Metal-organic frameworks for C2H2/CO2 separation: Recent development

Coordination Chemistry Reviews, Journal Year: 2023, Volume and Issue: 482, P. 215093 - 215093

Published: March 1, 2023

Language: Английский

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Immobilization of the Polar Group into an Ultramicroporous Metal–Organic Framework Enabling Benchmark Inverse Selective CO₂/C₂H₂ Separation with Record C₂H₂ Production

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(25), P. 13901 - 13911

Published: June 13, 2023

One-step harvest of high-purity light hydrocarbons without the desorption process represents an advanced and highly efficient strategy for purification target substances. The separation acetylene (C2H2) from carbon dioxide (CO2) by CO2-selective adsorbents are urgently demanded yet very challenging owing to their similar physicochemical properties. Here, we employ pore chemistry adjust environment immobilizing polar groups into ultramicroporous metal-organic framework (MOF), achieving one-step manufacture C2H2 CO2/C2H2 mixtures. Embedding methyl prototype stable MOF (Zn-ox-trz) not only changes but also improves discrimination guest molecules. methyl-functionalized Zn-ox-mtz thus exhibits benchmark reverse uptake ratio 12.6 (123.32/9.79 cm3 cm-3) exceptionally high equimolar selectivity 1064.9 at ambient conditions. Molecular simulations reveal that synergetic effect confinement surfaces decorated with provides recognition CO2 molecules through multiple van der Waals interactions. column breakthrough experiments suggest dramatically achieved capacity mixture a record productivity 2091 mmol kg-1, surpassing all reported so far. In addition, excellent chemical stability under different pH values aqueous solutions (pH = 1-12). Moreover, inverse selective performance showcase its promising application as splitter industrial manufacture. This work paves way developing reverse-selective gas process.

Language: Английский

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Engineering Pore Environments of Sulfate‐Pillared Metal‐Organic Framework for Efficient C₂H₂/CO₂ Separation with Record Selectivity

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(20)

Published: March 1, 2023

Engineering pore environments exhibit great potential in improving gas adsorption and separation performances but require specific means for acetylene/carbon dioxide (C2 H2 /CO2 ) due to their identical dynamic diameters similar properties. Herein, a novel sulfate-pillared MOF adsorbent (SOFOUR-TEPE-Zn) using 1,1,2,2-tetra(pyridin-4-yl) ethene (TEPE) ligand with dense electronegative surfaces is reported. Compared the prototype SOFOUR-1-Zn, SOFOUR-TEPE-Zn exhibits higher C2 uptake (89.1 cm3 g-1 ), meanwhile CO2 reduces 14.1 , only 17.4% of that on SOFOUR-1-Zn (81.0 ). The high affinity toward than demonstrated by benchmark selectivity (16 833). Furthermore, breakthrough experiments confirm its application feasibility good cyclability at various flow rates. During desorption cycle, 60.1 99.5% purity or 33.2 99.99% can be recovered stepped purging mild heating. simulated pressure swing processes reveal 75.5 99.5+% recovery 99.82% produced counter-current blowdown process. Modeling studies disclose four favorable sites packing .

Language: Английский

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Topological Design of Unprecedented Metal‐Organic Frameworks Featuring Multiple Anion Functionalities and Hierarchical Porosity for Benchmark Acetylene Separation

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(37)

Published: July 17, 2023

Separation of acetylene (C2 H2 ) from carbon dioxide (CO2 or ethylene H4 is industrially important but still challenging so far. Herein, we developed two novel robust metal organic frameworks AlFSIX-Cu-TPBDA (ZNU-8) with znv topology and SIFSIX-Cu-TPBDA (ZNU-9) wly for efficient capture C2 CO2 . Both ZNU-8 ZNU-9 feature multiple anion functionalities hierarchical porosity. Notably, more anionic binding sites three distinct cages displays both an extremely large capacity (7.94 mmol/g) a high /CO2 (10.3) /C2 (11.6) selectivity. The calculated per (4.94 mol/mol at 1 bar) the highest among all pillared frameworks. Theoretical calculation indicated that strong cooperative hydrogen bonds exist between SiF62- anions in confined cavity, which further confirmed by situ IR spectra. practical separation performance was explicitly demonstrated dynamic breakthrough experiments equimolar mixtures 1/99 under various conditions excellent recyclability benchmark productivity pure (5.13 (48.57 mmol/g).

Language: Английский

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A Microporous Hydrogen Bonded Organic Framework for Highly Selective Separation of Carbon Dioxide over Acetylene

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(39)

Published: Aug. 11, 2023

The separation of acetylene (C2 H2 ) from carbon dioxide (CO2 is a very important but challenging task due to their similar molecular dimensions and physical properties. In terms porous adsorbents for this separation, the CO2 -selective materials are superior C2 ones because cost- energy-efficiency have been rarely achieved. Herein we report our unexpected discovery first hydrogen bonded organic framework (HOF) constructed simple linker 2,4,6-tri(1H-pyrazol-4-yl)pyridine (PYTPZ) (termed as HOF-FJU-88) highly material. HOF-FJU-88 two-dimensional HOFs with pore pocket about 7.6 Å. activated takes up high amount (59.6 cm3 g-1 at ambient conditions record IAST selectivity 1894. Its performance /C2 has further confirmed through breakthrough experiments, in situ diffuse reflectance infrared spectroscopy simulations.

