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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.
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Introducing dynamic behavior into periodic frameworks has borne fruit in the form of flexible porous crystals. The detailed molecular design of frameworks in order to control their collective dynamics is of particular interest, for example, to achieve stimulus-induced behavior. Herein, by varying the degree of rigidity of ditopic pillar linkers, two isostructural flexible metal-organic frameworks (MOFs) with common rigid supermolecular building bilayers were constructed. The subtle substitution of single (in bibenzyl-4,4'-dicarboxylic acid; H2BBDC) with double (in 4,4'-stilbenedicarboxylic acid; H2SDC) C-C bonds in pillared linkers led to markedly different flexible behavior of these two MOFs. Upon the removal of guest molecules, both frameworks clearly show reversible single-crystal-to-single-crystal transformations involving the cis-trans conformation change and a resulting swing of the corresponding pillar linkers, which gives rise to Flex-Cd-MOF-1a and Flex-Cd-MOF-2a, respectively. Strikingly, a more favorable gas-induced dynamic behavior in Flex-Cd-MOF-2a was verified in detail by stepwise C3H6/C3H8 sorption isotherms and the corresponding in situ powder X-ray diffraction experiments. These insights are strongly supported by molecular modeling studies on the sorption mechanism that explores the sorption landscape. Furthermore, a consistency between the macroscopic elasticity and microscopic flexibility of Flex-Cd-MOF-2 was observed. This work fuels a growing interest in developing MOFs with desired chemomechanical functions and presents detailed insights into the origins of flexible MOFs.
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The efficient single-step purification of ethylene from ternary C2 mixtures containing ethane and acetylene is challenging and demanding. Herein, we introduce a novel cerium-based metal-organic framework (MOF) of Ce-NTB-rtk synthesized via a ligand-conformer strategy. The Ce-NTB-rtk features a rare tetranuclear cerium cluster and 2D kgd layers pillared by a 3D rtl framework concomitant with an extraordinary (3,3,12)-c network. The compound encompasses microporous cavities replete with a nonpolar microenvironment. Gas sorption and breakthrough experiments demonstrate its superior affinity for C2H6 and C2H2 over C2H4, enabling effective single-step ethylene purification. Computational simulations reveal that preferential adsorptions are facilitated by different interaction strengths of C-H···O hydrogen bonds. The performance of Ce-NTB-rtk in separation selectivity and regeneration capacity makes it a promising candidate for sustainable and cost-effective ethylene purification, showcasing the potential of MOFs in advanced gas separation applications.
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An emerging strategy in the design of efficient gas storage technologies is the development of stimuli-responsive physisorbents which undergo transformations in response to a particular stimulus, such as pressure, heat or light. Herein, we report two isostructural light modulated adsorbents (LMAs) containing bis-3-thienylcyclopentene (BTCP), LMA-1 [Cd(BTCP)(DPT)2 ] (DPT=2,5-diphenylbenzene-1,4-dicarboxylate) and LMA-2 [Cd(BTCP)(FDPT)2 ] (FDPT=5-fluoro-2,diphenylbenzene-1,4-dicarboxylate). Both LMAs undergo pressure induced switching transformations from non-porous to porous via adsorption of N2 , CO2 and C2 H2 . LMA-1 exhibited multi-step adsorption while LMA-2 showed a single-step adsorption isotherm. The light responsive nature of the BTPC ligand in both frameworks was exploited with irradiation of LMA-1 resulting in a 55 % maximum reduction of CO2 uptake at 298â K. This study reports the first example of a switching sorbent (closed to open) that can be further modulated by light.
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The removal of carbon dioxide (CO2) from acetylene (C2H2) is a critical industrial process for manufacturing high-purity C2H2. However, it remains challenging to address the tradeoff between adsorption capacity and selectivity, on account of their similar physical properties and molecular sizes. To overcome this difficulty, here we report a novel strategy involving the regulation of a hydrogen-bonding nanotrap on the pore surface to promote the separation of C2H2/CO2 mixtures in three isostructural metal-organic frameworks (MOFs, named MIL-160, CAU-10H, and CAU-23, respectively). Among them, MIL-160, which has abundant hydrogen-bonding acceptors as nanotraps, can selectively capture acetylene molecules and demonstrates an ultrahigh C2H2 storage capacity (191 cm3 g-1, or 213 cm3 cm-3) but much less CO2 uptake (90 cm3 g-1) under ambient conditions. The C2H2 adsorption amount of MIL-160 is remarkably higher than those for the other two isostructural MOFs (86 and 119 cm3 g-1 for CAU-10H and CAU-23, respectively) under the same conditions. More importantly, both simulation and experimental breakthrough results show that MIL-160 sets a new benchmark for equimolar C2H2/CO2 separation in terms of the separation potential (Δqbreak = 5.02 mol/kg) and C2H2 productivity (6.8 mol/kg). In addition, in situ FT-IR experiments and computational modeling further reveal that the unique host-guest multiple hydrogen-bonding interaction between the nanotrap and C2H2 is the key factor for achieving the extraordinary acetylene storage capacity and superior C2H2/CO2 selectivity. This work provides a novel and powerful approach to address the tradeoff of this extremely challenging gas separation.
