Exhaled Anesthetic Xenon Regeneration by Gas Separation Using a Metal-Organic Framework with Sorbent-Sorbate Induced-Fit.

Noble gas xenon (Xe) is an excellent anesthetic gas, but its rarity, high cost and constrained production prohibits wide use in medicine. Here, we have developed a closed-circuit anesthetic Xe recovery and reusage process with highly effective CO2-specific adsorbent CUPMOF-5 that is promising to solve the anesthetic Xe supply problem. CUPMOF-5 possesses spacious cage cavities interconnected in four directions by confinement throat apertures of ~3.4 Å, which makes it an ideal molecular sieving of CO2 from Xe, O2, N2 with the benchmark selectivity and high uptake capacity of CO2. In situ single-crystal X-ray diffraction (SCXRD) and computational simulation solidly revealed the vital sieving role of the confined throat and the sorbent-sorbate induced-fit strengthening binding interaction to CO2. CUPMOF-5 can remove 5 % CO2 even from actual moist exhaled anesthetic gases, and achieves the highest Xe recovery rate (99.8 %) so far, as verified by breakthrough experiments. This endows CUPMOF-5 great potential for the on-line CO2 removal and Xe recovery from anesthetic closed-circuits.

Insight into the Gas-Induced Phase Transformations in a 2D Switching Coordination Network via Coincident Gas Sorption and In Situ PXRD.

Switching coordination networks (CNs) that reversibly transform between narrow or closed pore (cp) and large pore (lp) phases, though fewer than their rigid counterparts, offer opportunities for sorption-related applications. However, their structural transformations and switching mechanisms remain underexplored at the molecular level. In this study, we conducted a systematic investigation into a 2D switching CN, [Ni(bpy)2(NCS)2]n, sql-1-Ni-NCS (1 = bpy = 4,4'-bipyridine), using coincident gas sorption and in situ powder X-ray diffraction (PXRD) under low-temperature conditions. Gas adsorption measurements revealed that C2H4 (169 K) and C2H6 (185 K) exhibited single-step type F-IVs sorption isotherms with sorption uptakes of around 180-185 cm3 g-1, equivalent to four sorbate molecules per formula unit. Furthermore, parallel in situ PXRD experiments provided insight into sorbate-dependent phase switching during the sorption process. Specifically, CO2 sorption induced single-step phase switching (path I) solely between cp and lp phases consistent with the observed single-step type F-IVs sorption isotherm. By contrast, intermediate pore (ip) phases emerged during C2H4 and C2H6 desorption as well as C3H6 adsorption, although they remained undetectable in the sorption isotherms. To our knowledge, such a cp-lp-ip-cp transformation (path II) induced by C2H4/6 and accompanied by single-step type F-IVs sorption isotherms represents a novel type of phase transition mechanism in switching CNs. By virtue of Rietveld refinements and molecular simulations, we elucidated that the phase transformations are governed by cooperative local and global structural changes involving NCS- ligand reorientation, bpy ligand twist and rotation, cavity edge (Ni-bpy-Ni) deformation, and interlayer expansion and sliding.

Ethane/Ethylene Separations in Flexible Diamondoid Coordination Networks via an Ethane-Induced Gate-Opening Mechanism.

Separating ethane (C2H6) from ethylene (C2H4) is an essential and energy-intensive process in the chemical industry. Here, we report two flexible diamondoid coordination networks, X-dia-1-Ni and X-dia-1-Ni0.89Co0.11, that exhibit gate-opening between narrow-pore (NP) and large-pore (LP) phases for C2H6, but not for C2H4. X-dia-1-Ni0.89Co0.11 thereby exhibited a type F-IV isotherm at 273 K with no C2H6 uptake and a high uptake (111 cm3 g-1, 1 atm) for the NP and LP phases, respectively. Conversely, the LP phase exhibited a low uptake of C2H4 (12.2 cm3 g-1). This C2H6/C2H4 uptake ratio of 9.1 for X-dia-1-Ni0.89Co0.11 far surpassed those of previously reported physisorbents, many of which are C2H4-selective. In situ variable-pressure X-ray diffraction and modeling studies provided insight into the abrupt C2H6-induced structural NP to LP transformation. The promise of pure gas isotherms and, more generally, flexible coordination networks for gas separations was validated by dynamic breakthrough studies, which afforded high-purity (99.9%) C2H4 in one step.

