Designer Metal–Organic Frameworks for Size‐Exclusion‐Based Hydrocarbon Separations: Progress and Challenges

Advanced Materials, Journal Year: 2020, Volume and Issue: 32(44)

Published: July 9, 2020

Abstract The separation of hydrocarbons is primary importance in the petrochemical industry but remains a challenging process. Hydrocarbon separations have traditionally relied predominantly on costly and energy‐intensive heat‐driven procedures such as low‐temperature distillations. Adsorptive based porous solids represents an alternative technology that potentially more energy efficient for some hydrocarbons. Great efforts been made recently not only development adsorbents with optimal performance also toward subsequent implementation adsorption‐based technology. Emerging relatively new class multifunctional materials, metal–organic frameworks (MOFs) hold substantial promise highly This because their exceptional intrinsic porosity tunability, which enables size‐exclusion‐based render highest possible selectivity. In this review, recent advances MOFs selected groups are reviewed, including methane/C 2 hydrocarbons, normal alkanes, alkane isomers, alkane/alkene/alkyne C 8 alkylaromatics, particular focus size‐exclusion mechanism. Insights into tailor‐made structures, material design strategies, structure–property relationships will be elucidated. addition, existing challenges future directions important research field discussed.

Language: Английский

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Achieving High Performance Metal–Organic Framework Materials through Pore Engineering

Accounts of Chemical Research, Journal Year: 2021, Volume and Issue: 54(17), P. 3362 - 3376

Published: Aug. 17, 2021

Achieving high performance functional materials has been a long-term goal for scientists and engineers that can significantly promote science technology development thus benefit our society human beings. As well-known porous materials, metal-organic frameworks (MOFs) are crystalline open made up of molecular building blocks linked by strong coordination bonds, affording pore space storing trapping guest molecules. In terms porosity, MOFs outperform traditional including zeolites activated carbon, showing exceptional porosity with internal surface area to thousands square meters per gram sample periodic sizes ranging from sub-nanometer nanometers. Numerous have synthesized potential applications gaseous fuels separating intractable industrial gas mixtures, sensing physical chemical stimulus, transmitting protons conduction. Compared distinguished their capability adjustment interior modification through engineering, which them preeminent platform exploring performance.Rational combinations rigid units different geometry multibranched organic linkers provided diverse structures, spherical cylindrical, slit, tubular ones isolating or interconnecting in directions, be optimized high-capacity storage. Based on the isoreticular principle approach MOF chemistry, performed exquisite precision, making suitable address industrially important separation. The large cavities readily available encapsulation species, resulting novel composite various functions.In this Account, we summarize recent research progress engineering achieve high-performance materials. We able tune optimize immobilize specific sites, incorporate species into target hydrogen storage, methane light-hydrocarbon purification, proton conduction, especially separations acetylene removal ethylene propylene purification. By chemistry endows multiple functionalities, endeavors brought about customization corresponding application scenarios.

Language: Английский

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Selective Ethane/Ethylene Separation in a Robust Microporous Hydrogen-Bonded Organic Framework

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 142(1), P. 633 - 640

Published: Dec. 14, 2019

The separation of ethane (C2H6) from ethylene (C2H4) is prime importance in the production polymer-grade C2H4 for industrial manufacturing. It very challenging and still remains unexploited to fully realize efficient C2H6/C2H4 emerging hydrogen-bonded organic frameworks (HOFs) due weak nature hydrogen bonds. We herein report benchmark example a novel ultrarobust HOF adsorbent (termed as HOF-76a) with Brunauer–Emmett–Teller surface area exceeding 1100 m2 g–1, exhibiting preferential binding C2H6 over thus highly selective C2H6/C2H4. Theoretical calculations indicate key role nonpolar suitable triangular channel-like pores HOF-76a sterically "match" better nonplanar molecule than planar C2H4, affording overall stronger multipoint van der Waals interactions C2H6. exceptional performance was clearly demonstrated by gas adsorption isotherms, ideal adsorbed solution theory calculations, simulated experimental breakthrough curves. Breakthrough experiments on reveal that can be straightforwardly produced 50/50 (v/v) mixtures during first cycle high productivity 7.2 L/kg at 298 K 1.01 bar 18.8 5.0 bar, respectively.

