Metalation of metal–organic frameworks: fundamentals and applications

Chemical Society Reviews, Год журнала: 2024, Номер 53(11), С. 5626 - 5676

Опубликована: Янв. 1, 2024

Metalation of metal-organic frameworks (MOFs) has been developed as a prominent strategy for materials functionalization pore chemistry modulation and property optimization. By introducing exotic metal ions/complexes/nanoparticles onto/into the parent framework, many metallized MOFs have exhibited significantly improved performance in wide range applications. In this review, we focus on research progress metalation during last five years, spanning design principles, synthetic strategies, potential Based crystal engineering minor change MOF composition through would lead to leveraged variation properties. This review starts from general strategies established incorporation species within MOFs, followed by principles graft desired functionality while maintaining porosity frameworks. Facile contributed great number bespoke with excellent performance, summarize their applications gas adsorption separation, heterogeneous catalysis, detection sensing, energy storage conversion. The underlying mechanisms are also investigated state-of-the-art techniques analyzed gaining insight into structure-property relationships, which turn facilitate further development principles. Finally, current challenges opportunities discussed, promising future directions customizing next-generation advanced outlined well.

Язык: Английский

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Tailoring Hydrophobicity and Pore Environment in Physisorbents for Improved Carbon Dioxide Capture under High Humidity

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(6), С. 3943 - 3954

Опубликована: Янв. 31, 2024

CALF-20, a Zn-triazolate-based metal–organic framework (MOF), is one of the most promising adsorbent materials for CO2 capture. However, competitive adsorption water severely limits its performance when relative humidity (RH) exceeds 40%, limiting potential implementation CALF-20 in practical settings where saturated with moisture, such as postcombustion flue gas. In this work, three newly designed MOFs related to denoted NU-220, CALF-20M-w, and CALF-20M-e that feature hydrophobic methyltriazolate linkers, are presented. Inclusion methyl groups linker proposed strategy improve uptake presence water. Notably, both CALF-20M-w retain over 20% their initial capture efficiency at 70% RH─a threshold which shows negligible uptake. Grand canonical Monte Carlo simulations reveal group hinders network formation pores enhances selectivity N2 high moisture content. Moreover, calculated radial distribution functions indicate introducing into triazolate increases distance between molecules Zn coordination bonds, offering insights origin enhanced stability observed CALF-20. Overall, straightforward design has afforded more robust sorbents can potentially meet challenge effectively capturing industrial applications.

Язык: Английский

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

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(39)

Опубликована: Авг. 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.

Язык: 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, Год журнала: 2024, Номер 146(11), С. 7341 - 7351

Опубликована: Март 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.

Язык: Английский

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Benchmarking selective capture of trace CO2 from C2H2 using an amine-functionalized adsorbent

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Март 16, 2025

Purifying C2H2 by removing trace CO2 is critically needed yet challenged their analogous physical properties. Herein, we report a commercial resin adsorbent HP20 (Diaion® HP-20 Resin) loaded with polyethyleneimine (PEI@HP20) which selectively captures and excludes C2H2. PEI@HP20 possesses high adsorption capacity (4.35 mmol/g) at 100 kPa 298 K record CO2/C2H2 uptake ratio compared all reported CO2-selective adsorbents. The ideal adsorbed solution theory selectivity reaches 1.33×107. pilot-scale pressure-temperature swing on 2 kg further validated that it can obtain >99.99% purity from CO2/C2H2(1/99, v/v) mixtures yield of 344.7 g per cycle. combination multinuclear solid-state Nuclear Magnetic Resonance, Fourier Transform infrared spectroscopy density functional calculations reveal the performance relies dual chemisorption/physisorption mechanism. This work highlights promising method to develop green, low cost, efficiency, readily scalable adsorbent. but challenging due authors production for selective capture traces exclusion

Язык: Английский

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Pore Space Partition Enabled by Lithium(I) Chelation of a Metal–Organic Framework for Benchmark C₂H₂/CO₂ Separation

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Март 20, 2025

Adsorptive separation of acetylene (C2H2) from carbon dioxide (CO2) offers a promising approach to purify C2H2 with low-energy footprints. However, the development ideal adsorbents simultaneous high adsorption and selectivity remains great challenge due their very small molecular sizes physical properties. Herein, we report lithium(I)-chelation strategy for pore space partition (PSP) in microporous MOF (Li+@NOTT-101-(COOH)2) achieve uptake selectivity. The chelation model Li+ ions within framework was visually identified by single-crystal X-ray diffraction studies. immobilized were found have two functions: (1) partitioning large cages into smaller ones while maintaining surface area (2) providing specific binding sites selectively take up over CO2. resulting Li+@NOTT-101-(COOH)2 exhibits rare combination capture capacity (205 cm3 g-1) C2H2/CO2 (13) at ambient conditions, far surpassing that NOTT-101-(COOH)2 (148 g-1 3.8, respectively) most top-tier materials reported. Theoretical calculations gas-loaded SCXRD studies reveal chelated combined segmented can bind amount through unique π-complexation, accounting improved Breakthrough experiments validated its excellent actual mixtures, one highest productivities 118.9 L kg-1 (>99.5% purity) single adsorption-desorption cycle.

Язык: Английский

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Room-temperature aqueous synthesis of MOF-808(Zr) for selective adsorption of dye mixtures

Separation and Purification Technology, Год журнала: 2023, Номер 333, С. 125957 - 125957

Опубликована: Дек. 6, 2023

Язык: Английский

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Efficient C2H2/CO2 and C2H2/C2H4 separations in a novel fluorinated metal–organic framework

Separation and Purification Technology, Год журнала: 2023, Номер 332, С. 125777 - 125777

Опубликована: Ноя. 21, 2023

Язык: Английский

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Efficient carbon dioxide capture from flue gas and natural gas by a robust metal–organic framework with record selectivity and excellent granulation performance

Separation and Purification Technology, Год журнала: 2024, Номер 343, С. 127099 - 127099

Опубликована: Март 13, 2024

Язык: Английский

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Scalable Synthesis of Robust MOF for Challenging Ethylene Purification and Propylene Recovery with Record Productivity

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(15)

Опубликована: Фев. 19, 2024

Abstract Ethylene (C 2 H 4 ) purification and propylene 3 6 recovery are highly relevant in polymer synthesis, yet developing physisorbents for these industrial separation faces the challenges of merging easy scalability, economic feasibility, high moisture stability with great efficiency. Herein, we reported a robust scalable MOF (MAC‐4) simultaneous C . Through creating nonpolar pores decorated by accessible N/O sites, MAC‐4 displays top‐tier uptakes selectivities over at ambient conditions. Molecular modelling combined infrared spectroscopy revealed that molecules were trapped framework stronger contacts relative to Breakthrough experiments demonstrated exceptional performance binary /C as well ternary mixtures, simultaneously affording record productivities 27.4 36.2 L kg −1 high‐purity (≥99.9 %) (≥99.5 %). was facilely prepared deckgram‐scale under reflux condition within hours, making it smart address challenging gas separations.

Язык: Английский

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