Ultramicroporous Lonsdaleite Topology MOF with High Propane Uptake and Propane/Methane Selectivity for Propane Capture from Simulated Natural Gas.

Propane (C3H8) is a widely used fuel gas. Metal-organic framework (MOF) physisorbents that are C3H8 selective offer the potential to significantly reduce the energy footprint for capturing C3H8 from natural gas, where C3H8 is typically present as a minor component. Here we report the C3H8 recovery performance of a previously unreported lonsdaleite, lon, topology MOF, a chiral metal-organic material, [Ni(S-IEDC)(bipy)(SCN)]n, CMOM-7. CMOM-7 was prepared from three low-cost precursors: Ni(SCN)2, S-indoline-2-carboxylic acid (S-IDECH), and 4,4'-bipyridine (bipy), and its structure was determined by single crystal X-ray crystallography. Pure gas adsorption isotherms revealed that CMOM-7 exhibited high C3H8 uptake (2.71 mmol g-1) at 0.05 bar, an indication of a higher affinity for C3H8 than both C2H6 and CH4. Dynamic column breakthrough experiments afforded high purity C3H8 capture from a gas mixture comprising C3H8/C2H6/CH4 (v/v/v = 5/10/85). Despite the dilute C3H8 stream, CMOM-7 registered a high dynamic uptake of C3H8 and a breakthrough time difference between C3H8 and C2H6 of 79.5 min g-1, superior to those of previous MOF physisorbents studied under the same flow rate. Analysis of crystallographic data and Grand Canonical Monte Carlo simulations provides insight into the two C3H8 binding sites in CMOM-7, both of which are driven by C-H···π and hydrogen bonding interactions.

Supramolecular isomerism and structural flexibility in coordination networks sustained by cadmium rod building blocks.

Bifunctional N-donor carboxylate linkers generally afford dia and sql topology coordination networks of general formula ML2 that are based upon the MN2(CO2)2 molecular building block (MBB). Herein, we report on a new N-donor carboxylate linker, ß-(3,4-pyridinedicarboximido)propionate (PyImPr), which afforded Cd(PyImPr)2via reaction of PyImPrH with Cd(acetate)2·2H2O. We observed that, depending upon whether Cd(PyImPr)2 was prepared by layering or solvothermal methods, 2D or 3D supramolecular isomers, respectively, of Cd(PyImPr)2 were isolated. Single crystal X-ray diffraction studies revealed that both supramolecular isomers are comprised of the same carboxylate bridged rod building block, RBB. We were interested to determine if the ethylene moiety of PyImPr could enable structural flexibility. Indeed, open-to-closed structural transformations occurred upon solvent removal for both phases, but they were found to be irreversible. A survey of the Cambridge Structural Database (CSD) was conducted to analyse the relative frequency of RBB topologies in related ML2 coordination networks in order to provide insight from a crystal engineering perspective.

Water vapour and gas induced phase transformations in an 8-fold interpenetrated diamondoid metal-organic framework.

