Adsorption Site Selective Occupation Strategy within a Metal–Organic Framework for Highly Efficient Sieving Acetylene from Carbon Dioxide

Yang, Lingzhi; Yan, Liting; Wang, Ying; Liu, Zhi; He, Jiangxiu; Fu, Qiuju; Liu, Dandan; Gu, Xin; Dai, Pinqiang; Li, Liangjun; Zhao, Xuebo

doi:10.1002/anie.202013965

Cited by 129 publications

(89 citation statements)

References 64 publications

(12 reference statements)

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“…However, the copper(I)‐chelated Cu Ι @UiO‐66‐(COOH) 2 exhibits a drastically enhanced C 2 H 2 /CO 2 selectivity (185.0) at 298 K and 1.0 bar. To the best of our knowledge, this selectivity is the highest among all the robust MOFs reported so far (Figure 3 f and Table S4), significantly higher than that of the previous benchmark CPL‐1‐NH 2 (119), [9f] ATC‐Cu (53.6), [11f] ZJU‐74a (36.5), [11e] NKMOF‐1‐Ni (25.0), [11b] and FeNi‐M′MOF (24) [11d] . As shown in Figure 3 f, Cu Ι @UiO‐66‐(COOH) 2 also shows a relatively high C 2 H 2 volumetric uptake (3.7 mmol cm −3 ) at the partial pressure of 0.5 bar and 298 K, even comparable to that of NKMOF‐1‐Ni (4.3 mmol cm −3 ), [11b] JCM‐1 (3.8 mmol cm −3 ) [11c] and ZJU‐74a (4.6 mmol cm −3 ) [11e] .…”

Section: Resultsmentioning

confidence: 65%

Benchmark C₂H₂/CO₂Separation in an Ultra‐Microporous Metal–Organic Framework via Copper(I)‐Alkynyl Chemistry

et al. 2021

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Separation of acetylene from carbon dioxide remains a daunting challenge because of their very similar molecular sizes and physical properties. We herein report the first example of using copper(I)‐alkynyl chemistry within an ultra‐microporous MOF (CuI@UiO‐66‐(COOH)2) to achieve ultrahigh C2H2/CO2 separation selectivity. The anchored CuI ions on the pore surfaces can specifically and strongly interact with C2H2 molecule through copper(I)‐alkynyl π‐complexation and thus rapidly adsorb large amount of C2H2 at low‐pressure region, while effectively reduce CO2 uptake due to the small pore sizes. This material thus exhibits the record high C2H2/CO2 selectivity of 185 at ambient conditions, significantly higher than the previous benchmark ZJU‐74a (36.5) and ATC‐Cu (53.6). Theoretical calculations reveal that the unique π‐complexation between CuI and C2H2 mainly contributes to the ultra‐strong C2H2 binding affinity and record selectivity. The exceptional separation performance was evidenced by breakthrough experiments for C2H2/CO2 gas mixtures. This work suggests a new perspective to functionalizing MOFs with copper(I)‐alkynyl chemistry for highly selective separation of C2H2 over CO2.

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Section: Resultsmentioning

confidence: 65%

Benchmark C₂H₂/CO₂Separation in an Ultra‐Microporous Metal–Organic Framework via Copper(I)‐Alkynyl Chemistry

et al. 2021

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“…Since the CO 2 adsorption sites were now occupied by the amino groups on the pillars, a significantly lower amount of CO 2 was adsorbed onto the framework leading to a high C 2 H 2 /CO 2 selectivity of 119 at ambient conditions. [25]…”

Section: Separation Of Acetylene From Carbon Dioxidementioning

confidence: 99%

New Paradigms in Porous Framework Materials for Acetylene Storage and Separation

Verma

Ren

Kumar³

et al. 2021

Eur J Inorg Chem

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Acetylene is an important precursor in the petrochemical, plastics and electronic industries, as well as the prominent fuel for welding and metal cutting. The high flammability and explosive nature of acetylene, however hinder its safe storage and transportation. Porous materials are highly promising for acetylene storage and as they can provide strong binding interactions and an optimal pore environment. Furthermore, high selectivity and separation can be achieved for acetylene over other gases such as CO 2 and small hydrocarbons. In this review, we divulge into the recent advancements and paradigms in acetylene storage and separation with a focus on porous metal-organic frameworks (MOFs). An overview of the benchmark materials for acetylene storage and separation, along with some recent developments in the strategies to balance the trade-off between the uptake capacity and selectivity is provided. The approaches of designing small pores and highly functionalized pore environments for strong binding with the acetylene adsorbate; along with the pore space partition, window space directed assembly and inverse CO 2 / C 2 H 2 adsorption for the separation of acetylene from CO 2 , CH 4 , C 2 H 4 and other hydrocarbons are reviewed to provide a summary and help further augment the research in this direction.

