Vertex Strategy in Layered 2D MOFs: Simultaneous Improvement of Thermodynamics and Kinetics for Record C₂H₂/CO₂ Separation Performance

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(16), P. 9254 - 9263

Published: April 13, 2023

Developing adsorbents with multiple merits in capacity, selectivity, mass transfer, and stability toward C2H2/CO2 separation is crucial challenging for producing high-purity C2H2 advanced polymers the electronic industry. Here, we demonstrate a vertex strategy to create combining these through rationally designing groups of wavy-shaped framework layered 2D metal-organic frameworks (MOFs) finely regulate local conformation stacking interactions, which creates optimal inter- intralayer space realize simultaneous improvement adsorption thermodynamics kinetics. Two new hydrolytically stable MOFs, ZUL-330 ZUL-430, were prepared, diverse experiments modeling on both equilibrium diffusion performed. Record selectivities coupled extraordinary dynamic capacities achieved mixtures different proportions (50/50 or 10/5, v/v), along small barrier fast transfer. Consequently, polymer-grade (99.9%) electronic-grade (99.99%) obtained excellent productivities up ∼6 mmol cm-3.

Language: Английский

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pH-Stable Zn(II) Coordination Polymer as a Multiresponsive Turn-On and Turn-Off Fluorescent Sensor for Aqueous Medium Detection of Al(III) and Cr(VI) Oxo-Anions

Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 62(34), P. 14124 - 14133

Published: Aug. 17, 2023

Nowadays, coordination polymers (CPs) are promising candidates as sensory materials for their high sensitivity, improved selectivity, fast responsive nature, well good recyclability. However, poor chemical stability often makes practical usage limited. Herein, employing a mixed ligand approach, we constructed chemically robust CP, {[Zn2L2(DPA)2]·3H2O}n (IITKGP-70, IITKGP stands the Indian Institute of Technology Kharagpur), which exhibited excellent framework robustness not only in water but also over broad range pH solutions (pH = 3–11). The developed displayed selectivity and sensitivity detection trivalent Al3+ ions toxic hexavalent Cr(VI)-oxo anions an aqueous medium. medium turn-on phenomenon with limit (LOD) value 1.29 μM, whereas turn-off effect was observed oxo-anions (Cr2O72– CrO42–) having LOD values 0.27 0.71 respectively. Both mechanisms speculated via spectroscopic methods coupled several ex situ studies. Such multiresponsive nature (both turn-off) targeted cations simultaneously single platform robustness, ease scalability, recyclability, fast-responsive IITKGP-70 highly fascinating material real-world applications.

Language: Английский

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

Separation and Purification Technology, Journal Year: 2023, Volume and Issue: 332, P. 125777 - 125777

Published: Nov. 21, 2023

Language: Английский

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Pore Chemistry and Architecture Control in Anionic Functional Ultramicroporous Materials for Record Dense Packing of Xenon

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(36), P. 24956 - 24965

Published: Aug. 5, 2024

Adsorptive separation of Xe and Kr is an industrially promising but challenging process because their identical shape similar physicochemical properties. Herein, we demonstrate a strategy through rationally designing the linkers anionic functional ultramicroporous materials (FUMs) to finely regulate pore chemistry architecture, which creates unique stepped channels incorporating dense polar nanotraps generate larger effective space enables packing Xe. A new hydrolytically stable FUM (ZUL-530) was prepared, for first time achieves density exceeding liquid at atmospheric conditions in metal−organic frameworks (MOFs) (based on experimental data), resulting both excellent uptake (2.55 mmol g–1 0.2 bar) high IAST selectivity (20.5). GCMC DFT-D calculations reveal essential role traps Breakthrough experiments remarkable productivities high-purity (6.70 g–1) (1.78 Xe/Kr (20:80) mixture. In model nuclear industry exhaust gas, ZUL-530 exhibits top-class dynamic capacity (28.8 kg–1) trace Xe, proves it one best candidates separation.

Language: Английский

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A Highly Stable Microporous Calcium-Based MOF for C₂H₂/CO₂ Separation with Low Regenerative Energy

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(18), P. 8329 - 8335

Published: April 22, 2024

Most of the porous materials used for acetylene/carbon dioxide separation have problems poor stability and high energy requirements regeneration, which significantly hinder their practical application in industries. Here, we report a novel calcium-based metal–organic framework (NKM-123) with excellent chemical against water, acids, bases. Additionally, it has exceptional thermal stability, retaining its structural integrity at temperatures up to 300 °C. This material exhibits promising potential separating C2H2 CO2 gases. Furthermore, demonstrates an adsorption heat 29.3 kJ mol–1 C2H2, is lower than that observed majority MOFs C2H2/CO2 separations. The preferential over confirmed by dispersion-corrected density functional theory (DFT-D) calculations. In addition, industrial feasibility NKM-123 transient breakthrough tests. robust cycle performance during multiple tests show great light hydrocarbons.