In this work, we report the synthesis, structural characterisation and sorption properties of an 8-fold interpenetrated diamondoid (dia) metal-organic framework (MOF) that is sustained by a new extended linker ligand, [Cd(Imibz)2], X-dia-2-Cd, HImibz or 2 = 4-((4-(1H-imidazol-1-yl)phenylimino)methyl)benzoic acid. X-dia-2-Cd was found to exhibit reversible single-crystal-to-single-crystal (SC-SC) transformations between four distinct phases: an as-synthesised (from N,N-dimethylformamide) wide-pore phase, X-dia-2-Cd-α; a narrow-pore phase, X-dia-2-Cd-ß, formed upon exposure to water; a narrow-pore phase obtained by activation, X-dia-2-Cd-γ; a medium-pore CO2-loaded phase X-dia-2-Cd-δ. While the space group remained constant in the four phases, the cell volumes and calculated void space ranged from 4988.7 Å3 and 47% (X-dia-2-Cd-α), respectively, to 3200.8 Å3 and 9.1% (X-dia-2-Cd-γ), respectively. X-dia-2-Cd-γ also exhibited a water vapour-induced structural transformation to the water-loaded X-dia-2-Cd-ß phase, resulting in an S-shaped sorption isotherm. The inflection point occurred at 18% RH with negligible hysteresis on the desorption profile. Water vapour temperature-humidity swing cycling (60% RH, 300 K to 0% RH, 333 K) indicated hydrolytic stability of X-dia-2-Cd and working capacity was retained after 128 cycles of sorbent regeneration. CO2 (at 195 K) was also observed to induce a structural transformation in X-dia-2-Cd-γ and in situ PXRD studies at 1 bar of CO2, 195 K revealed the formation of X-dia-2-Cd-δ, which exhibited 31% larger unit cell volume than X-dia-2-Cd-γ.

One Atom Can Make All the Difference: Gas-Induced Phase Transformations in Bisimidazole-Linked Diamondoid Coordination Networks.

Coordination networks (CNs) that undergo gas-induced transformation from closed (nonporous) to open (porous) structures are of potential utility in gas storage applications, but their development is hindered by limited control over their switching mechanisms and pressures. In this work, we report two CNs, [Co(bimpy)(bdc)]n (X-dia-4-Co) and [Co(bimbz)(bdc)]n (X-dia-5-Co) (H2bdc = 1,4-benzendicarboxylic acid; bimpy = 2,5-bis(1H-imidazole-1-yl)pyridine; bimbz = 1,4-bis(1H-imidazole-1-yl)benzene), that both undergo transformation from closed to isostructural open phases involving at least a 27% increase in cell volume. Although X-dia-4-Co and X-dia-5-Co only differ from one another by one atom in their N-donor linkers (bimpy = pyridine, and bimbz = benzene), this results in different pore chemistry and switching mechanisms. Specifically, X-dia-4-Co exhibited a gradual phase transformation with a steady increase in the uptake when exposed to CO2, whereas X-dia-5-Co exhibited a sharp step (type F-IV isotherm) at P/P0 ≈ 0.008 or P ≈ 3 bar (195 or 298 K, respectively). Single-crystal X-ray diffraction, in situ powder XRD, in situ IR, and modeling (density functional theory calculations, and canonical Monte Carlo simulations) studies provide insights into the nature of the switching mechanisms and enable attribution of pronounced differences in sorption properties to the changed pore chemistry.

Structural Phase Transformations Induced by Guest Molecules in a Nickel-Based 2D Square Lattice Coordination Network.

Herein, we report the crystal structure and guest binding properties of a new two-dimensional (2D) square lattice (sql) topology coordination network, sql-(azpy)(pdia)-Ni, which is comprised of two linker ligands with diazene (azo) moieties, (E)-1,2-di(pyridin-4-yl)diazene(azpy) and (E)-5-(phenyldiazenyl)isophthallate(pdia). sql-(azpy)(pdia)-Ni underwent guest-induced switching between a closed (nonporous) ß phase and several open (porous) α phases, but unlike the clay-like layer expansion to distinct phases previously reported in switching sql networks, a continuum of phases was formed. In effect, sql-(azpy)(pdia)-Ni exhibited elastic-like properties induced by adaptive guest binding. Single-crystal X-ray diffraction (SCXRD) studies of the α phases revealed that the structural transformations were enabled by the pendant phenyldiazenyl moiety on the pdia2- ligand. This moiety functioned as a type of hinge to enable parallel slippage of layers and interlayer expansion for the following guests: N,N-dimethylformamide, water, dichloromethane, para-xylene, and ethylbenzene. The slippage angle (interplanar distances) ranged from 54.133° (4.442 Å) in the ß phase to 69.497° (5.492 Å) in the ethylbenzene-included phase. Insight into the accompanying phase transformations was also gained from variable temperature powder XRD studies. Dynamic water vapor sorption studies revealed a stepped isotherm with little hysteresis that was reversible for at least 100 cycles. The isotherm step occurred at ca. 50% relative humidity (RH), the optimal RH value for humidity control.