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The capture of the xenon and krypton from nuclear reprocessing off-gas is essential to the treatment of radioactive waste. Although various porous materials have been employed to capture Xe and Kr, the development of high-performance adsorbents capable of trapping Xe/Kr at very low partial pressure as in the nuclear reprocessing off-gas conditions remains challenging. Herein, we report a self-adjusting metal-organic framework based on multiple weak binding interactions to capture trace Xe and Kr from the nuclear reprocessing off-gas. The self-adjusting behavior of ATC-Cu and its mechanism have been visualized by the in-situ single-crystal X-ray diffraction studies and theoretical calculations. The self-adjusting behavior endows ATC-Cu unprecedented uptake capacities of 2.65 and 0.52â mmol g-1 for Xe and Kr respectively at 0.1â bar and 298â K, as well as the record Xe capture capability from the nuclear reprocessing off-gas. Our work not only provides a benchmark Xe adsorbent but proposes a new route to construct smart materials for efficient separations.
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Reticular chemistry and methane storage materials have been predominately focused on finite metal-cluster-based metal-organic frameworks (MOFs). In contrast, MOFs constructed from infinite rod secondary building units (SBUs), i.e., rod MOFs, are less developed, and the existing ones are typically built from simple one-way helical, zigzag, or (mixed)polyhedron SBUs. Herein, inspired by a recent unveiled structure of Zn6(H2O)3(BTP)4 and by means of an amide-functionalized preliminary single tricarboxylate, a subsequent mixed tricarboxylate, and dicarboxylate linkers, an intricate three-way rod MOF and the next three isoreticular three-way rod MOFs have been successfully realized, namely, 3W-ROD-1 and 3W-ROD-2-X (X = -OH, -F, and -CH3), respectively. The structural analyses disclosed that the four compounds were constructed from unprecedented three-way invariant nonintersecting trigonal rod-packing SBUs cross-linked via the noncovalent-interaction-driven self-assembly of pseudo hexacarboxylates with the original tricarboxylate or different functional ditopic linkers, resulting in cage-like pore geometries accessible via ultramicroporous apertures concomitant with the complex topology transitivity, namely, 18 42 and 18 44. Sorption studies show that the apparent surface areas of these materials are among the most highly porous materials for rod MOFs. Due to the presence of favorable pocket sites created by X, ketone, and proximal amide groups as revealed by Monte Carlo molecular dynamics (MCMD) computational calculations, the MOFs exhibit impressive methane storage working capacities, outperforming the well-known rod Ni-MOF-74 and representing the highest values among rigid rod MOFs.
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A combined experimental and theoretical study of C2H2 and CO2 adsorption and separation was performed in two isostructural molecular porous materials (MPMs): MPM-1-Cl ([Cu2(adenine)4Cl2]Cl2) and MPM-1-TIFSIX ([Cu2(adenine)4(TiF6)2]). It was revealed that MPM-1-Cl displayed higher low-pressure uptake, isosteric heat of adsorption (Qst), and selectivity for C2H2 than CO2, whereas the opposite was observed for MPM-1-TIFSIX. While MPM-1-Cl contains only one type of accessible channel, which has a greater preference toward C2H2, MPM-1-TIFSIX contains three distinct accessible channels, one of which is a confined region between two large channels that represents the primary binding site for both adsorbates. According to molecular simulations, the initial adsorption site in MPM-1-TIFSIX interacts more strongly with CO2 than C2H2, thus explaining the inversion of adsorbate selectivity relative to MPM-1-Cl.
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Pyrazine-linked hybrid ultramicroporous (pore size <7â 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.