Language: Английский

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Single-Molecule Traps in Covalent Organic Frameworks for Selective Capture of C ₂ H ₂ from C ₂ H ₄ -Rich Gas Mixtures

Research, Journal Year: 2024, Volume and Issue: 7

Published: Jan. 1, 2024

Removing trace amounts of acetylene (C 2 H ) from ethylene 4 )-rich gas mixtures is vital for the supply high-purity C to chemical industry and plastics sector. However, selective removal challenging due similar physical properties . Here, we report a “single-molecule trap” strategy that utilizes electrostatic interactions between one-dimensional (1D) channel covalent organic framework (denoted as COF-1) molecules massively enhance adsorption selectivity toward over are immobilized via with O atom C=O groups, N C≡N phenyl groups in 1D channels COF-1. Due its exceptionally high affinity , COF-1 delivered remarkable uptake 7.97 cm 3 /g at 298 K 0.01 bar, surpassing all reported COFs many other state-of-the-art adsorbents under conditions. Further, demonstrated outstanding performance separation breakthrough experiments dynamic adsorbed capacity 0.17 2,000 s/g when exposed 0.5 ml/min -rich mixture (99% K, directly producing rate 3.95 /g. Computational simulations showed strong single-molecule traps were responsible excellent performance. also robust, providing promising new efficient practical purification.

Language: Английский

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Gate-Opening Effect in a Flexible Metal–Organic Framework for Sieving Acetylene

Chem & Bio Engineering, Journal Year: 2024, Volume and Issue: 1(2), P. 150 - 156

Published: Feb. 15, 2024

Adsorptive separation employing porous materials is one of the most promising alternative technologies for C2H2 purification due to its energy-efficient and environmentally friendly advantages. Herein, we present design synthesis a dicopper-paddle-wheel-based metal-organic framework (termed JNU-5-Me) with carboxylate-azolate organic linker. The use such linker results in axial positions dicopper paddle wheels being occupied by azolates, therefore, much-improved chemical stability structure. JNU-5-Me shows negligible adsorption C2H4, C2H6, CO2 at 1.0 bar 298 K, while gate-opening effect large (4.7 mmol g-1) K. Dynamic breakthrough studies on demonstrate excellent performance from C2H2/CO2 (50/50, v/v) C2H2/CO2/C2H4/C2H6 (70/10/10/10, v/v/v/v) mixtures. Additionally, in-situ infrared spectroscopy Grand canonical Monte Carlo (GCMC) simulation reveal that carboxylate oxygens methyl groups are involved strong binding C2H2, which may be attributed JNU-5-Me.

Language: Английский

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Mechanistical Insights into the Ultrasensitive Detection of Radioactive and Chemotoxic UO₂²⁺ Ions by a Porous Anionic Co-Metal–Organic Framework

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(22), P. 10403 - 10413

Published: May 18, 2024

Development of a simple, cost-efficient, and portable UO22+ sensory probe with high selectivity sensitivity is highly desirable in the context monitoring radioactive contaminants. Herein, we report luminescent Co-based metal–organic framework (MOF), {[Me2NH2]0.5[Co(DATRz)0.5(NH2BDC)]·xG}n (1), equipped abundant amino functionalities for selective detection uranyl cations. The ionic structure consists two types channels decorated plentiful Lewis basic moieties, which trigger stronger acid–base interaction diffused cationic units thus can selectively quench fluorescence intensity presence other interfering ions. Furthermore, limit sensing was achieved to be as low 0.13 μM (30.94 ppb) rapid responsiveness multiple recyclabilities, demonstrating its excellent efficacy. Density functional theory (DFT) calculations further unraveled preferred binding sites ions tubular channel MOF structure. Orbital hybridization between NH2BDC/DATRz together significantly large electron-accepting ability identified responsible luminescence quenching. More importantly, prepared 1@PVDF {poly(vinylidene difluoride)} mixed-matrix membrane (MMM) displayed good activity comparable 1, great significance their practical employment MOF-based luminosensors real-world application.

Language: Английский

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Construction of Multiple-Component Covalent Organic Frameworks by an In-Situ Approach for Boosting Palladium Recovery from Strong Acid

ACS Materials Letters, Journal Year: 2023, Volume and Issue: 5(10), P. 2665 - 2672

Published: Aug. 31, 2023

Multiple-component covalent organic frameworks (COFs) show outstanding advantages in both structure and function over the common two-component COFs. Herein, we a simple but general synthesis of multiple-component COFs through an in-situ approach. In simplest C4 + C2 binary condensation system, observed substitute-induced formed linkers consequently conversion from sql COF to three-component sql-defect COF. However, another C3 topology- finally 3,4-connected hcb-defect Such difference topology between three- is very different established that same as comparable These new finds, evidenced by experimental theoretical results, mainly originated steric hindrance effect. Moreover, also disclosed structure–function relationship among palladium recovery, substitute effect, pore size COFs, one was found benchmark performance recovery strong acid (3 M). The results shed light on fundamental design for its advanced application.

Language: Английский

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Unveiling the potential of ingenious copper-based metal-organic frameworks in gas storage and separation

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 522, P. 216230 - 216230

Published: Sept. 26, 2024

Language: Английский

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