Language: Английский

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Isoreticular Contraction of Cage-like Metal–Organic Frameworks with Optimized Pore Space for Enhanced C₂H₂/CO₂ and C₂H₂/C₂H₄ Separations

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(11), P. 7341 - 7351

Published: March 5, 2024

The C2H2 separation from CO2 and C2H4 is of great importance yet highly challenging in the petrochemical industry, owing to their similar physical chemical properties. Herein, pore nanospace engineering cage-like mixed-ligand MFOF-1 has been accomplished via contracting size pyridine- carboxylic acid-functionalized linkers introducing a fluoride- sulfate-bridging cobalt cluster, based on reticular chemistry strategy. Compared with prototypical MFOF-1, constructed FJUT-1 same topology presents significantly improved adsorption capacity, selective performance due reduced cage cavity size, functionalized surface, appropriate volume. introduction cubane-type tetranuclear clusters bestows exceptional stability under harsh conditions while providing multiple potential binding sites, thus rendering adequate ability for practical application as confirmed by dynamic breakthrough experiments dry humid conditions. Additionally, distinct mechanism suggested theoretical calculations which supramolecular interactions involving C–H···O, C–H···F, other van der Waals forces play critical role separation.

Language: Английский

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CO₂-Based Stable Porous Metal–Organic Frameworks for CO₂ Utilization

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(21), P. 14835 - 14843

Published: May 10, 2024

The transformation of carbon dioxide (CO2) into functional materials has garnered considerable worldwide interest. Metal–organic frameworks (MOFs), as a distinctive class materials, have made great contributions to CO2 capture and conversion. However, facile conversion stable porous MOFs for utilization remains unexplored. Herein, we present methodology using synthesize zirconium-based MOFs. Two CO2–Zr-DEP CO2–Zr-DEDP with face-centered cubic topology were obtained via sequential desilylation–carboxylation–coordination reaction. exhibit excellent crystallinity, verified through powder X-ray diffraction high-resolution transmission electron microscopy analyses. They also notable porosity high surface area (SBET up 3688 m2 g–1) good adsorption capacity (up 12.5 wt %). resulting abundant alkyne moieties, confirmed 13C cross-polarization/magic angle spinning nuclear magnetic resonance Fourier transform infrared spectra. Leveraging the catalytic prowess Ag(I) in diverse CO2-involved reactions, incorporated MOFs, capitalizing on their interactions carbon–carbon π-bonds alkynes, thereby forming heterogeneous catalyst. This catalyst demonstrates outstanding efficiency catalyzing propargylic alcohols cyclic carbonates, achieving >99% yield at room temperature atmospheric pressure conditions. Thus, this work provides dual strategy, encompassing synthesis CO2-based (20–24 % from CO2) subsequent application processes. approach significantly enhances overall utilization.

Language: Английский

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Inverse CO2/C2H2 separation in a pillared-layer framework featuring a chlorine-modified channel by quadrupole-moment sieving

Separation and Purification Technology, Journal Year: 2021, Volume and Issue: 279, P. 119608 - 119608

Published: Aug. 30, 2021

Language: Английский

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Highly Selective Adsorption of Carbon Dioxide over Acetylene in an Ultramicroporous Metal–Organic Framework

Advanced Materials, Journal Year: 2021, Volume and Issue: 33(45)

Published: Sept. 17, 2021

Abstract Separating carbon dioxide from fuel gases like hydrocarbons by physical adsorbents is industrially important and more energy‐efficient than traditional liquid extraction or cryogenic distillation methods. It very while challenging to develop CO 2 ‐selective adsorbents, considering less polarizable light hydrocarbon molecules, particularly those simultaneously with almost identical molecular dimensions properties, such as acetylene. Herein, an ultramicroporous metal–organic framework constructed copper(II) 5‐fluoropyrimidin‐2‐olate, termed Cu‐F‐pymo , carefully studied under different activations for inverse separation of C H . The partially desolvated can exclusively capture over high selectivity exceeding 10 5 ambient conditions, the highest ever reported. Sorption experiments modeling studies reveal that sieving effect attributed suppression adsorption blockage preferential sites residual water molecules. further confirmed column breakthrough given highly pure acetylene (>99.9%) be directly harvested gas mixture. also shows remarkable stability harsh conditions.

Language: Английский

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Collaborative pore partition and pore surface fluorination within a metal–organic framework for high-performance C2H2/CO2 separation

Chemical Engineering Journal, Journal Year: 2022, Volume and Issue: 432, P. 134433 - 134433

Published: Jan. 3, 2022

Language: Английский

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