Recent Advances in Confining Polyoxometalates and the Applications

Small, Год журнала: 2023, Номер 19(24)

Опубликована: Март 17, 2023

Abstract Polyoxometalates (POMs) are widely used in catalysis, energy storage, biomedicine, and other research fields due to their unique acidity, photothermal, redox features. However, the leaching agglomeration problems of POMs greatly limit practical applications. Confining a host material is an efficient tool address above‐mentioned issues. POM@host materials have received extensive attention recent years. They not only inherent characteristics host, but also play significant synergistic effect from each component. This review focuses on advances development applications materials. Different types elaborated detail, including tubular, layered, porous Variations structures properties hosts before after confinement highlighted as well. In addition, overview for representative electrochemical, catalytic, biological provided. Finally, challenges future perspectives composites discussed.

Язык: Английский

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Precise Regulation of the Coordination Environment of Single Co(II) Sites in a Metal–Organic Framework for Boosting CO₂ Photoreduction

ACS Catalysis, Год журнала: 2023, Номер 13(13), С. 8760 - 8769

Опубликована: Июнь 16, 2023

While the coordination environment around catalytic metal sites plays a crucial role in catalysis, its precise design and modulation still remain challenge. Herein, coordinated N atom number single Co installed on UiO-type metal–organic framework has been modulated to afford UiO-Co-Nx (x = 2, 3, 4) for photocatalytic CO2 reduction. Significantly, performance is affected by site, which UiO-Co-N3 exhibits superior activity other counterparts. Photo-/electrochemical results support fastest charge transfer kinetics between photosensitizer UiO-Co-N3. Theoretical calculations, together with acquired from situ diffuse reflectance infrared Fourier transform spectra, manifest lowest energy barriers of rate-determining step desorption CO* over among all samples.

Язык: Английский

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Multi-compartmental MOF microreactors derived from Pickering double emulsions for chemo-enzymatic cascade catalysis

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Июнь 3, 2023

Bioinspired multi-compartment architectures are desired in synthetic biology and metabolic engineering, as credited by their cell-like structures intrinsic ability of assembling catalytic species for spatiotemporal control over cascade reactions like living systems. Herein, we describe a general Pickering double emulsion-directed interfacial synthesis method the fabrication multicompartmental MOF microreactors. This approach employs multiple liquid-liquid interfaces controllable platform self-completing growth dense layers, enabling microreactor with tailor-made inner selective permeability. Importantly, simultaneous encapsulation incompatible functionalities, including hydrophilic enzyme hydrophobic molecular catalyst, can be realized single operating chemo-enzymatic reactions. As exemplified Grubb' catalyst/CALB lipase driven olefin metathesis/ transesterification reaction glucose oxidase (GOx)/Fe-porphyrin catalyzed oxidation reaction, exhibits 2.24-5.81 folds enhancement efficiency comparison to homogeneous counterparts or physical mixture individual analogues, due restrained mutual inactivation substrate channelling effects. Our study prompts further design multicompartment systems development artificial cells capable complex cellular transformations.

Язык: Английский

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Heteroatom‐Doped Ag₂₅ Nanoclusters Encapsulated in Metal–Organic Frameworks for Photocatalytic Hydrogen Production

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(17)

Опубликована: Фев. 26, 2024

Atomically precise metal nanoclusters (NCs) with unique optical properties and abundant catalytic sites are promising in photocatalysis. However, their light-induced instability the difficulty of utilizing photogenerated carriers for photocatalysis pose significant challenges. Here, MAg

Язык: Английский

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MXenes@metal-organic framework hybrids for energy storage and electrocatalytic application: Insights into recent advances

Chemical Engineering Journal, Год журнала: 2023, Номер 470, С. 144247 - 144247

Опубликована: Июнь 19, 2023

Язык: Английский

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Noncentrosymmetric Lanthanide-Based MOF Materials Exhibiting Strong SHG Activity and NIR Luminescence of Er³⁺: Application in Nonlinear Optical Thermometry

ACS Applied Materials & Interfaces, Год журнала: 2023, Номер 15(2), С. 3244 - 3252

