Heterometallic YbCo–Organic Framework for Efficiently Catalyzing Cycloaddition of CO₂ with Epoxides and Knoevenagel Condensation

Crystal Growth & Design, Год журнала: 2023, Номер 23(4), С. 2882 - 2892

Опубликована: Фев. 27, 2023

Due to the excellent catalytic performance of Co-MOFs and Ln-MOFs on chemical fixation CO2, self-assembly microporous heterometallic compounds with aid designed functional ligands is carried out in our group. Herein, solvothermal Co2+, Yb3+, 2,6-bis(2,4-dicarboxylphenyl)-4-(4-carboxylphenyl)pyridine (H5BDCP) generated a rarely reported {CoYb}n-chain-based framework {[CoYb(BDCP)(H2O)]·3DMF·3H2O}n (NUC-70) quasi-nanoporous channels (aperture ca. 11.4 Å) shaped by six rows {CoYb(CO2)5(H2O)}n nodes. To best knowledge, this rare 3d-4f chain staggered arrangement Co2+ Yb3+. After removing associated water molecules, NUC-70a possesses characteristics large specific surface area, unsaturated open metal sites Yb3+ as Lewis acid sites, high heat/water-resistant physicochemical properties. Catalytic experiments showed that possessed activity cycloaddition reactions epoxides CO2 under mild conditions. Furthermore, performed confirmed Knoevenagel condensation aldehydes malononitrile could be efficiently catalyzed NUC-70a. This work illustrates characteristic ligand design plays key role MOFs functions.

Язык: Английский

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Enhancement of Luminescence, Multiple-Sensing, and Differentiated Live-Cell-Imaging Properties of High-Nuclear Lanthanide Nanoclusters via the Zn(II)-Chelate-Controlled Dual Antenna Effect

ACS Materials Letters, Год журнала: 2024, Номер 6(8), С. 3312 - 3326

Опубликована: Июнь 26, 2024

Enhancing the "antenna effect" of ligands and promoting energy transfer to a lanthanide metal center is one most effective ways construct complex-based emitters with bright emissions. Herein, highly stable nanoclusters (Ln9Zn8; Ln = Dy, Tb, Eu, or Gd) were constructed using Zn(II) metalloligand protection strategy, "dual antenna was selectively turned on enhance luminescence Eu9Zn8. The enabled dual effect for Eu9Zn8, resulting in its solid state being significantly stronger than that Tb9Zn8. Eu9Zn8 has excellent optical sensing properties Al3+, Fe3+, Cr2O72–. Notably, ultrasmall nanocluster showed cellular uptake labeling capabilities after incubation HeLa, MDA–MB–231, HepG2, H9c2, 4T1, SK–OV–3, MCF–7 cells. This work opens up new horizons application biological imaging.

Язык: Английский

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Optimizing d‐p Orbital Hybridization with Abundant Unfilled Antibonding Orbital in Multi‐Metal Layered Double Hydroxide: Motivating Efficient Oxygen Evolving

Advanced Functional Materials, Год журнала: 2024, Номер 34(22)

Опубликована: Фев. 4, 2024

Abstract Manipulating the electronic structure and coordination configuration of heterogeneous electrocatalyst is an advantageous strategy to motivate intrinsic activity but remains challenging. Herein, guided by theoretical mechanism d‐band center valence‐bond theory, high‐valence metal‐modulated nickel‐vanadium layered double hydroxides (M‐NiV LDH, M = Zr, Mo) with interfacial oxygen bridge bonding are rationally designed fabricated, affording a 3D vertically staggered porous nanosheets array network. Benefitting from abundant unfilled antibonding orbitals induced optimized Zr d‐orbital O p‐orbital hybridization, introduction site beneficial accelerate charge transfer kinetics optimize deprotonation OH* as well lower O* → OOH* free energy. As result, as‐prepared Zr‐NiV LDH exhibits promising evolution reaction performance low overpotential favorable long‐term stability. This work provides valuable insights into design electrocatalysts for regulation improvement.

Язык: Английский

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Boosting Enzyme Activity in Enzyme Metal–Organic Framework Composites

Chem & Bio Engineering, Год журнала: 2024, Номер 1(2), С. 99 - 112

Опубликована: Фев. 8, 2024

Enzymes, as highly efficient biocatalysts, excel in catalyzing diverse reactions with exceptional activity and selective properties under mild conditions. Nonetheless, their broad applications are hindered by inherent fragility, including low thermal stability, limited pH tolerance, sensitivity to organic solvents denaturants. Encapsulating enzymes within metal–organic frameworks (MOFs) can protect them from denaturation these harsh environments. However, this often leads a compromised enzyme activity. In recent years, extensive research efforts have been dedicated enhancing enzymatic MOFs, leading the development of new enzyme–MOF composites that not only preserve catalytic potential but also outperform free counterparts. This Review provides comprehensive review on developments specific emphasis enhanced compared enzymes.

Язык: Английский

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Low thermal quenching of metal halide-based metal–organic framework phosphor for light-emitting diodes

Chemical Science, Год журнала: 2024, Номер 15(35), С. 14202 - 14208

Опубликована: Янв. 1, 2024

A green MOF phosphor can maintain 84% of its initial emission intensity after being heated to 150 °C, exceeding several commercial inorganic phosphors.

