Metal-organic framework composites as green/sustainable catalysts

Coordination Chemistry Reviews, Год журнала: 2021, Номер 436, С. 213827 - 213827

Опубликована: Фев. 21, 2021

Язык: Английский

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Metal–organic framework (MOF)-, covalent-organic framework (COF)-, and porous-organic polymers (POP)-catalyzed selective C–H bond activation and functionalization reactions

Chemical Society Reviews, Год журнала: 2022, Номер 51(18), С. 7810 - 7882

Опубликована: Янв. 1, 2022

Although C–H functionalization is one of the simplest reactions, it requires use highly active and selective catalysts. Recently, C–H-active transformations using porous materials such as crystalline metal-organic frameworks (MOFs) covalent-organic (COFs) well amorphous porous-organic polymers (POPs) new emerging heterogeneous catalysts have attracted significant attention due to their promising activity potential material tunability. These solids offer exceptional structural uniformity, facile tunability permanent porosity. In addition, tuning catalytic selectivity these can be achieved through engineering site microenvironments, metal node substitution, linker changes, node/linker functionalization, pore modification. The present review provides an overview current state art on MOFs, COFs POPs advanced for various bond activation providing details about chemo-, regio-, stereo-selectivity control, comparing performance with that other catalysts, triggering additional research by showing limitations challenges in this area, a perspective future developments.

Язык: Английский

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Neighboring Zn–Zr Sites in a Metal–Organic Framework for CO₂ Hydrogenation

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(23), С. 8829 - 8837

Опубликована: Июнь 7, 2021

ZrZnOx is active in catalyzing carbon dioxide (CO2) hydrogenation to methanol (MeOH) via a synergy between ZnOx and ZrOx. Here we report the construction of Zn2+–O–Zr4+ sites metal–organic framework (MOF) reveal insights into structural requirement for MeOH production. The are obtained by postsynthetic treatment Zr6(μ3-O)4(μ3-OH)4 nodes MOF-808 ZnEt2 mild thermal remove capping ligands afford exposed metal catalysis. resultant MOF-808-Zn catalyst exhibits >99% selectivity CO2 at 250 °C high space-time yield up 190.7 mgMeOH gZn–1 h–1. catalytic activity stable least 100 h. X-ray absorption spectroscopy (XAS) analyses indicate presence centers instead ZnmOn clusters. Temperature-programmed desorption (TPD) hydrogen H/D exchange tests show activation H2 Zn2+ centers. Open Zr4+ also critical, as supported on Zr-based other MOFs without open fail produce MeOH. TPD reveals importance bicarbonate decomposition under reaction conditions generating activation. well-defined local structures metal-oxo provide unique opportunity elucidate details bifunctional

Язык: Английский

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Prospects, advances and biological applications of MOF-based platform for the treatment of lung cancer

Biomaterials Science, Год журнала: 2024, Номер 12(15), С. 3725 - 3744

Опубликована: Янв. 1, 2024

Herein, we reviewed the recent development in use of MOF materials as a platform for treatment lung cancer.

Язык: Английский

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Entropy engineering activation of UiO-66 for boosting catalytic transfer hydrogenation

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

Опубликована: Янв. 3, 2025

High-entropy metal-organic frameworks (HE-MOFs) hold promise as versatile materials, yet current rare examples are confined to low-valence elements in the fourth period, constraining their design and optimization for diverse applications. Here, a novel high-entropy, defect-rich small-sized (32 nm) UiO-66 (ZrHfCeSnTi HE-UiO-66) has been synthesized first time, leveraging increased configurational entropy achieve high tolerance doping with metal ions. The lattice distortion of HE-UiO-66 induces exposure nodes create coordination unsaturated sites concentration 322.4 μmol/g, which increases abundance Lewis acid-base sites, thereby achieving significant improvement performance catalytic transfer hydrogenation (CTH) reaction. Systematic investigation manifests that special electronic structure enhances interaction bonding substrate molecules reduces energy barrier hydrogen process. Our approach offers new strategy constructing MOFs. offer potential but existing largely limited restricting various defect-rich, framework enhance hydrogenation.