Pillar Modularity in fsc Topology Hybrid Ultramicroporous Materials Based upon Tetra(4-pyridyl)benzene.

Hybrid ultramicroporous materials (HUMs) are porous coordination networks composed of combinations of organic and inorganic linker ligands with a pore diameter of <7 Å. Despite their benchmark gas sorption selectivity for several industrially relevant gas separations and their inherent modularity, the structural and compositional diversity of HUMs remains underexplored. In this contribution, we report a family of six HUMs (SIFSIX-22-Zn, TIFSIX-6-Zn, SNFSIX-2-Zn, GEFSIX-4-Zn, ZRFSIX-3-Zn, and TAFSEVEN-1-Zn) based on Zn metal centers and the tetratopic N-donor organic ligand tetra(4-pyridyl)benzene (tepb). The incorporation of fluorinated inorganic pillars (SiF6 2-, TiF6 2-, SnF6 2-, GeF6 2-, ZrF6 2-, and TaF7 2-, respectively) resulted in (4,6)-connected fsc topology as verified using single-crystal X-ray diffraction. Pure-component gas sorption studies with N2, CO2, C2H2, C2H4, and C2H6 revealed that the large voids and narrow pore windows common to all six HUMs can be leveraged to afford high C2H2 uptakes while retaining high ideal adsorbed solution theory (IAST) selectivities for industrially relevant gas mixtures: >10 for 1:99 C2H2/C2H4 and >5 for 1:1 C2H2/CO2. The approach taken, systematic variation of pillars with retention of structure, enables differences in selectivity to be attributed directly to the choice of the inorganic pillar. This study introduces fsc topology HUMs as a modular platform that is amenable to fine-tuning of structure and properties.

Trace removal of benzene vapour using double-walled metal-dipyrazolate frameworks.

In principle, porous physisorbents are attractive candidates for the removal of volatile organic compounds such as benzene by virtue of their low energy for the capture and release of this pollutant. Unfortunately, many physisorbents exhibit weak sorbate-sorbent interactions, resulting in poor selectivity and low uptake when volatile organic compounds are present at trace concentrations. Herein, we report that a family of double-walled metal-dipyrazolate frameworks, BUT-53 to BUT-58, exhibit benzene uptakes at 298 K of 2.47-3.28 mmol g-1 at <10 Pa. Breakthrough experiments revealed that BUT-55, a supramolecular isomer of the metal-organic framework Co(BDP) (H2BDP = 1,4-di(1H-pyrazol-4-yl)benzene), captures trace levels of benzene, producing an air stream with benzene content below acceptable limits. Furthermore, BUT-55 can be regenerated with mild heating. Insight into the performance of BUT-55 comes from the crystal structure of the benzene-loaded phase (C6H6@BUT-55) and density functional theory calculations, which reveal that C-H···X interactions drive the tight binding of benzene. Our results demonstrate that BUT-55 is a recyclable physisorbent that exhibits high affinity and adsorption capacity towards benzene, making it a candidate for environmental remediation of benzene-contaminated gas mixtures.

Improving Ethane/Ethylene Separation Performance under Humid Conditions by Spatially Modified Zeolitic Imidazolate Frameworks.

