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

---

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

---

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

---

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

---

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

---

Reversed CO2/C2H2 separation via combined adsorption kinetics and diffusion differences in MOF-polymer mixed matrix membrane

Journal of Membrane Science, Год журнала: 2025, Номер unknown, С. 123827 - 123827

Опубликована: Фев. 1, 2025

Язык: Английский

---

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

---

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

---

Fluorinated MOF‐Based Hexafluoropropylene Nanotrap for Highly Efficient Purification of Octafluoropropane Electronic Specialty Gas

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

Опубликована: Фев. 16, 2024

Abstract High‐purity octafluoropropane (C 3 F 8 ) electronic specialty gas is a key chemical raw material in semiconductor and integrated circuit manufacturing industry, while selective removal of hexafluoropropylene 6 impurity for C purification essential but challenging task. Here we report fluorinated cage‐like MOF Zn‐bzc‐CF (bzc=5‐(trifluoromethyl)‐1H‐pyrazole‐4‐carboxylic acid) /C separation. The incorporation −CF groups not only provides suitable pore aperture size highly efficient size‐exclusive separation, also creates hydrophobic microenvironments, endowing Zn‐bz‐CF high stability. Remarkably, exhibits adsorption capacity excluding , achieving ideal molecular‐sieving Breakthrough experiments show that can efficiently separate mixture high‐purity (99.9 %) be obtained.

Язык: Английский

---

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

---