrane for ethanol dehydration via PV technology. Both the experimental and molecular simulation results confirmed the UiO-66-X counterbalancing factors of enhanced polarity and suitable pore size gave rise to the optimal performance in ethanol dehydration. The PV performances could be tuned by the type and quantity of functional groups carried by UiO-66-X nanoparticles. As a result, the pore aperture of UiO-66-(COOH)2 nanoparticles provided continuous channel for water diffusion, and water molecules could also be activated attributed to the strong interaction between the UiO-66-(COOH)2 nanoparticles and water molecules which enhanced the penetration and diffusion of water molecular in hybrid membrane to increase the water flux. The optimized hybrid membranes with UiO-66-(COOH)2 loading of 8 wt% exhibited the total flux of 979 ± 7 g/(m2·h) and a separation factor of 2084 ± 21.

Selective Adsorption of CO2 on Zeolites NaK-ZK-4 with Si/Al of 1.8-2.8.

Zeolites with appropriately narrow pore apertures can kinetically enhance the selective adsorption of CO2 over N2. Here, we showed that the exchangeable cations (e.g., Na+ or K+) on zeolite ZK-4 play an important role in the CO2 selectivity. Zeolites NaK ZK-4 with Si/Al = 1.8–2.8 had very high CO2 selectivity when an intermediate number of the exchangeable cations were K+ (the rest being Na+). Zeolites NaK ZK-4 with Si/Al = 1.8 had high CO2 uptake capacity and very high CO2-over-N2 selectivity (1190). Zeolite NaK ZK-4 with Si/Al = 2.3 and 2.8 also had enhanced CO2 selectivity with an intermediate number of K+ cations. The high CO2 selectivity was related to the K+ cation in the 8-rings of the α-cage, together with Na+ cations in the 6-ring, obstructing the diffusion of N2 throughout the zeolite. The positions of the K+ cation in the 8-ring moved slightly (max 0.2 Å) toward the center of the α-cage upon the adsorption of CO2, as revealed by in situ X-ray diffraction. The CO2-over-N2 selectivity was somewhat reduced when the number of K+ cations approached 100%. This was possibly due to the shift in the K+ cation positions in the 8-ring when the number of Na+ was going toward 0%, allowing N2 diffusion through the 8-ring. According to in situ infrared spectroscopy, the amount of chemisorbed CO2 was reduced on zeolite ZK-4s with increasing Si/Al ratio. In the context of potential applications, a kinetically enhanced selection of CO2 could be relevant for applications in carbon capture and bio- and natural gas upgrading.

Preparation of an extra-large pore titanosilicate with 14 × 12-ring channels and its catalytic performance in epoxidation

An interlayer expanded zeolite, IEZ-PLS-3(Si–O–Si), was post-synthesized by the simple interlayer silylation of layered ECNU-9(P), which was derived from a lamellar precursor (PLS-3) using dichlorotetramethyldisiloxane (DCTMS) as the silylation reagent. The IEZ-PLS-3(Si–O–Si) was composed of ferrierite sheets and an intersected 14 × 12-ring (R) extra-large pore system. The results revealed that the IEZ-PLS-3(Si–O–Si) was composed of nanosized crystals, indicating that it is favorable for catalysis. Ti active sites were introduced into the framework of the IEZ-PLS-3(Si–O–Si) by solid-phase stirring in H2TiF6 aqueous solution at room temperature. The catalytic properties of the resulting material (Ti-IEZ-PLS-3(Si–O–Si)) were tested by carrying out the epoxidation of propene and allyl chloride, both of which have industrial application value. The Ti-IEZ-PLS-3(Si–O–Si) showed a higher catalytic activity compared to the typical well-known titanosilicate zeolites, including titanium silicalite-1 (TS-1) and Ti-MWW, which are currently used in industries. We also conducted the epoxidation of cyclohexene using bulk tert-butyl peroxide (TBHP) in decane as the oxidant to explore the pore properties of the Ti-IEZ-PLS-3(Si–O–Si). The Ti-IEZ-PLS-3(Si–O–Si) exhibited better catalytic performance than the TS-1 and Ti-MWW for cyclohexene due to its larger pore aperture.