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Porous materials with open metal sites have been investigated to separate various gas mixtures. However, open metal sites show the limitation in the separation of some challenging gas mixtures, such as C2 H2 /CO2 . Herein, we propose a new type of ultra-strong C2 H2 nano-trap based on multiple binding interactions to efficiently capture C2 H2 molecules and separate C2 H2 /CO2 mixture. The ultra-strong acetylene nano-trap shows a benchmark Qst of 79.1â kJ mol-1 for C2 H2 , a record high pure C2 H2 uptake of 2.54â mmol g-1 at 1×10-2 â bar, and the highest C2 H2 /CO2 selectivity (53.6), making it as a new benchmark material for the capture of C2 H2 and the separation of C2 H2 /CO2 . The locations of C2 H2 molecules within the MOF-based nanotrap have been visualized by the in situ single-crystal X-ray diffraction studies, which also identify the multiple binding sites accountable for the strong interactions with C2 H2 .
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Structural changes at the active site of an enzyme induced by binding to a substrate molecule can result in enhanced activity in biological systems. Herein, we report that the new hybrid ultramicroporous material sql-SIFSIX-bpe-Zn exhibits an induced fit binding mechanism when exposed to acetylene, C2 H2 . The resulting phase change affords exceptionally strong C2 H2 binding that in turn enables highly selective C2 H2 /C2 H4 and C2 H2 /CO2 separation demonstrated by dynamic breakthrough experiments. sql-SIFSIX-bpe-Zn was observed to exhibit at least four phases: as-synthesised (α); activated (ß); and C2 H2 induced phases (ß' and γ). sql-SIFSIX-bpe-Zn-ß exhibited strong affinity for C2 H2 at ambient conditions as demonstrated by benchmark isosteric heat of adsorption (Qst ) of 67.5â kJ mol-1 validated through in situ pressure gradient differential scanning calorimetry (PG-DSC). Further, in situ characterisation and DFT calculations provide insight into the mechanism of the C2 H2 induced fit transformation, binding positions and the nature of host-guest and guest-guest interactions.
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Acetylene (C2 H2 ) capture is a step in a number of industrial processes, but it comes with a high-energy footprint. Although physisorbents have the potential to reduce this energy footprint, they are handicapped by generally poor selectivity versus other relevant gases, such as CO2 and C2 H4 . In the case of CO2 , the respective physicochemical properties are so similar that traditional physisorbents, such as zeolites, silica, and activated carbons cannot differentiate well between CO2 and C2 H2 . Herein, we report that a family of three isostructural, ultramicroporous (<7â Å) diamondoid metal-organic frameworks, [Cu(TMBP)X] (TMBP=3,3',5,5'-tetramethyl-4,4'-bipyrazole), TCuX (X=Cl, Br, I), offer new benchmark C2 H2 /CO2 separation selectivity at ambient temperature and pressure. We attribute this performance to a new type of strong binding site for C2 H2 . Specifically, halogenâ â â HC interactions coupled with other noncovalent in a tight binding site is C2 H2 specific versus CO2 . The binding site is distinct from those found in previous benchmark sorbents, which are based on open metal sites or electrostatic interactions enabled by inorganic fluoro or oxo anions.
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The high energy footprint of commodity gas purification and increasing demand for gases require new approaches to gas separation. Kinetic separation of gas mixtures through molecular sieving can enable separation by molecular size or shape exclusion. Physisorbents must exhibit the right pore diameter to enable separation, but the 0.3-0.4â nm range relevant to small gas molecules is hard to control. Herein, dehydration of the ultramicroporous metal-organic framework Ca-trimesate, Ca(HBTC)â H2 O (H3 BTC=trimesic acid), bnn-1-Ca-H2 O, affords a narrow pore variant, Ca(HBTC), bnn-1-Ca. Whereas bnn-1-Ca-H2 O (pore diameter 0.34â nm) exhibits ultra-high CO2 /N2 , CO2 /CH4 , and C2 H2 /C2 H4 binary selectivity, bnn-1-Ca (pore diameter 0.31â nm) offers ideal selectivity for H2 /CO2 and H2 /N2 under cryogenic conditions. Ca-trimesate, the first physisorbent to exhibit H2 sieving under cryogenic conditions, could be a prototype for a general approach to exert precise control over pore diameter in physisorbents.
