Separation of Acetylene from Carbon Dioxide and Ethylene by a Water‐Stable Microporous Metal–Organic Framework with Aligned Imidazolium Groups inside the Channels

Lee, Jaechul; Chuah, Chong Yang; Kim, Jaheon; Kim, Young-Suk; Ko, Nakeun; Seo, Younggyu; Kim, Kimoon; Bae, Tae‐Hyun; Lee, Eunsung

doi:10.1002/anie.201804442

Cited by 228 publications

(169 citation statements)

References 62 publications

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“…Notably, the adsorption selectivity of Ni‐gallate at 1 kPa reached 112, significantly higher than SIFSIX‐2‐Cu‐i (51.7) . Meanwhile, the calculated IAST selectivities of C 2 H 2 /C 2 H 4 (1:99, v/v) for Co‐gallate and Mg‐gallate were 15.0 and 20.9 at 298 K and 1 bar, respectively, revealing an excellent C 2 H 2 /C 2 H 4 separation performance compared with some porous materials, such as M′MOF‐3 (24), UTSA‐100 (10.7), SIFSIX‐1‐Cu (10.6), Fe‐MOF‐74 (2.08), SIFSIX‐3‐Zn (8.8), and JMC‐1 (8.1) . Additionally, the calculated IAST selectivities for different ratios of C 2 H 2 and C 2 H 4 mixtures of M‐gallate (1:99 and 50:50, v/v) at the range 0–1 bar and different temperatures are displayed in Figures S8–S10 (in the Supporting Information).…”

Section: Resultssupporting

confidence: 87%

Adsorptive Separation of Acetylene from Ethylene in Isostructural Gallate‐Based Metal–Organic Frameworks

Wang

Guo

et al. 2019

Chemistry A European J

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The separation of acetylene from ethylene is of paramount importancei nt he purification of chemicalf eedstocks fori ndustrial manufacturing. Herein, an isostructural series of gallate-based metal-organic frameworks (MOFs), Mgallate (M = Ni, Mg, Co), featuring three-dimensionallyi nterconnected zigzag channels, the aperture size of which can be finely tunedw ithin 0.3 by metalr eplacement. Controlling the apertures ize of M-gallate materials slightly from 3.69 down to 3.47 could result in ad ramatic enhancement of C 2 H 2 /C 2 H 4 separation performance.A st he smallest radius amongt he studied metal ions, Ni-gallate exhibits the best C 2 H 2 /C 2 H 4 adsorption separation performance owingt ot he strongestc onfinement effect,r ankinga fter the state-of-theart UTSA-200a with aC 2 H 4 productivity of 85.6 mol L À1 from 1:99 C 2 H 2 /C 2 H 4 mixture. The isostructural gallate-based MOFs, readilys ynthesized from inexpensive gallic acid, are demonstratedt ob ean ew

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Section: Resultssupporting

confidence: 87%

Adsorptive Separation of Acetylene from Ethylene in Isostructural Gallate‐Based Metal–Organic Frameworks

Wang

Guo

et al. 2019

Chemistry A European J

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“…Kitagawa's group introduced the prototypal C 2 H 2 selective sorbent in 2005, and there has been a recent upsurge in interest . Although there are fourteen previous reports of dynamic gas‐mixture breakthrough tests conducted using MOFs (Table S1 in the Supporting Information), separation selectivity values determined from 1:1 C 2 H 2 /CO 2 breakthrough experiments are limited to four sorbents: FJU‐22 a , UTSA‐74 a , JCM‐1 , and NKMOF‐1‐Ni …”

Section: Methodsmentioning

confidence: 99%

Halogen–C₂H₂ Binding in Ultramicroporous Metal–Organic Frameworks (MOFs) for Benchmark C₂H₂/CO₂ Separation Selectivity