Two-dimensional d-π conjugated metal-organic framework based on hexahydroxytrinaphthylene

The development of new two-dimensional (2D) d-π conjugated metal-organic frameworks (MOFs) holds great promise for the construction of a new generation of porous and semiconductive materials. This paper describes the synthesis, structural characterization, and electronic properties of a new d-π conjugated 2D MOF based on the use of a new ligand 2,3,8,9,14,15-hexahydroxytrinaphthylene. The reticular self-assembly of this large π-conjugated organic building block with Cu(II) ions in a mixed solvent system of 1,3-dimethyl-2-imidazolidinone (DMI) and H2O with the addition of ammonia water or ethylenediamine leads to a highly crystalline MOF Cu3(HHTN)2, which possesses pore aperture of 2.5 nm. Cu3(HHTN)2 MOF shows moderate electrical conductivity of 9.01 × 10−8 S·cm−1 at 385 K and temperature-dependent band gap ranging from 0.75 to 1.65 eV. After chemical oxidation by I2, the conductivity of Cu3(HHTN)2 can be increased by 360 times. This access to HHTN based MOF adds an important member to previously reported MOF systems with hexagonal lattice, paving the way towards systematic studies of structure-property relationships of semiconductive MOFs.

Molecular Sieving of C2 -C3 Alkene from Alkyne with Tuned Threshold Pressure in Robust Layered Metal-Organic Frameworks.

C2 -C3 alkyne/alkene separation is of great importance; however, designing materials for an efficient molecular sieving of alkenes from alkynes remains challenging. Now, two hydrolytically stable layered MOFs, [Cu(dps)2 (GeF6 )] (GeFSIX-dps-Cu, dps=4,4'-dipyridylsulfide) and [Zn(dps)2 (GeF6 )] (GeFSIX-dps-Zn), can achieve almost complete exclusion of both C3 H6 and C2 H4 from their alkyne analogues. GeFSIX-dps-Cu displays a notable advanced threshold pressure for alkynes adsorption and thus substantial uptakes at lower pressures, providing record C3 H4 /C3 H6 uptake ratios and capacity-enhanced C2 H2 /C2 H4 sieving for a wide composition range. Metal substitution (Zn to Cu) affords fine tuning of linker rotation and layer stacking, creating slightly expanded pore aperture and interlayer space coupled with multiple hydrogen-bonding sites, allowing easier entrance of alkyne while excluding alkene. Breakthrough experiments confirmed tunable sieving by these MOFs for C3 H4 /C3 H6 and C2 H2 /C2 H4 mixtures.

Molecular Sieving of C2‐C3 Alkene from Alkyne with Tuned Threshold Pressure in Robust Layered Metal–Organic Frameworks

AbstractC2‐C3 alkyne/alkene separation is of great importance; however, designing materials for an efficient molecular sieving of alkenes from alkynes remains challenging. Now, two hydrolytically stable layered MOFs, [Cu(dps)2(GeF6)] (GeFSIX‐dps‐Cu, dps=4,4′‐dipyridylsulfide) and [Zn(dps)2(GeF6)] (GeFSIX‐dps‐Zn), can achieve almost complete exclusion of both C3H6 and C2H4 from their alkyne analogues. GeFSIX‐dps‐Cu displays a notable advanced threshold pressure for alkynes adsorption and thus substantial uptakes at lower pressures, providing record C3H4/C3H6 uptake ratios and capacity‐enhanced C2H2/C2H4 sieving for a wide composition range. Metal substitution (Zn to Cu) affords fine tuning of linker rotation and layer stacking, creating slightly expanded pore aperture and interlayer space coupled with multiple hydrogen‐bonding sites, allowing easier entrance of alkyne while excluding alkene. Breakthrough experiments confirmed tunable sieving by these MOFs for C3H4/C3H6 and C2H2/C2H4 mixtures.