Язык: Английский

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COFcap2, a recyclable tandem catalysis reactor for nitrogen fixation and conversion to chiral amines

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

Опубликована: Янв. 24, 2025

Two or more catalysts conducting multistep reactions in the same reactor, concurrent tandem catalysis, could enable (bio)pharmaceutical and fine chemical manufacturing to become much sustainable. Herein we report that co-immobilization of metal nanoparticles a biocatalytic system within synthetic covalent organic framework capsule, COFcap-2, functions like an artificial cell that, whereas are trapped 300-400 nm cavities, substrates/products can ingress/egress through ca. 2 windows. The COFcap-2 reactor is first coated onto electrode surface then used prepare eleven homochiral amines using dinitrogen as feedstock. amines, including drug product intermediates active pharmaceutical ingredient, prepared >99% enantiomeric excess under ambient conditions water. Importantly, recycled 15 times with retention performance, addressing relative instability poor recyclability enzymes has hindered their broad implementation for energy-efficient, low waste production chemicals (bio)pharmaceuticals. Concurrent two would be beneficial manufacturing. Here, authors multienzyme employ it

Язык: Английский

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Polysaccharides-Directed Biomineralization of Enzymes in Hierarchical Zeolite Imidazolate Frameworks for Electrochemical Detection of Phenols

ACS Applied Materials & Interfaces, Год журнала: 2025, Номер unknown

Опубликована: Янв. 14, 2025

Biomineralization of enzymes inside rigid metal-organic frameworks (MOFs) is appealing due to its biocompatibility and simplicity. However, this strategy has hitherto been limited microporous MOFs, leading low apparent enzymatic activity. In study, polysaccharide sodium alginate introduced during the biomineralization in zeolitic imidazolate (ZIFs) competitively coordinate with metal ions, which endows encapsulated enzyme a 7-fold higher activity than that ZIFs. Mechanism investigation showed introduction generates hierarchical porous structures enhances hydrophilicity, contributes enhanced enzyme. Moreover, ZIFs protect embedded tyrosinase under detrimental conditions, allows for fast detection phenol, limit 0.03 mM (S/N = 3). Engineering MOFs enhance stability anticipated extend application biocatalysis biosensors.

Язык: Английский

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Construction of enzyme-MOFs composite with carbon dots: A strategy to enhance the activity and increase the growth rate of the enzyme-ZIF-8 composite

International Journal of Biological Macromolecules, Год журнала: 2025, Номер unknown, С. 139985 - 139985

Опубликована: Янв. 1, 2025

Язык: Английский

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ZIF‐8 Functionalized Separator Regulating Na‐Ion Flux and Enabling High‐Performance Sodium‐Metal Batteries

Small Methods, Год журнала: 2025, Номер unknown

Опубликована: Фев. 13, 2025

Abstract The practical application of sodium metal batteries faces significant challenges, such as unpredictable Na dendrite growth and the instability solid‐electrolyte interphase. Herein, a novel separator composed glass fiber (GF) impregnated with zeolitic imidazolate framework (ZIF‐8) layer, referred to GF@ZIF‐8 is introduced. This optimized exhibits enhanced anti‐puncture strength, high transference number, fast Na‐ion conductivity. ZIF‐8 layer effectually regulates spatial concentration distribution ions their flux vectors, leading homogeneous deposition Na. Consequently, Na||Na symmetric cells utilizing demonstrate outstanding cyclability, achieving 850 h at 0.5 mA cm −2 420 1 , outperforming bare GF (<180 h). Furthermore, assembled 3 V 2 (PO 4 ) ||GF@ZIF‐8||Na full exhibit remarkably improves rate performance (81 g −1 30 C), cyclability (93.5% capacity retention over 900 cycles 10 low‐temperature applicability (78 under 0.2 C −40 °C). simulations reveal that, except for regulating flux, introduction porous on also enhances local electric field near anode, thereby boosting transfer + which contributes improved storage performance.

Язык: Английский

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Highly Enantioselective Catalysis by Enzyme Encapsulated in Metal Azolate Frameworks with Micelle-Controlled Pore Sizes

ACS Central Science, Год журнала: 2024, Номер 10(2), С. 358 - 366

Опубликована: Янв. 18, 2024

Encapsulating enzymes within metal–organic frameworks has enhanced their structural stability and interface tunability for catalysis. However, the small apertures of restrict effectiveness to organic molecules. Herein, we present a green strategy directed by visible linker micelles aqueous synthesis MAF-6 that enables catalytic asymmetric chiral Due large pore aperture (7.6 Å), double size benchmark ZIF-8 (3.4 allows encapsulated enzyme BCL access larger substrates do so faster. Through optimization surfactants' effect during synthesis, BCL@MAF-6-SDS (SDS = sodium dodecyl sulfate) displayed efficiency (Kcat/Km) was 420 times greater than BCL@ZIF-8. This biocomposite efficiently catalyzed drug precursor molecules with 94–99% enantioselectivity nearly quantitative yields. These findings represent deeper understanding de novo synthetic encapsulation in MOFs, thereby unfolding great potential enzyme@MAF catalysts organics pharmaceuticals.

Язык: Английский

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