Mukherjee

Franz

et al. 2020

Chemistry A European J

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Acetylene (C 2 H 2 )c apturei sastep in an umber of industrial processes, but it comes with ah igh-energy footprint. Although physisorbents have the potential to reduce this energy footprint, they are handicappedb y generally poor selectivity versusother relevant gases, such as CO 2 and C 2 H 4 .I nt he case of CO 2 ,t he respective physicochemical properties are so similar that traditional physisorbents, such as zeolites, silica, anda ctivated carbons cannot differentiate well between CO 2 and C 2 H 2 .H erein, we report that af amily of three isostructural, ultramicroporous (< 7 )d iamondoidm etal-organic frameworks, [Cu(TMBP)X] (TMBP = 3,3',5,5'-tetramethyl-4,4'-bipyrazole), TCuX (X = Cl, Br,I ), offer new benchmark C 2 H 2 /CO 2 separation selectivity at ambient temperature and pressure.W e attribute this performance to an ew type of strong binding site for C 2 H 2 .S pecifically,h alogen···HC interactions coupledw ith othern oncovalent in at ight binding site is C 2 H 2 specific versus CO 2 .T he binding site is distinct from those found in previous benchmark sorbents, which are based on open metal sites or electrostatic interactionse nabled by inorganic fluoro or oxo anions.That C 2 H 2 poses an immediate fire and explosive hazard at > 2.5 %c oncentrations and features the widest knownf lammability range, [1] 2.5-81 %, underscores the need to develop energy-efficient C 2 H 2 -capture sorbent materials. [2] Further,i ts high reactivity can lead to undesirable chemicalr eactions duringi ndustrial processes, for example, traces of C 2 H 2 can poisonc atalystsb yf orming metal acetylides duringe thylene polymerization, leading to explosions. [3] Removal of C 2 H 2 as a trace contaminant is also important in the productiono fa crylic/vinyl derivatives and acetylenic alcohols. [4] With respect to bulk usage,C 2 H 2 is the most common gas used to fuel cutting torches. C 2 H 2 recovered in high purity can serve as af uel or buildingblock in polymer synthesis for example, polyvinyl chloride, PVC and polyvinylidene fluoride,PVDF. [4] In C 2 H 2 manufacturedb yp artial combustion (oxidative coupling)o fmethane [5] or thermal cracking of hydrocarbons, CO 2 is generated as ab y-product. [6] To enable C 2 H 2 capturef rom C 2 H 2 /CO 2 mixtures, three current methods were employed: 1) bulk extraction by organic solvents, for example, N,N-dimethylformamide, and acetone; [7] b) partial hydrogenation of C 2 H 2 to ethylene, C 2 H 4 using expensive Ag 0 /other noble-metalc atalysts; [8] and c) cryogenic distillation. [9] All three approaches are costly and energy intensive. Althoughp hysisorbentso ffer potentialf or reducing the energyf ootprint of C 2 H 2 capture, zeolites, silica, and activated carbonsc annot effectively separate C 2 H 2 from CO 2[10] because of their similarp hysicochemical properties (size:C 2 H 2 = 3.32 3.34 5.7 3 ;C O 2 = 3.18 3.33 5.36 3 ;k inetic diameter = 3.3 for both;b oilingp oint:C 2 H 2 = 189.3 K, CO 2 = 194.7 K). [11] In this context,a ne merging class of physisorbents, namely, metal-organic m...

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“…As shown in Figure c, at 100 kPa and 298 K, the C 2 H 2 /CO 2 (50:50) selectivity of FeNi‐M′MOF is 24. The selectivity of FeNi‐M′MOF is higher than those of most MOFs, such as Zn‐MOF‐74 (1.92), FJU‐90 a (4.3), UTSA‐74 a (8.2), JCM‐1 (13.4), DICRO‐4‐Ni‐i (13.9), and benchmark HOF‐3 a (21) . It should be noted that both the uptake capacity and separation selectivity can significantly affect the practical performance of an adsorbent.…”

Section: Figurementioning

confidence: 99%

Mixed Metal–Organic Framework with Multiple Binding Sites for Efficient C₂H₂/CO₂Separation

et al. 2020

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The separation of C2H2/CO2 is particularly challenging owing to their similarities in physical properties and molecular sizes. Reported here is a mixed metal–organic framework (M′MOF), [Fe(pyz)Ni(CN)4] (FeNi‐M′MOF, pyz=pyrazine), with multiple functional sites and compact one‐dimensional channels of about 4.0 Å for C2H2/CO2 separation. This MOF shows not only a remarkable volumetric C2H2 uptake of 133 cm3 cm−3, but also an excellent C2H2/CO2 selectivity of 24 under ambient conditions, resulting in the second highest C2H2‐capture amount of 4.54 mol L−1, thus outperforming most previous benchmark materials. The separation performance of this material is driven by π–π stacking and multiple intermolecular interactions between C2H2 molecules and the binding sites of FeNi‐M′MOF. This material can be facilely synthesized at room temperature and is water stable, highlighting FeNi‐M′MOF as a promising material for C2H2/CO2 separation.

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Separation of Acetylene from Carbon Dioxide and Ethylene by a Water‐Stable Microporous Metal–Organic Framework with Aligned Imidazolium Groups inside the Channels

Cited by 228 publications

References 62 publications

Adsorptive Separation of Acetylene from Ethylene in Isostructural Gallate‐Based Metal–Organic Frameworks

Adsorptive Separation of Acetylene from Ethylene in Isostructural Gallate‐Based Metal–Organic Frameworks

Halogen–C₂H₂ Binding in Ultramicroporous Metal–Organic Frameworks (MOFs) for Benchmark C₂H₂/CO₂ Separation Selectivity

Mixed Metal–Organic Framework with Multiple Binding Sites for Efficient C₂H₂/CO₂Separation

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Separation of Acetylene from Carbon Dioxide and Ethylene by a Water‐Stable Microporous Metal–Organic Framework with Aligned Imidazolium Groups inside the Channels

Cited by 228 publications

References 62 publications

Adsorptive Separation of Acetylene from Ethylene in Isostructural Gallate‐Based Metal–Organic Frameworks

Adsorptive Separation of Acetylene from Ethylene in Isostructural Gallate‐Based Metal–Organic Frameworks

Halogen–C2H2 Binding in Ultramicroporous Metal–Organic Frameworks (MOFs) for Benchmark C2H2/CO2 Separation Selectivity

Mixed Metal–Organic Framework with Multiple Binding Sites for Efficient C2H2/CO2Separation

Contact Info

Product

Resources

About

Halogen–C₂H₂ Binding in Ultramicroporous Metal–Organic Frameworks (MOFs) for Benchmark C₂H₂/CO₂ Separation Selectivity

Mixed Metal–Organic Framework with Multiple Binding Sites for Efficient C₂H₂/CO₂Separation