Fabrication of highly CO2/N2 selective polycrystalline UiO-66 membrane with two-dimensional transition metal dichalcogenides as zirconium source via tertiary solvothermal growth

Zirconium-based MOF (Zr-MOF) membranes have attracted widespread attention due to their highly tailorable pore aperture and adsorption behavior achieved by functional group decoration and ligand/cluster-missing defect regulation as well as extraordinary chemical/thermal stability. Nevertheless, it has remained a great challenge to further improve the separation performance of Zr-MOF membranes due to very limited available zirconium sources and heating modes. In this study, we prepared polycrystalline UiO-66 membranes exhibiting unprecedented CO2/N2 selectivity (31.3). The use of layered ZrS2, a representative of transition-metal dichalcogenides (TMDCs), as zirconium source during tertiary solvothermal growth was found to be indispensable for improving the separation performance of UiO-66 membranes. As far as we know, the CO2/N2 selectivity reported in this study was the highest among all pristine polycrystalline MOF membranes measured under ambient conditions. More importantly, our study highlighted the importance of concurrent metal source and fabrication process innovation in performance enhancement of polycrystalline MOF membranes.

A mini‐review and recent outlooks on the synthesis and applications of zeolite imidazolate framework‐8 (ZIF‐8) membranes on polymeric substrate

AbstractZeolite imidazolate framework (ZIF) is one of the subclasses of metal–organic frameworks (MOFs) that has been widely investigated in the last decade. Among the ZIF members, a particular interest has been devoted to ZIF‐8 due to various factors, such as mild and fast synthesis conditions, framework stability and the right pore aperture to perform various separations. Recently, there has also been growing interest in developing ZIF‐8 as a thin layer membrane on polymeric substrates as they are considerably cheaper than the inorganic ones. This review then discusses recent advances in this field, focusing on various fabrication strategies and promising future applications. The challenges and future perspectives are also discussed with an emphasis on employing this approach in industrial scale. © 2020 Society of Chemical Industry

Enhancement in the selectivity of O2/N2 via ZIF-8/CA mixed-matrix membranes and the development of a thermodynamic model to predict the permeability of gases.

Zeolitic imidazolate framework-8 (ZIF-8) has a sodalite topology. ZIF-8 is composed of zinc ion coordinated by four imidazolate rings. The pore aperture of ZIF-8 is 3.4Å, which readily retains large gas molecules like N2. In this work, mixed-matrix membranes (MMMs) have been fabricated by utilizing ZIF-8 and pristine cellulose acetate (CA) for O2/N2 separation. Membranes of pristine CA and MMMs of ZIF-8/CA at various ZIF-8 concentrations were prepared in tetrahydrofuran (THF). Permeation results of the fabricated membranes revealed increasing selectivity for O2/N2 with increasing pressure as well as ZIF-8/CA concentration up to 5% (w/w). The selectivity of O2/N2 increased 4 times for MMMs containing 5% (w/w) of ZIF-8/CA as compared with the pristine CA membrane. A thermodynamic model has also been developed to predict the permeability of gases through polymeric membranes. The results were compared with literature data as well as the pristine CA membrane produced in this work for model validation.

High-Flux Vertically Aligned 2D Covalent Organic Framework Membrane with Enhanced Hydrogen Separation.

In this study, we propose a new concept of vertically aligned 2D covalent organic framework (COF) layers forming a membrane for efficient gas separation on the basis of precise size exclusion. Gas transport takes place through the COF interlayer space (typically 0.3-0.4 nm) rather than through the nanometer-sized pore apertures. Construction of such a unique membrane architecture was implemented via in situ oriented growth of 2D COFs inside a skeleton of vertically aligned CoAl-layered double hydroxide (LDH) nanosheets. The resultant vertical COF-LZU1 membrane exhibits a high H2 permeance of ∼3600 GPU together with a desirable separation selectivity for gas mixtures such as H2/CO2 (31.6) and H2/CH4 (29.5), thus surpassing the 2008 Robeson upper bounds. The universality of this approach was demonstrated by successfully producing two types of high-quality vertical COF membranes with superior performance as well as outstanding running stability.