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Physical adsorption of gas molecules in microporous materials is an exothermic process, with desorption entropy driving a decrease in uptake with temperature. Enhanced gas sorption with increasing temperature is rare in porous materials and is indicative of sorbate initiated structural change. Here, sorption of C2H6, C3H6, and C3H8 in a flexible microporous metal-organic framework (MOF) {Cu(FPBDC)]·DMF}n (NKU-FlexMOF-1) (H2FPBDC = 5-(5-fluoropyridin-3-yl)-1,3-benzenedicarboxylic acid) that increases with rising temperature over a practically useful temperature and pressure range is reported along with other small molecule and hydrocarbon sorption isotherms. Single X-ray diffraction studies, temperature-dependent gas sorption isotherms, in situ and variable temperature powder X-ray diffraction experiments, and electronic structure calculations were performed to characterize the conformation-dependent sorption behavior in NKU-FlexMOF-1. In total, the data supports that the atypical sorption behavior is a result of loading-dependent structural changes in the flexible framework of NKU-FlexMOF-1 induced by sorbate-specific guest-framework interactions. The sorbates cause subtle adaptations of the framework distinct to each sorbate providing an induced-fit separation mechanism to resolve chemically similar hydrocarbons through highly specific sorbate-sorbent interactions. The relevant intermolecular contacts are shown to be predominantly repulsion and dispersion interactions. NKU-FlexMOF-1 is also found to be stable in aqueous solutions including toleration of pH changes. These experiments demonstrate the potential of this flexible microporous MOF for cost and energy efficient industrial hydrocarbon separation and purification processes. The efficacy for the separation of C3H6/C3H8 mixtures is explicitly demonstrated using NKU-FlexMOF-1a (i.e., activated NKU-FlexMOF-1) for a particular useful temperature range.
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In the context of porous crystalline materials toward CO2 separation and capture, a new 2-fold interpenetrated 3D microporous Co-MOF, IITKGP-11 (IITKGP denotes Indian Institute of Technology Kharagpur), has been synthesized consisting of a 1D channel of â¼3.6 × 5.0 Å2 along the [101] direction with a cavity volume of 35.20%. This microporous framework with a BET surface area of 253 m2g-1 shows higher uptake of CO2 (under 1 bar, 3.35 and 2.70 mmol g-1 at 273 and 295 K, respectively), with high separation selectivities for CO2/N2 and CO2/CH4 gas mixtures under ambient conditions as estimated through IAST calculation. Moreover, real time dynamic breakthrough studies reveal the high adsorption selectivity toward CO2 for these binary mixed gases at 295 K and 1 bar. Besides high gas separation selectivity, capacity considerations in mixed gas phases are also important to check the performance of a given adsorbent. CO2 loading amounts in mixed gas phases are quite high as predicted through IAST calculation and experimentally determined from dynamic breakthrough studies. In order to get insight into the phenomena, GCMC simulation was performed demonstrating that the CO2 molecules are electrostatically trapped via interactions between oxygen on CO2 and hydrogen on pyridyl moieties of the spacers.
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The energy costs associated with the separation and purification of industrial commodities, such as gases, fine chemicals and fresh water, currently represent around 15 per cent of global energy production, and the demand for such commodities is projected to triple by 2050 (ref. 1). The challenge of developing effective separation and purification technologies that have much smaller energy footprints is greater for carbon dioxide (CO2) than for other gases; in addition to its involvement in climate change, CO2 is an impurity in natural gas, biogas (natural gas produced from biomass), syngas (CO/H2, the main source of hydrogen in refineries) and many other gas streams. In the context of porous crystalline materials that can exploit both equilibrium and kinetic selectivity, size selectivity and targeted molecular recognition are attractive characteristics for CO2 separation and capture, as exemplified by zeolites 5A and 13X (ref. 2), as well as metal-organic materials (MOMs). Here we report that a crystal engineering or reticular chemistry strategy that controls pore functionality and size in a series of MOMs with coordinately saturated metal centres and periodically arrayed hexafluorosilicate (SiF(2-)(6)) anions enables a 'sweet spot' of kinetics and thermodynamics that offers high volumetric uptake at low CO2 partial pressure (less than 0.15 bar). Most importantly, such MOMs offer an unprecedented CO2 sorption selectivity over N2, H2 and CH4, even in the presence of moisture. These MOMs are therefore relevant to CO2 separation in the context of post-combustion (flue gas, CO2/N2), pre-combustion (shifted synthesis gas stream, CO2/H2) and natural gas upgrading (natural gas clean-up, CO2/CH4).