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“…Both materials are flexible and show lower gate opening pressure for C 2 H 2 and higher gate opening pressure for CO 2 . However, the uptake of C 2 H 2 on UTSA‐300a (68.9 cm 3 g −1 ) [6a] and CPL‐1‐NH 2 (41.2 cm 3 g −1 ) [6b] under 1 bar and 298 K is relatively modest, and co‐adsorption of CO 2 is inevitable after the pore expansion induced by C 2 H 2 in practical breakthrough experiments. Other two porous materials with high IAST selectivity (>50) are ATC‐Cu [6c] and Cu@UiO‐66‐(COOH) 2 [6d] .…”

Section: Introductionmentioning

confidence: 99%

Interpenetration Symmetry Control Within Ultramicroporous Robust Boron Cluster Hybrid MOFs for Benchmark Purification of Acetylene from Carbon Dioxide

et al. 2021

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The separation of C 2 H 2 /CO 2 is an important process in industry but challenged by the trade-off of capacity and selectivity owning to their similar physical properties and identical kinetic molecular size. We report the first example of symmetrically interpenetrated dodecaborate pillared MOF, ZNU-1, for benchmark selective separation of C 2 H 2 from CO 2 with ahigh C 2 H 2 capacity of 76.3 cm 3 g À1 and recordC 2 H 2 /CO 2 selectivity of 56.6 (298 K, 1bar) among all the robust porous materials without open metal sites.S ingle crystal structure analysis and modeling indicated that the interpenetration shifting from asymmetric to symmetric mode provided optimal pore chemistry with ideal synergistic "2+ +2" dihydrogen bonding sites for tight C 2 H 2 trapping.The exceptional separation performance was further evidenced by simulated and experimental breakthroughs with excellent recyclability and high productivity (2.4 mol kg À1 )o f9 9.5 %p urity C 2 H 2 during stepped desorption process.

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Adsorption Site Selective Occupation Strategy within a Metal–Organic Framework for Highly Efficient Sieving Acetylene from Carbon Dioxide

Cited by 129 publications

References 64 publications

Benchmark C₂H₂/CO₂Separation in an Ultra‐Microporous Metal–Organic Framework via Copper(I)‐Alkynyl Chemistry

Benchmark C₂H₂/CO₂Separation in an Ultra‐Microporous Metal–Organic Framework via Copper(I)‐Alkynyl Chemistry

New Paradigms in Porous Framework Materials for Acetylene Storage and Separation

Interpenetration Symmetry Control Within Ultramicroporous Robust Boron Cluster Hybrid MOFs for Benchmark Purification of Acetylene from Carbon Dioxide

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Adsorption Site Selective Occupation Strategy within a Metal–Organic Framework for Highly Efficient Sieving Acetylene from Carbon Dioxide

Cited by 129 publications

References 64 publications

Benchmark C2H2/CO2Separation in an Ultra‐Microporous Metal–Organic Framework via Copper(I)‐Alkynyl Chemistry

Benchmark C2H2/CO2Separation in an Ultra‐Microporous Metal–Organic Framework via Copper(I)‐Alkynyl Chemistry

New Paradigms in Porous Framework Materials for Acetylene Storage and Separation

Interpenetration Symmetry Control Within Ultramicroporous Robust Boron Cluster Hybrid MOFs for Benchmark Purification of Acetylene from Carbon Dioxide

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Product

Resources

About

Benchmark C₂H₂/CO₂Separation in an Ultra‐Microporous Metal–Organic Framework via Copper(I)‐Alkynyl Chemistry

Benchmark C₂H₂/CO₂Separation in an Ultra‐Microporous Metal–Organic Framework via Copper(I)‐Alkynyl Chemistry