Ultrathin 2D Porphyrin‐Based Zr‐MOF Nanosheets as Heterogeneous Catalysts for Styrene Epoxidation and Benzylic C‐H Oxidation

ChemCatChem, Год журнала: 2024, Номер 16(15)

Опубликована: Фев. 27, 2024

Abstract Selective oxidation of hydrocarbons using molecular oxygen as sole oxidant under mild conditions remains a challenging task. In this context, metal‐organic frameworks (MOFs) have been widely used in various reactions due to their porosity, high surface area and designability. However, the slow diffusion substrates/products micropores three‐dimensional (3D) bulk MOFs hinders efficient catalytic performance such materials. Herein an ultrathin two‐dimensional (2D) porphyrin‐based Zr‐MOF nanosheet (Zr‐TCPP) is synthesized through modulator‐control strategy. Subsequently, metal ions are anchored into porphyrin ring by post synthesis modification afford series 2D Zr‐TCPP(M) (M=Mn, Fe, Co, Ni, Cu Zn). Various structural characterization techniques indicate nanoflower structure with nanoplate petals which provides fully exposed accessible active sites. Among them, Zr‐TCPP(Fe) shows excellent styrene epoxidation benzylic C−H O 2 ambient temperature pressure. The remarkable activity arises from density porphyrin‐Fe sites, low barriers for substrates products, well similar homogeneous reaction space. Furthermore, easily recycled centrifugation reused at least five times without significant loss activity.

Язык: Английский

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Recent advance in metal-organic frameworks based catalysts for production of fine chemicals via thermal catalysis

Molecular Catalysis, Год журнала: 2025, Номер 573, С. 114811 - 114811

Опубликована: Янв. 7, 2025

Язык: Английский

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Co(II) and Zn(II) Coordination Polymers with π‐Conjugated Ligands for Enhanced Iodine Uptake in Vapor and Aqueous Media

Chemistry - An Asian Journal, Год журнала: 2025, Номер unknown

Опубликована: Апрель 14, 2025

Abstract The efficient removal of radioiodine from an aqueous solution is crucial for the sustainable advancement nuclear energy and environmental conservation. In this work, two π‐conjugated nonporous coordination polymers, namely, {[Co(bqdc)(dpe) 2 (H O) ]·H O} n ( Co‐CP ) [Zn(bqdc)(dpe)] Zn‐CP (bqdc 2− = 2,2′‐biquinoline‐4,4′‐dicarboxylate dpe 1,2‐di(4‐pyridyl)ethylene) were successfully synthesized characterized. Single crystal X‐ray analysis demonstrated that have different structures. displays 1D chain via bidentate monodentate modes bqdc dpe, respectively, whereas presents a threefold interpenetrated 3D framework through bridging bidentated ligands. Both CPs exhibit nature with high π‐electron richness in structural framework. compounds can adsorb iodine vapor phases adsorption capacity. capacities phase at 70 °C are 3.54 1.57 g/g , respectively. addition, effective solutions 2315.86 2032.97 mg/g, kinetics, isotherms, competing anion adsorption, real water samples studied. mechanism due to electron transfer sorption sites iodine, forming charge complex, which was confirmed by FTIR, PXRD, EDX, XPS techniques. They also be reused capture ability retain level effectiveness.

Язык: Английский

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High-Capacity Iodine Adsorption and Nonporous to Porous Structural Transformation in an Originally Nonporous Coordination Polymer

Inorganic Chemistry Frontiers, Год журнала: 2023, Номер 11(3), С. 769 - 778

Опубликована: Ноя. 6, 2023

A rare example of the high-capacity uptake iodine guest molecules by nonporous CP is reported. Moreover, release from loaded framework induces change to porous stage.

Язык: Английский

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Metal–Organic Layers with Photosensitizer and Pyridine Pairs Activate Alkyl Halides for Photocatalytic Heck-Type Coupling with Olefins

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(12), С. 7936 - 7941

Опубликована: Март 13, 2024

Photochemical generation of alkyl radicals from haloalkanes often requires strong energy input ultraviolet light or a photoreductant. Haloalkanes can alternatively be activated with nitrogen-based nucleophiles through sequential SN2 reaction and single-electron reduction to access radicals, but these two steps have opposite steric requirements on the nucleophiles. Herein, we report design Hf12 metal–organic layers (MOLs) iridium-based photosensitizer bridging ligands secondary-building-unit-supported pyridines for photocatalytic radical haloalkanes. By bringing pyridine pairs in proximity, MOL catalysts allowed facile pyridinium salts reactions between at same time enhanced electron transfer excited photosensitizers facilitate generation. Consequentially, MOLs efficiently catalyzed Heck-type cross-coupling olefinic substrates generate functionalized alkenes. The showed 4.6 times higher catalytic efficiency than homogeneous counterparts were recycled reused without loss activity.