Assuntos
Dióxido de Carbono/química , Dióxido de Carbono/isolamento & purificação , Adsorção , Biocombustíveis , Cinética , Porosidade , Especificidade por Substrato , TermodinâmicaRESUMO
As a major greenhouse gas, methane, which is directly vented from the coal-mine to the atmosphere, has not yet drawn sufficient attention. To address this problem, we report a methane nano-trap that features oppositely adjacent open metal sites and dense alkyl groups in a metal-organic framework (MOF). The alkyl MOF-based methane nano-trap exhibits a record-high methane uptake and CH4 /N2 selectivity at 298â K and 1â bar. The methane molecules trapped within the alkyl MOF were crystalographically identified by single-crystal X-ray diffraction experiments, which in combination with molecular simulation studies unveiled the methane adsorption mechanism within the MOF-based nano-trap. The IAST calculations and the breakthrough experiments revealed that the alkyl MOF-based methane nano-trap is a new benchmark for CH4 /N2 separation, thereby providing a new perspective for capturing methane from coal-mine methane to recover fuel and reduce greenhouse gas emissions.
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Simultaneous removal of trace amounts of propyne and propadiene from propylene is an important but challenging industrial process. We report herein a class of microporous metal-organic frameworks (NKMOF-1-M) with exceptional water stability and remarkably high uptakes for both propyne and propadiene at low pressures. NKMOF-1-M separated a ternary propyne/propadiene/propylene (0.5 : 0.5 : 99.0) mixture with the highest reported selectivity for the production of polymer-grade propylene (99.996 %) at ambient temperature, as attributed to its strong binding affinity for propyne and propadiene over propylene. Moreover, we were able to visualize propyne and propadiene molecules in the single-crystal structure of NKMOF-1-M through a convenient approach under ambient conditions, which helped to precisely understand the binding sites and affinity for propyne and propadiene. These results provide important guidance on using ultramicroporous MOFs as physisorbent materials.
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Grand canonical Monte Carlo (GCMC) simulations of gas sorption were performed in Cu-TDPAH, also known as rht-MOF-9, hereafter [1], a metal-organic framework (MOF) with rht topology consisting of Cu2+ ions coordinated to 2,5,8-tris(3,5-dicarboxyphenylamino)-1,3,4,6,7,9,9b-heptaazaphenalene (TDPAH) ligands. This MOF is notable for the presence of open-metal copper sites and high nitrogen content on the linkers. [1] Exhibits one of the highest experimental H2 uptakes at 77 K/1 atm within the extant rht-MOF family (ca. 2.72 wt%) and also has strong affinity for CO2 (5.83 mmol g-1 at 298 K/1 atm). Our simulations, which include explicit many-body polarization interactions, accurately modeled macroscopic thermodynamic properties (e.g., sorption isotherms and isosteric heats of adsorption (Qst)) as well as the binding sites for H2, CO2, CH4, C2H2, C2H4, and C2H6 in the MOF. Four different binding sites were observed through analysis of the radial distribution function (g(r)) about the two chemically distinct Cu2+ ions, simulated annealing calculations, and examination of the three-dimensional histogram showing the sites of occupancy: (1) at the Cu2+ ion facing toward the center of the linker (CuL), (2) at the Cu2+ ion facing away from the center of linker (CuC), (3) nestled between three [Cu2(O2CR)4] units in the corner of the truncated tetrahedral (T-Td) cage and (4) straddling the copper nuclei parallel to the axis of the Cu-Cu bond within the T-Td cage. The low-loading (initial) binding site in the MOF is highly sensitive to the partial charges of the Cu2+ ions that were used for parametrization. It was discovered that most sorbates prefer to sorb onto or near the Cu2+ ions that exhibit the greater partial positive charge (i.e., at site 1). The simulated H2 and CO2 sorption results obtained using a polarizable potential for the respective sorbates are in good agreement with the corresponding experimental data, especially near ambient pressure. Simulations of gas sorption were also performed in [1] using nonpolarizable potentials for the individual sorbates; these include potentials from the TraPPE force field for most sorbates.
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Highly selective separation and/or purification of acetylene from various gas mixtures is a relevant and difficult challenge that currently requires costly and energy-intensive chemisorption processes. Two ultramicroporous metal-organic framework physisorbents, NKMOF-1-M (M=Cu or Ni), offer high hydrolytic stability and benchmark selectivity towards acetylene versus several gases at ambient temperature. The performance of NKMOF-1-M is attributed to their exceptional acetylene binding affinity as revealed by modelling and several experimental studies: inâ situ single-crystal X-ray diffraction, FTIR, and gas mixture breakthrough tests. NKMOF-1-M exhibit better low-pressure uptake than existing physisorbents and possesses the highest selectivities yet reported for C2 H2 /CO2 and C2 H2 /CH4 . The performance of NKMOF-1-M is not driven by the same mechanism as current benchmark physisorbents that rely on pore walls lined by inorganic anions.