A hetero-supermolecular-building-block strategy for the assembly of porous (3,12,24)-connected uru metal–organic frameworks

Nature Synthesis, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 5, 2024

Language: Английский

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Quasicrystal approximants in isoreticular metal-organic frameworks via Cairo pentagonal tiling

Chem, Journal Year: 2024, Volume and Issue: 10(8), P. 2464 - 2472

Published: April 22, 2024

Language: Английский

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An Ultramicroporous Physisorbent Sustained by a Trifecta of Directional Supramolecular Interactions

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 2, 2025

2D and 3D porous coordination networks (PCNs) as exemplified by metal–organic frameworks, MOFs, have garnered interest for their potential utility sorbents molecular separations storage. The inherent modularity of PCNs has enabled the development crystal engineering strategies systematic fine-tuning pore size chemistry in families related PCNs. same cannot be said about one-dimensional (1D) polymers, CPs, which are understudied with respect to porosity. Here, we report that permanent porosity is exhibited previously reported family linear (L) 1D PCPs, formula [M(bipy)(NO3)2(H2O)2]n (L-chn-1-M-NO3: M = Co, Ni; bipy 4,4′-bipyridine). Their structure comprises channels sustained three types directional interaction: bonds; hydrogen offset π–π interactions. Heating L-chn-1-M-NO3 vacuo or above 383 K resulted removal aqua ligands concomitant transformation nonporous anhydrate phases ZZ-chn-1-Co-NO3 (ZZ zigzag) HT-Ni. Exposure these ambient humidity regeneration L-chn-1-M-NO3. That exhibits was supported CO2 water sorption measurements, afforded reversible type I stepped (S-shaped) isotherm profiles, respectively, making this work first demonstration a PCP. properties pertinent atmospheric harvesting: onset uptake at ca. 12% relative humidity; activation required only mild heat vacuum; relatively fast adsorption/desorption kinetics; performance retained over >100 cycles. We project harvesting productivity 3.3 L kg–1 d–1, on par some leading MOF desiccants. DFT Monte Carlo simulations provide insights into molecules channels, influence host framework, plausible argument experimental vapor isotherms. This demonstrates easily scalable potentially vast class materials, can exhibit structures supramolecular synthons offer desirable properties.

Language: Английский

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Proton-Conducting Hydrogen-Bonded Framework of a Cobalt(II) Single-Ion Magnet Sulfonate

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 13, 2025

Diamagnetic metal sulfonates have been widely reported, while paramagnetic species are very rare, especially those that exhibit interesting magnetic and/or proton conduction properties. Herein, we report the synthesis, structure, magnetic, and proton-conducting properties of a hydrogen-bonded cobalt(II) organosulfonate complex. The coordination self-assembly CoII salts 8-quinolinesulfonic acid ligands affords mononuclear sulfonate featuring both coordinated noncoordinated sulfonic O atoms axial water molecules. Notably, units further connected by short S–O···H–O hydrogen-bonding interactions between SO3– H2O, leading to three-dimensional (3D) network. This exhibits superior thermal stability, as proved variable-temperature single-crystal powder X-ray diffraction thermogravimetric analysis (TGA) analysis. Variable-temperature variable humidity ac impedance spectroscopy indicated this cobalt is good superionic conductor with highest measured conductivity 1.5 × 10–3 S cm–1 at 90 °C under 97% relative humility, originating from 1D zigzag chains. In addition, field-induced slow relaxation was observed via dynamic susceptibility measurements. These results show not only first Co(II) single-ion magnet but also ″magnetic anisotropic ion-organosulfonate-coordinated water″ approach for design preparation bifunctional metalo-hydrogen-bonded organic framework (MHOF) materials.

Language: Английский

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Manipulating Hydrogen-Bonding Donor/Acceptor in Ultra-Robust Isoreticular Zr(IV) Metal–Organic Frameworks for Efficient Regulation of Water Sorption Inflection Point and Steepness

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: 147(9), P. 7663 - 7670

Published: Feb. 20, 2025

The development of porous materials exhibiting steep and stepwise adsorption water vapor at desired humidity is crucial for implementing diverse applications such as control, heat allocation, atmospheric harvesting. precise molecular-level elucidation structural characteristics chemical components that dictate the sorption behaviors in confined nanospaces, metal-organic frameworks (MOFs) particular, fundamentally important, but this has yet to be largely explored. In work, by leveraging isoreticular principle, we crafted two pairs isostructural Zr-MOFs with linker backbones benzene pyrazine acting hydrogen-bonding donor acceptor, respectively. outstanding cyclic durability four permits persuasive investigation correlation inflection point steepness (the central figures-of-merit sorption) functionality. pyrazine-carrying both show uptake lower relative pressure slightly decreased steepness, which are quantitatively described Dubinin-Astakhov relation. We deciphered privileged clusters through single-crystal X-ray diffraction studies moiety formed stronger interactions guest molecules favored formation pentamers instead hexamers observed analog. donor/acceptor manipulation approach presented work may facilitate future research endeavors focusing on molecular attribute engineering predeterminedly ultrawater-resistant MOF platforms efficient regulation toward customized applications.

