Metal–Organic Framework Based Hydrogen-Bonding Nanotrap for Efficient Acetylene Storage and Separation

Journal of the American Chemical Society, Год журнала: 2021, Номер 144(4), С. 1681 - 1689

Опубликована: Дек. 29, 2021

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 their similar physical properties molecular sizes. To overcome this difficulty, here we report novel strategy involving regulation hydrogen-bonding nanotrap pore surface promote separation C2H2/CO2 mixtures in three isostructural metal-organic frameworks (MOFs, named MIL-160, CAU-10H, CAU-23, respectively). Among them, which has abundant acceptors as nanotraps, can selectively capture molecules demonstrates an ultrahigh C2H2 storage (191 cm3 g-1, or 213 cm-3) but much less CO2 uptake (90 g-1) under ambient conditions. amount MIL-160 remarkably higher than those other two MOFs (86 119 g-1 CAU-10H respectively) same More importantly, both simulation experimental breakthrough results show that sets new benchmark equimolar terms potential (Δqbreak = 5.02 mol/kg) productivity (6.8 mol/kg). In addition, situ FT-IR experiments computational modeling further reveal unique host-guest multiple interaction key factor achieving extraordinary superior selectivity. This work provides powerful approach extremely gas separation.

Язык: 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, Год журнала: 2022, Номер 144(6), С. 2614 - 2623

Опубликована: Фев. 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.

Язык: Английский

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Fluorinated metal–organic frameworks for gas separation

Chemical Society Reviews, Год журнала: 2022, Номер 51(17), С. 7427 - 7508

Опубликована: Янв. 1, 2022

Fluorinated metal-organic frameworks (F-MOFs) as fast-growing porous materials have revolutionized the field of gas separation due to their tunable pore apertures, appealing chemical features, and excellent stability. A deep understanding structure-performance relationships is critical for synthesis development new F-MOFs. This review has focused on several strategies precise design F-MOFs with structures tuned specific purposes. First, basic principles concepts well structure, modification structure property are studied. Then, applications in adsorption membrane discussed. detailed account capabilities various gases governing provided. In addition, exceptional characteristics highly stable engineered size put into perspective fabricate selective membranes separation. Systematic analysis position revealed that benchmark most challenging separations. The outlook future directions science engineering challenges highlighted tackle issues overcoming trade-off between capacity/permeability selectivity a serious move towards industrialization.

Язык: Английский

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Dense Packing of Acetylene in a Stable and Low‐Cost Metal–Organic Framework for Efficient C₂H₂/CO₂Separation

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(47), С. 25068 - 25074

Опубликована: Сен. 16, 2021

Porous materials for C2 H2 /CO2 separation mostly suffer from high regeneration energy, poor stability, or cost that largely dampen their industrial implementation. A desired adsorbent should have an optimal balance between excellent performance, and low cost. We herein report a stable, low-cost, easily scaled-up aluminum MOF (CAU-10-H) highly efficient separation. The suitable pore confinement in CAU-10-H can not only provide multipoint binding interactions with but also enable the dense packing of inside pores. This material exhibits one highest storage densities 392 g L-1 selective adsorption over CO2 at ambient conditions, achieved by enthalpy (27 kJ mol-1 ). Breakthrough experiments confirm its exceptional performance mixtures, affording both large uptake 3.3 mmol g-1 factor 3.4. achieves benchmark

Язык: Английский

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Efficient C₂H₂/CO₂ Separation in Ultramicroporous Metal–Organic Frameworks with Record C₂H₂ Storage Density

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(36), С. 14869 - 14876

Опубликована: Авг. 31, 2021

Physical separation of C2H2 from CO2 on metal–organic frameworks (MOFs) has received substantial research interest due to the advantages simplicity, security, and energy efficiency. However, that exhibit very close physical properties makes their exceptionally challenging. Previous work appeared mostly focused introducing open metal sites aims enhance affinity at desired sites, whereas reticular manipulation organic components rarely been investigated. In this work, by reticulating preselected amino hydroxy functionalities into isostructural ultramicroporous chiral MOFs—Ni2(l-asp)2(bpy) (MOF-NH2) Ni2(l-mal)2(bpy) (MOF-OH)—we targeted efficient uptake C2H2/CO2 separation, which outperforms most benchmark materials. Explicitly, MOF-OH adsorbs amount with record storage density 0.81 g mL–1 ambient conditions, even exceeds solid 189 K. addition, gave IAST selectivity 25 toward equimolar mixture C2H2/CO2, is nearly twice higher than MOF-NH2. Notably, adsorption enthalpies for zero converge in both MOFs are remarkably low (17.5 kJ mol–1 16.7 MOF-NH2), our knowledge lowest among rigid sorbents. The efficiencies validated multicycle breakthrough experiments. DFT calculations provide molecular-level insight over adsorption/separation mechanism. Moreover, can survive boiling water least 1 week be easily scaled up kilograms eco-friendly economically, crucial potential industrial implementation.