Язык: Английский

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Dimensional Reduction of Metal–Organic Frameworks for Photocatalytic Synthesis of Fused Tetracyclic Heterocycles

Inorganic Chemistry, Год журнала: 2024, Номер 63(21), С. 9854 - 9863

Опубликована: Май 16, 2024

Heterogeneous palladium catalysts with high efficiency, Pd atom utilization, simplified separation, and recycle have attracted considerable attention in the field of synthetic chemistry. Herein, we reported a zirconium-based two-dimensional metal–organic framework (2D-MOF)-based Pd(II) photocatalyst (Zr–Ir–Pd) by merging Ir photosensitizers species into skeletons 2D-MOF for Pd(II)-catalyzed oxidation reaction. Morphological structural characterization identified that Zr–Ir–Pd specific nanoflower-like structure consists ultrathin nanosheets (3.85 nm). Due to its excellent visible-light response absorption capability, faster transfer separation photogenerated carriers, more accessible active sites, low mass resistance, exhibited boosted photocatalytic activity catalyzing sterically hindered isocyanide insertion diarylalkynes construction fused tetracyclic heterocycles, up 12 times catalyst turnover number than existing catalytic systems. In addition, inhibited competitive agglomeration Pd(0) could be reused at least five times, owing stabilization on single-site sites. Finally, possible mechanism synthesis heterocycles catalyzed was proposed.

Язык: Английский

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Recent Advances in the Synthesis and Application of Monolayer 2D Metal‐Organic Framework Nanosheets

Small Science, Год журнала: 2024, Номер unknown

Опубликована: Июль 10, 2024

Monolayer 2D metal‐organic framework (MOF) nanosheets, characterized by abundant exposed active sites and tunable structure function (such as altering the metal nodes or organic ligands), have emerged a pivotal class of materials, demonstrating irreplaceable applications across diverse research domains in materials chemistry. This review provides comprehensive survey latest progress synthesis monolayer MOF nanosheets. Specifically, recent synthetic strategies, including top‐down bottom‐up methods, are delved their gas separation, catalysis, sensing platforms, energy storage explored. Additionally, challenges faced investigation nanosheets elucidated future opportunities for these novel generation outlined.

Язык: Английский

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2D pyrene-based metal–organic framework nanobelts as efficient photocatalysts for the coupling of thiols into disulfides

Inorganic Chemistry Frontiers, Год журнала: 2024, Номер 11(17), С. 5700 - 5708

Опубликована: Янв. 1, 2024

2D pyrene-based metal–organic framework nanobelts for the photocatalytic coupling of thiols into disulfides.

Язык: Английский

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Thermally‐stable single‐site Pd on CeO2 catalyst for selective amination of phenols to aromatic amines without external hydrogen

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Сен. 24, 2024

Abstract Developing a new route to produce aromatic amines as key chemicals from renewable phenols is benign alternative current fossil‐based routes like nitroaromatic hydrogenation, but challenging because of the high dissociation energy Ar−OH bond and difficulty in controlling side reactions. Herein, an aerosolizing‐pyrolysis strategy was developed prepare high‐density single‐site cationic Pd species immobilized on CeO 2 (Pd 1 /CeO ) with excellent sintering resistance. The obtained catalysts achieved remarkable selectivity important (yield up 76.2 %) amination without external hydrogen sources, while nano‐catalysts mainly afforded phenyl‐ring‐saturation products. catalytic properties are closely related high‐loading abundant surface defect sites suitable acid‐base properties. This report provides sustainable for producing feedstocks.

Язык: Английский

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Heterogenized molecular Pd(ii) catalyst on ultrathin 2D metal–organic frameworks with nanoflower-like morphology for isonitrile-involved cyclization reaction

Catalysis Science & Technology, Год журнала: 2023, Номер 13(24), С. 7036 - 7045

Опубликована: Янв. 1, 2023

An ultrathin 2D MOF based catalyst with fully exposed single-site Pd( ii ) active centers shows superior catalytic efficiency for the isonitrile-involved cyclization reaction compared to 3D and homogeneous counterpart.

Язык: Английский

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