Язык: Английский

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Hollow Mesoporous Metal–Organic Frameworks with Enhanced Diffusion for Highly Efficient Catalysis

ACS Catalysis, Год журнала: 2020, Номер 10(11), С. 5973 - 5978

Опубликована: Май 7, 2020

Metal–organic frameworks (MOFs) with uniform porous structures show great promise for size/shape-selective catalysis, but their microsized pores and narrow channels inherently limit the diffusion of catalytic substrates efficiency. Herein, we report fabrication a hollow mesoporous MOF macroporous core shell, featuring hierarchical structure that allows fast reactants. The shell were achieved by an elaborate design bimetallic stability differences in both metal–ligand bonds spatial distribution via boosted nucleation process, followed selective etching treatment. Impressively, greatly enhanced mass within framework, which is demonstrated experiments, molecular dynamics simulation, reaction using 4-chlorostyrene as probe. In addition, as-prepared exhibited superior performance when utilized Pd nanoparticles carrier, compared solid Pd/MOF commercial Pd/C catalysts toward benzyl alcohol oxidation.

Язык: Английский

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Reticular Materials for Artificial Photoreduction of CO₂

Advanced Energy Materials, Год журнала: 2020, Номер 10(46)

Опубликована: Окт. 21, 2020

Abstract Because of the energy crisis facing planet, reducing fossil fuel reliance is an urgent scientific task. Alternative fuels have recently been in high demand. Taking into account enormous amount CO 2 released from combustion, converting value‐added products using photochemistry—the catalytic transformation activated by ubiquitous sunlight mimicking photosynthesis natural plants—is paramount importance. Scientists developed various photocatalysts for photoreduction. Among them, reticular materials including metal–organic frameworks (MOFs) and covalent organic (COFs) employed many applications during past decade emerged as advanced platforms photoreduction . This Progress Report aims to provide fundamentals, mechanism, methods characterization gain insight process In addition, this highlights achievements catalysts discusses relationship between structural features MOFs/COFs with their photocatalytic performance. Based on comprehension advancements, opportunities, challenges photoreduction, future prospects technology are discussed direct exciting research designing better reduction photocatalysts.

Язык: Английский

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Chemical transformation approach for high-performance ternary NiFeCo metal compound-based water splitting electrodes

Applied Catalysis B Environment and Energy, Год журнала: 2021, Номер 294, С. 120246 - 120246

Опубликована: Апрель 21, 2021

Язык: Английский

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Dimensional Reduction of Lewis Acidic Metal–Organic Frameworks for Multicomponent Reactions

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(21), С. 8184 - 8192

Опубликована: Май 21, 2021

Owing to hindered diffusions, the application of porous catalytic materials has been limited relatively simple organic transformations with small substrates. Herein we report a dimensional reduction strategy construct two-dimensional metal–organic framework (MOF), Zr6OTf-BTB, 96% accessible Lewis acidic sites as probed by bulky base pivalonitrile. With nearly free substrate accessibility, Zr6OTf-BTB outperformed two three-dimensional MOF counterparts similar acidity (Zr6OTf-BPDC and Zr6OTf-BTC) in catalyzing sterically multicomponent reactions (MCRs) for construction tetrahydroquinoline aziridine carboxylate derivatives high turnover numbers (TONs). was also superior homogeneous benchmark Sc(OTf)3 14 times higher TON 9 longer catalyst lifetime. Furthermore, topology-activity relationships these Zr-based MOFs were rationalized comparing their acidity, sites, sites. successfully used several bioactive molecules via MCRs excellent efficiency. This should allow development other catalysts synthetically useful complicated transformations.

Язык: Английский

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Topology-Based Functionalization of Robust Chiral Zr-Based Metal–Organic Frameworks for Catalytic Enantioselective Hydrogenation

Journal of the American Chemical Society, Год журнала: 2020, Номер unknown

Опубликована: Май 2, 2020

The design and development of robust porous supported catalysts with high activity selectivity is extremely significant but very challenging for eco-friendly synthesis fine chemicals pharmaceuticals. We report here the highly stable chiral Zr(IV)-based MOFs different topologies to support Ir complexes demonstrate their network structures-dependent asymmetric catalytic performance. Guided by modulated isoreticular expansion strategy, five Zr-MOFs a flu or ith topology are constructed from enantiopure 1,1'-biphenol-derived tetracarboxylate linkers Zr6, Zr9, Zr12 clusters. obtained all show chemical stability in boiling water, strongly acidic, weakly basic aqueous solutions. two featuring dihydroxyl groups biphenol open large cages, after sequential postsynthetic modification P(NMe2)3 [Ir(COD)Cl]2, can be efficient recyclable heterogeneous hydrogenation α-dehydroamino acid esters up 98% ee, whereas three small cages cannot installed complex. Incorporation Ir-phosphorus into leads great enhancement stability, durability, even stereoselectivity. This work therefore not only advances as supports labile metal catalysis also provides new insight how active centers result due framework topology.

Язык: Английский

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