Опубликована: Янв. 5, 2023

Optically active luminescent materials based on lanthanide ions attract significant attention due to their unique spectroscopic properties, nonlinear optical activity, and the possibility of application as contactless sensors. Lanthanide metal-organic frameworks (Ln-MOFs) that exhibit strong second-harmonic generation (SHG) are optically in NIR region unexpectedly underrepresented. Moreover, such Ln-MOFs require ligands chiral and/or need multistep synthetic procedures. Here, we show pulsed laser irradiation noncentrosymmetric, isostructural Ln-MOF (MOF-Er3+ (1) codoped MOF-Yb3+/Er3+ (2)) constructed from simple, achiral organic substrates a one-step procedure results tunable SHG activity. The signals could be easily collected, exciting broad spectral range, ≈800 1500 nm, resulting intense color emission, observed entire visible region. upon excitation range ≈900 1025 also luminescence Er3+ ions, centered at ≈1550 nm. use 975 nm pulse allows simultaneous observations conventional emission signal, altogether tuned by composition materials. Taking benefits different thermal responses mentioned effects, have developed thermometer lanthanide-MOF In this system, signal decreases with temperature, whereas band slightly broadens, allowing ratiometric (Er3+ 1550 nm/SHG 488 nm) temperature monitoring. Our study provides groundwork for rational design readily available self-monitoring NLO-active desired electronic properties.

Язык: Английский

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Water‐Stable High‐Entropy Metal‐Organic Framework Nanosheets for Photocatalytic Hydrogen Production

Advanced Materials, Год журнала: 2024, Номер 36(26)

Опубликована: Апрель 8, 2024

Abstract Metal‐organic frameworks (MOFs) have emerged as promising platforms for photocatalytic hydrogen evolution reaction (HER) due to their fascinating physiochemical properties. Rationally engineering the compositions and structures of MOFs can provide abundant opportunities optimization. In recent years, high‐entropy materials (HEMs) demonstrated great potential in energy environment fields. However, there is still no report on development (HE‐MOFs) HER aqueous solution. Herein, authors synthesis a novel p ‐type HE‐MOFs single crystal (HE‐MOF‐SC) corresponding nanosheets (HE‐MOF‐NS) capable realizing visible‐light‐driven HER. Both HE‐MOF‐SC HE‐MOF‐NS exhibit higher activity than all single‐metal MOFs, which are supposed be ascribed interplay between different metal nodes that enables more efficient charge transfer. Moreover, impressively, demonstrates much its thin thickness enhanced surface area. At optimum conditions, rate H 2 ≈13.24 mmol h −1 g , among highest values reported water‐stable MOF photocatalysts. This work highlights importance developing advanced toward photocatalysis.

Язык: Английский

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Prussian blue and its analogs: A robust platform for efficient capacitive deionization

Desalination, Год журнала: 2024, Номер 574, С. 117278 - 117278

Опубликована: Янв. 2, 2024

Язык: Английский

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Modulating the Primary and Secondary Coordination Spheres of Single Ni(II) Sites in Metal–Organic Frameworks for Boosting Photocatalysis

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(15), С. 10798 - 10805

Опубликована: Апрель 5, 2024

Though the coordination environment of single metal sites has been recognized to be great importance in promoting catalysis, influence simultaneous precise modulation primary and secondary spheres on catalysis remains largely unknown. Herein, a series Ni(II) with altered have installed onto metal–organic frameworks (MOFs) UiO-67 skeleton, affording UiO–Ni–X–Y (X = S, O; Y H, Cl, CF3) X spheres, respectively. Upon deposition CdS nanoparticles, resulting composites present high photocatalytic H2 production rates, which optimized CdS/UiO–Ni–S–CF3 exhibits an excellent activity 13.44 mmol g–1, ∼500 folds pristine catalyst (29.6 μmol g–1 for CdS/UiO), 8 h, highlighting key role microenvironment around Ni sites. Charge kinetic analysis theoretical calculation results demonstrate that charge transfer dynamics reaction energy barrier are closely correlated their spheres. This work manifests advantages MOFs fabrication structurally catalysts elucidation particular influences catalytic performance.

Язык: Английский

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Nanoparticle proximity controls selectivity in benzaldehyde hydrogenation

Nature Catalysis, Год журнала: 2024, Номер 7(2), С. 172 - 184

Опубликована: Фев. 16, 2024

Язык: Английский

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