Язык: Английский

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Creating Optimal Pockets in a Clathrochelate-Based Metal–Organic Framework for Gas Adsorption and Separation: Experimental and Computational Studies

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(8), С. 3737 - 3745

Опубликована: Фев. 18, 2022

The rational design and synthesis of robust metal–organic frameworks (MOFs) based on novel organic building blocks are fundamental aspects reticular chemistry. Beyond simply fabricating new linkers, however, it is important to elucidate structure–property relationships at the molecular level develop high-performing materials. In this work, we successfully targeted a highly porous cage-type MOF (NU-200) with an nbo-derived fof topology through deliberate assembly cyclohexane-functionalized iron(II)-clathrochelate-based meta-benzenedicarboxylate linker Cu2(CO2)4 secondary unit (SBU). NU-200 exhibited outstanding adsorption capacity xenon high ideal adsorbed solution theory (IAST) predicted selectivity for 20/80 v/v mixture (Xe)/krypton (Kr) 298 K 1.0 bar. Our extensive computational simulations grand canonical Monte Carlo (GCMC) density functional (DFT) indicated that MOF's hierarchical bowl-shaped nanopockets surrounded by custom-designed cyclohexyl groups─instead conventionally believed open metal sites (OMSs)─played crucial role in reinforcing Xe-binding affinity. optimally sized pockets firmly trapped Xe numerous supramolecular interactions including Xe···H, Xe···O, Xe···π. Additionally, validated unique pocket confinement effect experimentally computationally employing similarly probe, sulfur dioxide (SO2), which provided significant insights into underpinnings uptake SO2 (11.7 mmol g–1), especially low pressure 0.1 bar (8.5 g–1). This work therefore can facilitate judicious blocks, producing MOFs featuring tailor-made boost gas separation performances.

Язык: Английский

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Surface-Clean Au₂₅ Nanoclusters in Modulated Microenvironment Enabled by Metal–Organic Frameworks for Enhanced Catalysis

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(48), С. 22008 - 22017

Опубликована: Ноя. 21, 2022

Metal nanoclusters (NCs) with atomically precise structures have sparked interest in catalysis. Unfortunately, their high aggregation tendency and the spatial resistance of surface ligands pose significant challenges. Herein, Au25 NCs are encapsulated into isoreticular metal-organic frameworks (MOFs), namely UiO-66-X (X = H, NH2, OH, NO2), followed by removal on NCs. The resulting surface-clean NCs, protected MOF confinement, exhibit much superior activity stability respect to pristine oxidative esterification furfural. Remarkably, experimental theoretical results jointly demonstrate that diverse functional groups modulate electronic state, giving rise discriminated substrate adsorption energy Au25@UiO-66-X. As a result, electron density suitable ability dominate trend: Au25@UiO-66-NH2 > Au25@UiO-66-OH Au25@UiO-66 Au25@UiO-66-NO2. This work develops new strategy for stabilization metal pore wall-engineered MOFs enhanced

Язык: Английский

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Photochromic crystalline hybrid materials with switchable properties: Recent advances and potential applications

Coordination Chemistry Reviews, Год журнала: 2022, Номер 475, С. 214918 - 214918

Опубликована: Окт. 31, 2022

Язык: Английский

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A Microporous Metal‐Organic Framework with Unique Aromatic Pore Surfaces for High Performance C₂H₆/C₂H₄ Separation

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(21)

Опубликована: Март 20, 2023

Developing adsorptive separation processes based on C2 H6 -selective sorbents to replace energy-intensive cryogenic distillation is a promising alternative for H4 purification from /C2 mixtures, which however remains challenging. During our studies two isostructural metal-organic frameworks (Ni-MOF 1 and Ni-MOF 2), we found that 2 exhibited significantly higher performance than Ni-MOF-1, as clearly established by gas sorption isotherms breakthrough experiments. Density-Functional Theory (DFT) showed the unblocked unique aromatic pore surfaces within induce more stronger C-H⋅⋅⋅π with over while suitable spaces enforce its high uptake capacity, featuring one of best porous materials this very important separation. It generates 12 L kg-1 polymer-grade product equimolar mixtures at ambient conditions.

Язык: Английский

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Synergistic binding sites in a hybrid ultramicroporous material for one-step ethylene purification from ternary C ₂ hydrocarbon mixtures

Science Advances, Год журнала: 2022, Номер 8(23)

Опубликована: Июнь 8, 2022

One-step separation of C 2 H 4 from ternary /C 6 hydrocarbon mixtures is great significance in the industry but challenging due to similar sizes and physical properties , . Here, we report an anion-pillared hybrid ultramicroporous material, CuTiF -TPPY, that has ability selective recognition over The 4,6-connected fsc framework -TPPY exhibits semi–cage-like one-dimensional channels sustained by porphyrin rings TiF 2− pillars, which demonstrates noticeably enhanced adsorption Dynamic breakthrough experiments confirm direct facile high-purity (>99.9%) production a gas mixture (1/9/90, v/v/v) under ambient conditions. Computational studies situ infrared reveal moieties with large π-surfaces form multiple van der Waals interactions ; meanwhile, polar pillars C–H•••F hydrogen bonding In contrast, sites for are less marked.

Язык: Английский

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