Gas separation performances are usually degraded under humid conditions for many crystalline porous materials because of the lack of water stability and/or the competition of water vapor toward the interaction sites (e.g., open metal sites). Zeolitic imidazolate frameworks (ZIFs) are suitable candidates for practical applications in gas separation because of their excellent physical/chemical stabilities. However, the limitation of substituent positions in common ZIFs has prevented extensive pore engineering to improve their separation performance. In a type of gyroidal ZIFs with gie topology, the Schiff base moiety provides additional substituent positions, making it possible to modify the spatial arrangement of hydrophobic methyl groups. Herein, a new gyroidal ZIF, ZnBAIm (H2BAIm = 1,2-bis(1-(1H-imidazol-4-yl)ethylidene)hydrazine), is designed, synthesized, and characterized. The spatially modified ZnBAIm exhibits improved thermal/chemical/mechanical stabilities compared to ZnBIm (H2BIm = 1,2-bis((5H-imidazol-4-yl)methylene)hydrazine). ZnBAIm can remain intact up to about 480 °C in a N2 atmosphere and tolerate harsh treatments (e.g., 5 M NaOH aqueous solution at room temperature for 24 h and 190 MPa high pressure in the presence of water). Moreover, the modified pore and window sizes have improved significantly the ethane/ethylene selectivity and separation performance under humid conditions for ZnBAIm. Breakthrough experiments demonstrate efficient separation of a C2H6/C2H4 (50/50, v/v) binary gas mixture under ambient conditions; more importantly, the C2H6/C2H4 separation performance is unaffected under highly humid conditions (up to 80% RH). The separation performance is attributed to combined thermodynamic (stronger dispersion interaction with C2H6 than with C2H4) and kinetic factors (diffusion), determined by density functional theory calculations and kinetic adsorption study, respectively.

Breaking the trade-off between selectivity and adsorption capacity for gas separation.

The trade-off between selectivity and adsorption capacity with porous materials is a major roadblock to reducing the energy footprint of gas separation technologies. To address this matter, we report herein a systematic crystal engineering study of C2H2 removal from CO2 in a family of hybrid ultramicroporous materials (HUMs). The HUMs are composed of the same organic linker ligand, 4-(3,5-dimethyl-1H-pyrazol-4-yl)pyridine, pypz, three inorganic pillar ligands, and two metal cations, thereby affording six isostructural pcu topology HUMs. All six HUMs exhibited strong binding sites for C2H2 and weaker affinity for CO2. The tuning of pore size and chemistry enabled by crystal engineering resulted in benchmark C2H2/CO2 separation performance. Fixed-bed dynamic column breakthrough experiments for an equimolar (v/v = 1:1) C2H2/CO2 binary gas mixture revealed that one sorbent, SIFSIX-21-Ni, was the first C2H2 selective sorbent that combines exceptional separation selectivity (27.7) with high adsorption capacity (4 mmol·g-1).

One-step ethylene production from a four-component gas mixture by a single physisorbent.

One-step adsorptive purification of ethylene (C2H4) from four-component gas mixtures comprising acetylene (C2H2), ethylene (C2H4), ethane (C2H6) and carbon dioxide (CO2) is an unmet challenge in the area of commodity purification. Herein, we report that the ultramicroporous sorbent Zn-atz-oba (H2oba = 4,4-dicarboxyl diphenyl ether; Hatz = 3-amino-1,2,4-triazole) enables selective adsorption of C2H2, C2H6 and CO2 over C2H4 thanks to the binding sites that lie in its undulating pores. Molecular simulations provide insight into the binding sites in Zn-atz-oba that are responsible for coadsorption of C2H2, C2H6 and CO2 over C2H4. Dynamic breakthrough experiments demonstrate that the selective binding exhibited by Zn-atz-oba can produce polymer-grade purity (>99.95%) C2H4 from binary (1:1 for C2H4/C2H6), ternary (1:1:1 for C2H2/C2H4/C2H6) and quaternary (1:1:1:1 for C2H2/C2H4/C2H6/CO2) gas mixtures in a single step.