Language: Английский

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Hydrolytically Stable Phosphonate‐Based Metal–Organic Frameworks for Harvesting Water from Low Humidity Air

Small, Journal Year: 2025, Volume and Issue: unknown

Published: April 18, 2025

Abstract Harvesting water from air offers a promising solution to the global crisis. However, existing sorbents often struggle in arid climates due limitations such as low sorption capacities, hydrolytic instability, slow mass transport, high desorption enthalpy, and costly operation. Phosphonate‐based metal–organic frameworks (MOFs), known for their exceptional stability, have not been extensively explored harvesting. This study systematically investigates performance of STA‐12 (M═Co, Ni, Mg) STA‐16 Ni), series stable phosphonate‐based MOFs, sorbents. MOFs demonstrate remarkable adsorption at ultra‐low humidity (<10%), while STA‐16(Co) exhibits uptake capacity 0.54 g −1 10–50% relative (RH) 0.72 34% RH. Molecular simulations solid‐state NMR identified liquid‐like water, critical harvesting applications, key contributor superior STA‐16(Co). Scalable aqueous synthesis methods are developed, producing tens grams per batch without high‐pressure equipment. A prototype device incorporating STA‐12(Ni) demonstrated feasibility these materials real‐world harvesting, showcasing potential address scarcity regions.

Language: Английский

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Interconnected hollow metal–organic framework network towards excellent proton transfer for proton exchange membrane

Separation and Purification Technology, Journal Year: 2023, Volume and Issue: 335, P. 126224 - 126224

Published: Dec. 31, 2023

Language: Английский

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Moisture buffer value for hygroscopic materials with different thicknesses

Building and Environment, Journal Year: 2024, Volume and Issue: 258, P. 111581 - 111581

Published: April 26, 2024

Moisture buffer value (MBV) is a critical parameter for assessing hygroscopic material's ability to moderate indoor humidity variation. The original MBV theory strictly valid only semi-infinite (or "very thick") material. When the material thinner than semi-infinite, thickness will affect its moisture buffering ability. existing inapplicable. This study proposed new numerical method calculate at different thicknesses. model simple and efficient. relation between optimal can be obtained without extensive experimental measurement. What's more, adsorption desorption isotherms, as well hysteresis loop scanning are incorporated in model, making it applicable advanced desiccant materials like Metal-Organic Frameworks (MOFs). MIL-100(Fe), one of most promising MOF candidates control, was used validate newly developed model. MBVs MIL-100(Fe) samples with thicknesses were measured, data closely matched simulated results. Finally, building energy consumption simulation based on A panel placed BESTEST typical office room located Copenhagen. results show that reduce about 30 % air conditioning purely passive way.

Language: Английский

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A highly sensitive SERS aptasensor using a novel truncated aptamer for the detection of Deoxynivalenol

Sensors and Actuators B Chemical, Journal Year: 2024, Volume and Issue: 424, P. 136908 - 136908

Published: Nov. 7, 2024

Language: Английский

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Metal–Organic Framework on Fullerene (MOFOF) as a Hierarchical Composite by the Integration of Coordination Chemistry and Supramolecular Chemistry

ACS Applied Materials & Interfaces, Journal Year: 2024, Volume and Issue: 16(31), P. 41363 - 41370

Published: July 26, 2024

There is a synergy between coordination chemistry and supramolecular that has led to the development of innovative hierarchical composites with diverse functionalities. Here, we present novel approach for synthesis characterization metal–organic framework on fullerene (MOFOF) composites, achieved through integration principles. The nature MOFOF harnesses inherent properties frameworks fullerenes. two-step procedure involves controlled assembly fullerenes as tube-like nanostructures (fullerene nanotube: FNT), their surface functionalization, on-surface growth MOF (in this case, ZIF-67). method permits precise tuning morphology, effective distribution MOF-on-FNT, tight compositional control. materials were comprehensively structurally characterized using electron microscopy, spectroscopic techniques, other methods elucidate unique features interactions within composites. main findings reveal demonstrate successful designing fabricating advanced tailored properties, including micro- mesopore channels, interfacial facets, defect sites. These are expected lead numerous potential applications such gas storage separation, catalysis, sensing, energy storage, environmental remediation. However, only capability acid vapor sensing was tested described here.

Language: Английский

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