Language: Английский

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An Ultramicroporous Metal–Organic Framework for High Sieving Separation of Propylene from Propane

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(41), P. 17795 - 17801

Published: Sept. 29, 2020

Highly selective adsorptive separation of olefin/paraffin through porous materials can produce high purity olefins in a much more energy-efficient way than the traditional cryogenic distillation. Here we report an ultramicroporous cobalt gallate metal-organic framework (Co-gallate) for highly sieving propylene/propane at ambient conditions. This material possesses optimal pore structure exact confinement propylene molecules while excluding slightly large propane molecules, as clearly demonstrated neutron diffraction crystal Co-gallate⊃0.38C

Language: Английский

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A MOF‐based Ultra‐Strong Acetylene Nano‐trap for Highly Efficient C₂H₂/CO₂ Separation

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(10), P. 5283 - 5288

Published: Jan. 7, 2021

Abstract Porous materials with open metal sites have been investigated to separate various gas mixtures. However, show the limitation in separation of some challenging mixtures, such as C 2 H /CO . Herein, we propose a new type ultra‐strong nano‐trap based on multiple binding interactions efficiently capture molecules and mixture. The acetylene shows benchmark Q st 79.1 kJ mol −1 for , record high pure uptake 2.54 mmol g at 1×10 −2 bar, highest selectivity (53.6), making it material locations within MOF‐based nanotrap visualized by situ single‐crystal X‐ray diffraction studies, which also identify accountable strong

Language: Английский

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Immobilization of Lewis Basic Sites into a Stable Ethane-Selective MOF Enabling One-Step Separation of Ethylene from a Ternary Mixture

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(6), P. 2614 - 2623

Published: Feb. 2, 2022

Purification of C2H4 from a ternary C2H2/C2H6/C2H4 mixture by one-step adsorption separation is prime importance but challenging in the petrochemical industry; however, effective strategies to design high-performance adsorbents are lacking. We herein report for first time incorporation Lewis basic sites into C2H6-selective MOF, enabling efficient production polymer-grade mixtures. Introduction amino groups highly stable UiO-67 can not only partition large pores smaller cagelike pockets provide suitable pore confinement also offer additional binding simultaneously enhance C2H2 and C2H6 capacities over C2H4. The amino-functionalized UiO-67-(NH2)2 thus exhibits exceptionally high uptakes as well benchmark C2H2/C2H4 C2H6/C2H4 selectivities, surpassing all C2H2/C2H6-selective materials reported so far. Theoretical calculations combined with situ infrared spectroscopy indicate that synergetic effect functional surfaces decorated provides overall stronger multipoint van der Waals interactions exceptional performance was evidenced breakthrough experiments mixtures under dry wet conditions, providing remarkable productivity 0.55 mmol g-1 at ambient conditions.

Language: Английский

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Supramolecular control of MOF pore properties for the tailored guest adsorption/separation applications

Coordination Chemistry Reviews, Journal Year: 2021, Volume and Issue: 434, P. 213709 - 213709

Published: Feb. 11, 2021

Language: Английский

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Progress and potential of metal-organic frameworks (MOFs) for gas storage and separation: A review

Journal of environmental chemical engineering, Journal Year: 2022, Volume and Issue: 10(5), P. 108300 - 108300

Published: July 20, 2022

Language: Английский

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Bottom-Up Synthesis of 8-Connected Three-Dimensional Covalent Organic Frameworks for Highly Efficient Ethylene/Ethane Separation

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(12), P. 5643 - 5652

Published: March 21, 2022

Developing cost-/energy-efficient separation techniques for purifying ethylene from an ethylene/ethane mixture is highly important but very challenging in the industrial process. Herein, using a bottom-up [8 + 2] construction approach, we rationally designed and synthesized three three-dimensional covalent organic frameworks (COFs) with 8-connected bcu networks, which can selectively remove ethane high efficiency. These COF materials, are fabricated by condensation reaction of customer-designed octatopic aldehyde monomer linear diamino linkers, possess crystallinity, good structural robustness, porosity. Attributed to well-organized micro-sized pores nonpolar/inert pore environment, these COFs display adsorption capacity selectivity over ethylene, making them among best ethane-selective adsorbents purification. Their excellent performance validated dynamic breakthrough experiments high-purity (>99.99%) produced through single The surpasses all reported C2H6-selective even some benchmark metal-organic frameworks. This work provides guidance design new value-added gas

Language: Английский

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Separation and Purification of Hydrocarbons with Porous Materials

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(35), P. 18930 - 18949

Published: March 30, 2021

This Minireview focuses on the developments of adsorptive separation methane/nitrogen, ethene/ethane, propene/propane mixtures as well C8 aromatics (i.e. xylene isomers) with a wide variety materials, including carbonaceous zeolites, metal-organic frameworks, and porous organic frameworks. Some recent important for these separations are also highlighted. The advantages disadvantages each material category discussed guidelines design improved materials proposed. Furthermore, challenges future type processes discussed.

Language: Английский

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