Bimetallic ions regulate pore size and chemistry of zeolites for selective adsorption of ethylene from ethane

The petrochemical industry currently accomplishes olefin/paraffin separation by energy-intensive cryogenic distillation at an enormous scale. We report a sequential Ca2+/Ag+ ion-exchanged zeolite that achieves nearly ideal molecular sieving of C2H4/C2H6 and superior C2H4 adsorption capacity. Sequential and partial ion exchange regulates the pore size in ±0.2 Å increments, ranging between 3.8 and 4.2 Å. The demonstrated C2H4 adsorption capacity of 3.7 mmol/g, under ambient conditions, is the highest among zeolite-based materials. Elaborated with DFT calculations, Ag+-induced the stretching of the C-H bond and reduction of H-C-H bond angle of the C2H4 molecule in confined pore, providing C2H4 with the molecular basis and favorable kinetics for selective admission to pore size even less than 4 Å. The strategy of using bimetallic ions to regulate pore aperture size and selective admission of gas molecules with favorable kinetics provides a general path to be extended to other analogous molecular separation processes.

Separation of hexane isomers by introducing “triangular-like and quadrilateral-like channels” in a bcu-type metal-organic framework

The separation of hexane isomers is of vital importance to produce high quality gasoline in the petrochemical industry. However, the similar vapor pressure and boiling point of hexane isomers bring great difficulties and challenges in the separation process. Sieving effect, which allowing smaller molecules pass through and preventing others, should be a powerful strategy to solve this problem by making good use of porous materials. Therefore, physical separation by metal-organic framework (MOF) materials appears and becomes a burgeoning separation technique in industry. Due to the weak interaction between hexane isomers with absorbents, it puts forward higher requirements for the accurate design of MOF materials with optimal pore system. To address this issue, a novel MOF [Zn9(tba)9(dabco)3]·12DMA·6MeOH (abbreviation: Zn9(tba)9(dabco)3; H2tba = 4-(1H-tetrazol-5-yl)-benzoic acid; dabco = 1,4-diazabicyclo[2.2.2]octane; DMA = N, N-dimethylacetamide) with bcu network has been designed and synthesized by reticular chemistry strategy. Benefiting from the pre-designed topology and suitable linear ligand H2tba and dabco, the structure of Zn9(tba)9(dabco)3 exhibits two types of channels with triangular-like and quadrilateral-like geometry. Zn9(tba)9(dabco)3 with appropriate channel size and shape displays potential selective adsorption capacity of vapor-phase hexane isomers through sieving effect. Moreover, outstanding gas adsorptive separation properties of Zn9(tba)9(dabco)3 could also be speculated by theoretical ideal adsorbed solution theory (IAST), suggesting Zn9(tba)9(dabco)3 can be regarded as a potential adsorbent material for purification natural gas. Breakthrough experiments show that Zn9(tba)9(dabco)3 is capable of discriminating all four hexane isomers at 298 K, and the corresponding research octane number (RON) of the eluted mixture closes to 95, which is higher than the standard for industrially refined hexane blends (about 83). We speculate that sieving effect and diffusion are a synergetic contributory factor in their elution dynamics, which may be ascribed to temperature-dependent interaction between pore aperture and each isomer. This work presents a typical example for design of efficient MOF absorbents by reticular chemistry strategy.

The Role of Proteases in Determining Stomatal Development and Tuning Pore Aperture: A Review.