Scalable Room-Temperature Synthesis of Highly Robust Ethane-Selective Metal-Organic Frameworks for Efficient Ethylene Purification.

The development of new techniques and materials that can separate ethylene from ethane is highly relevant in modern applications. Although adsorption-based separation techniques using metal-organic frameworks (MOFs) have gained increasing attention, the relatively low stability (especially water resistance) and unscalable synthesis of MOFs severely limit their application in real industrial scenarios. Addressing these challenges, we rationally designed and synthesized two new C2H6-selective MOF adsorbents (NKMOF-8-Br and -Me) with ultrahigh chemical and thermal stability, including water resistance. Attributed to the nonpolar/hydrophobic pore environments and appropriate pore apertures, the MOFs can capture C2 hydrocarbon gases at ambient conditions even in high humidity. The single-crystal structures of gas@NKMOF-8 realized the direct visualization of adsorption sites of the gases. Both the single-crystal data and simulated data elucidate the mechanism of selective adsorption. Moreover, the NKMOF-8 possesses high C2H6 adsorption capacity and high selectivity, allowing for efficient C2H6/C2H4 separation, as verified by experimental breakthrough tests. Most importantly, NKMOF-8-Br and -Me can be scalably synthesized through stirring at room temperature in minutes, which confers them with great potential for industrial application. This work offers new adsorbents that can address major chemical industrial challenges and provides an in-depth understanding of the gas binding sites in a visual manner.

Amino-Functionalised Hybrid Ultramicroporous Materials that Enable Single-Step Ethylene Purification from a Ternary Mixture.

Pyrazine-linked hybrid ultramicroporous (pore size <7 Å) materials (HUMs) offer benchmark performance for trace carbon capture thanks to strong selectivity for CO2 over small gas molecules, including light hydrocarbons. That the prototypal pyrazine-linked HUMs are amenable to crystal engineering has enabled second generation HUMs to supersede the performance of the parent HUM, SIFSIX-3-Zn, mainly through substitution of the metal and/or the inorganic pillar. Herein, we report that two isostructural aminopyrazine-linked HUMs, MFSIX-17-Ni (17=aminopyrazine; M=Si, Ti), which we had anticipated would offer even stronger affinity for CO2 than their pyrazine analogs, unexpectedly exhibit reduced CO2 affinity but enhanced C2 H2 affinity. MFSIX-17-Ni are consequently the first physisorbents that enable single-step production of polymer-grade ethylene (>99.95 % for SIFSIX-17-Ni) from a ternary equimolar mixture of ethylene, acetylene and CO2 thanks to coadsorption of the latter two gases. We attribute this performance to the very different binding sites in MFSIX-17-Ni versus SIFSIX-3-Zn.

Pore Engineering for One-Step Ethylene Purification from a Three-Component Hydrocarbon Mixture.

Ethylene production from C2 hydrocarbon mixtures through one separation step is desirable but challenging because of the similar size and physical properties of acetylene, ethylene, and ethane. Herein, we report three new isostructural porous coordination networks (NPU-1, NPU-2, NPU-3; NPU represents Northwestern Polytechnical University) that are sustained by 9-connected nodes based upon a hexanuclear metal cluster of composition [Mn6(µ3-O)2(CH3COO)3]6+. NPU-1/2/3 exhibit a dual cage structure that was systematically fine-tuned in terms of cage size to realize selective adsorption of C2H2 and C2H6 over C2H4. Dynamic breakthrough experiments demonstrated that NPU-1 produces ethylene in >99.9% purity from a three-component gas mixture (1:1:1 C2H2/C2H4/C2H6). Molecular modeling studies revealed that the dual adsorption preference for C2H2 and C2H6 over C2H4 originates from (a) strong hydrogen-bonding interactions between electronegative carboxylate O atoms and C2H2 molecules in one cage and (b) multiple non-covalent interactions between the organic linkers of the host network and C2H6 molecules in the second cage.