Plant proteases, the proteolytic enzymes that catalyze protein breakdown and recycling, play an essential role in a variety of biological processes including stomatal development and distribution, as well as, systemic stress responses. In this review, we summarize what is known about the participation of proteases in both stomatal organogenesis and on the stomatal pore aperture tuning, with particular emphasis on their involvement in numerous signaling pathways triggered by abiotic and biotic stressors. There is a compelling body of evidence demonstrating that several proteases are directly or indirectly implicated in the process of stomatal development, affecting stomatal index, density, spacing, as well as, size. In addition, proteases are reported to be involved in a transient adjustment of stomatal aperture, thus orchestrating gas exchange. Consequently, the proteases-mediated regulation of stomatal movements considerably affects plants’ ability to cope not only with abiotic stressors, but also to perceive and respond to biotic stimuli. Even though the determining role of proteases on stomatal development and functioning is just beginning to unfold, our understanding of the underlying processes and cellular mechanisms still remains far from being completed.

Tailoring Pore Aperture and Structural Defects in Zirconium-Based Metal–Organic Frameworks for Krypton/Xenon Separation

Krypton and xenon are important gases in many applications, including, but not limited to, electronics, lighting, and medicine. Separation of these two gases by cryogenic distillation is highly ene...

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.

Separation of Xe from Kr with Record Selectivity and Productivity in Anion‐Pillared Ultramicroporous Materials by Inverse Size‐Sieving

AbstractThe separation of xenon/krypton (Xe/Kr) mixture is of great importance to industry, but the available porous materials allow the adsorption of both, Xe and Kr only with limited selectivity. Herein we report an anion‐pillared ultramicroporous material NbOFFIVE‐2‐Cu‐i (ZU‐62) with finely tuned pore aperture size and structure flexibility, which for the first time enables an inverse size‐sieving effect in separation along with record Xe/Kr selectivity and ultrahigh Xe capacity. Evidenced by single‐crystal X‐ray diffraction, the rotation of anions and pyridine rings upon contact of larger‐size Xe atoms adapts cavities to the shape/size of Xe and allows strong host‐Xe interaction, while the smaller‐size Kr is excluded. Breakthrough experiments confirmed that ZU‐62 has a real practical potential for producing high‐purity Kr and Xe from air‐separation byproducts, showing record Kr productivity (206 mL g−1) and Xe productivity (42 mL g−1, in desorption) as well as good recyclability.

Separation of Xe from Kr with Record Selectivity and Productivity in Anion-Pillared Ultramicroporous Materials by Inverse Size-Sieving.

The separation of xenon/krypton (Xe/Kr) mixture is of great importance to industry, but the available porous materials allow the adsorption of both, Xe and Kr only with limited selectivity. Herein we report an anion-pillared ultramicroporous material NbOFFIVE-2-Cu-i (ZU-62) with finely tuned pore aperture size and structure flexibility, which for the first time enables an inverse size-sieving effect in separation along with record Xe/Kr selectivity and ultrahigh Xe capacity. Evidenced by single-crystal X-ray diffraction, the rotation of anions and pyridine rings upon contact of larger-size Xe atoms adapts cavities to the shape/size of Xe and allows strong host-Xe interaction, while the smaller-size Kr is excluded. Breakthrough experiments confirmed that ZU-62 has a real practical potential for producing high-purity Kr and Xe from air-separation byproducts, showing record Kr productivity (206 mL g-1 ) and Xe productivity (42 mL g-1 , in desorption) as well as good recyclability.

Mixed donor, phenanthroline photoactive MOFs with favourable CO2 selectivity.

Mixed donor phenanthroline-carboxylate linkers were combined with MnII or ZnII to form photoactive MOFs with large pore apertures. The MOFs display high CO2 adsorption capacities, which consequently causes structural framework flexibility, and align with favorable metrics for selective CO2 capture. The photophysical properties of the MOFs were investigated, with the MnII MOF giving rise to short triplet LMCT lifetimes.

Quantum sieving of H2/D2 in MOFs: a study on the correlation between the separation performance, pore size and temperature

In quantum sieving of H2/D2, a local optimal operational temperature domain is dominant at local temperatures for specific pore apertures.