Metal-Organic Material Polymer Coatings for Enhanced Gas Sorption Performance and Hydrolytic Stability under Humid Conditions.

Physisorbent metal-organic materials (MOMs) have shown benchmark performance for highly selective CO2 capture from bulk and trace gas mixtures. However, gas stream moisture can be detrimental to both adsorbent performance and hydrolytic stability. One of the most effective methods to solve this issue is to transform the adsorbent surface from hydrophilic to hydrophobic. Herein, we present a facile approach for coating MOMs with organic polymers to afford improved hydrophobicity and hydrolytic stability under humid conditions. The impact of gas stream moisture on CO2 capture for the composite materials was found to be negligible under both bulk and trace CO2 capture conditions with significant improvements in regeneration times and energy requirements.

Fabrication of Large Single Crystals for Platinum-Based Linear Polymers with Controlled-Release and Photoactuator Performance.

Preparation of large single crystals of linear polymers for X-ray analysis is very challenging. Herein, we employ a coordination-driven self-assembly strategy to secure the appropriate head-to-tail alignment of anthracene moieties, and for the first time obtained large-sized Pt-based linear polymer crystals through a [4+4] cycloaddition of anthracene in a single-crystal to single-crystal fashion. Using X-ray diffraction to determine the polymer crystal structure, we found that both the polymerisation and depolymerisation steps proceed via a stable intermediate. Taking advantage of the temperature-dependent slow depolymerization, the Pt-based linear polymer showed potential as a sustained release anticancer drug platform. Utilizing the reversible contraction effect of unit-cell volume upon irradiation or heating, the stimuli-responsive crystals were hybridized with polyvinylidene fluoride to obtain a "smart material" with outstanding photoactuator performance.

Synergistic sorbent separation for one-step ethylene purification from a four-component mixture.

Purification of ethylene (C2H4), the largest-volume product of the chemical industry, currently involves energy-intensive processes such as chemisorption (CO2 removal), catalytic hydrogenation (C2H2 conversion), and cryogenic distillation (C2H6 separation). Although advanced physisorbent or membrane separation could lower the energy input, one-step removal of multiple impurities, especially trace impurities, has not been feasible. We introduce a synergistic sorbent separation method for the one-step production of polymer-grade C2H4 from ternary (C2H2/C2H6/C2H4) or quaternary (CO2/C2H2/C2H6/C2H4) gas mixtures with a series of physisorbents in a packed-bed geometry. We synthesized ultraselective microporous metal-organic materials that were readily regenerated, including one that was selective for C2H6 over CO2, C2H2, and C2H4.

Soft Porous Crystal Based upon Organic Cages That Exhibit Guest-Induced Breathing and Selective Gas Separation.

Soft porous crystals (SPCs) that exhibit stimuli-responsive dynamic sorption behavior are attracting interest for gas storage/separation applications. However, the design and synthesis of SPCs is challenging. Herein, we report a new type of SPC based on a [2 + 3] imide-based organic cage (NKPOC-1) and find that it exhibits guest-induced breathing behavior. Various gases were found to induce activated NKPOC-1 crystals to reversibly switch from a "closed" nonporous phase (α) to two porous "open" phases (ß and γ). The net effect is gate-opening behavior induced by CO2 and C3 hydrocarbons. Interestingly, NKPOC-1-α selectively adsorbs propyne over propylene and propane under ambient conditions. Thus, NKPOC-1-α has the potential to separate binary and ternary C3 hydrocarbon mixtures, and the performance was subsequently verified by fixed bed column breakthrough experiments. In addition, molecular dynamics calculations and in situ X-ray diffraction experiments indicate that the gate-opening effect is accompanied by reversible structural transformations. The adsorption energies from molecular dynamics simulations aid are consistent with the experimentally observed selective adsorption phenomena. The understanding gained from this study of NKPOC-1 supports the further development of SPCs for applications in gas separation/storage because SPCs do not inherently suffer from the recyclability problems often encountered with rigid materials.