Engineering functional group decorated ZIFs to high-performance Pd@ZIF-92 nanocatalysts for C(sp2)-C(sp2) couplings in aqueous medium

You, Li-Xin; Zhao, Bai-Bei; Yao, Shan-Xin; Xiong, Gang; Drăguţan, Ileana; Drăguţan, Valerian; Ding, Fu; Sun, Yizhen

doi:10.1016/j.jcat.2020.09.024

Cited by 10 publications

(3 citation statements)

References 107 publications

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“…Previous studies on polymer-supported palladium nanoparticles in Suzuki−Miyaura coupling have reported that catalysts reduced with MeOH afforded higher TOFs than those reduced with NaBH 4 , that is, catalysts with a higher Pd(II) content. 65 However, individual Pd(II) species also catalyze this reaction, 66 and the coaction of the two oxidation states cannot be ruled out (Table 1). Tetrakis(triphenyl-phosphine)palladium immobilization decreases the yield of Suzuki−Miyaura coupling by limiting the access to the active sites.…”

Section: ■ Methodsmentioning

confidence: 99%

Sonogashira Synthesis of New Porous Aromatic Framework-Entrapped Palladium Nanoparticles as Heterogeneous Catalysts for Suzuki–Miyaura Cross-Coupling

Căta

Terenti

Cociug

et al. 2022

ACS Appl. Mater. Interfaces

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Palladium nanoparticles entrapped in porous aromatic frameworks (PAFs) or covalent organic frameworks may promote heterogeneous catalytic reactions. However, preparing such materials as active nanocatalysts usually requires additional steps for palladium entrapment and reduction. This paper reports as a new approach, a simple procedure leading to the self-entrapment of Pd nanoparticles within the PAF structure. Thus, the selected Sonogashira synthesis affords PAF-entrapped Pd nanoparticles that can catalyze the C–C Suzuki–Miyaura cross-coupling reactions. Following this new concept, PAFs were synthesized via Sonogashira cross-coupling of the tetraiodurated derivative of tetraphenyladamantane or spiro-9,9′-bifluorene with 1,6-diethynylpyrene, then characterized them using powder X-ray diffraction, diffuse reflectance infrared Fourier transform spectroscopy, X-ray photoelectron spectroscopy, high-resolution scanning transmission electron microscopy, and textural properties (i.e., adsorption–desorption isotherms). The PAF-entrapped Pd nanocatalysts showed high catalytic activity in Suzuki–Miyaura coupling reactions (demonstrated by preserving the turnover frequency values) and stability (demonstrated by palladium leaching and recycling experiments). This new approach presents a new class of PAFs with unique structural, topological, and compositional complexities as entrapped metal nanocatalysts or for other diverse applications.

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Section: ■ Methodsmentioning

confidence: 99%

Sonogashira Synthesis of New Porous Aromatic Framework-Entrapped Palladium Nanoparticles as Heterogeneous Catalysts for Suzuki–Miyaura Cross-Coupling

Căta

Terenti

Cociug

et al. 2022

ACS Appl. Mater. Interfaces

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“…Imine‐functionalized ZIF‐92 (zeolitic imidazolate framework 92) can coordinate Pd ions through the N and O atoms of hydroxyethyl imine motifs in the imidazolate linker. The resulting Pd@ZIF‐92 MOFs exhibited superior catalytic performance for Suzuki–Miyaura coupling reactions 18 . Alternatively, the functionalization of a MOF with organic functional groups such as squaramides demonstrated excellent performance as active catalysts for the Friedel–Crafts reaction, or as sensors for the selective luminescence‐based detection of lactose in milk 19 …”

Section: Introductionmentioning

confidence: 99%

Plasmonic metal‐organic frameworks

et al. 2021

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Plasmonic metal‐organic frameworks are composite nanoparticles comprising plasmonic metal nanoparticles (NPs) embedded within a metal‐organic framework (MOF) matrix. As a result, not only the functionalities of the individual components are retained, but synergistic effects additionally provide improved chemical and physical properties. Recent progress in plasmonic MOFs has demonstrated the potential for nanofabrication and various nanotechnology applications. Synthetic challenges toward plasmonic MOFs have been recently addressed, resulting in new opportunities toward practical applications, such as surface‐enhanced Raman scattering, therapy, and catalysis. The impact of key parameters (thermodynamic vs. kinetic) on the synthetic pathways of plasmonic MOFs is reviewed, while providing insight into related progress toward structure‐derived applications.

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“…The formation of carbon–carbon bonds has long been regraded as one of the most prevalent and challenging methodologies in synthetic organic chemistry. , Among these strategies, Suzuki–Miyaura cross-coupling is recognized as the protagonist for the facile preparation of various asymmetric and symmetric biphenyl compounds that shows great significance in practical pharmaceutical applications. − In principle, the above coupling reaction proceeds conveniently with the addition of metal catalysts, among which palladium (Pd) is the most commonly used due to its high activity. , With this method, attaching Pd species to a heterogeneous carrier yields a catalyst that combines the advantages of homogeneous catalysis (catalytically active sites) and sustainable heterogeneous catalysis (high stability and convenient separation). Although many reports on Suzuki–Miyaura coupling over diverse Pd-based heterogeneous nanomaterials have been unveiled, − there is no report on well-designed catalysts with size-selective reaction to date . Meanwhile, it is worth mentioning that the Pd-based catalyst for the Suzuki–Miyaura coupling should be water-resistant in aqueous systems for better recovery and reuse …”

mentioning

confidence: 99%

Size-Selective Suzuki–Miyaura Coupling Reaction over Ultrafine Pd Nanocatalysts in a Water-Stable Indium–Organic Framework

Chen

Wei

et al. 2022

Inorg. Chem.

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Metal nanoparticles stabilized by crystalline metal−organic frameworks (MOFs) are highly promising for green heterogeneous catalysis. In this work, in situ formed ultrafine Pd nanocatalysts with an average size of 3.14 nm have been successfully immobilized into the mesopores or defects of a water-stable indium-based MOF by the double-solvent method and subsequent reduction. Significantly, the obtained Pd@InOF-1 displays an obvious and satisfactory size-selective effect in the Suzuki−Miyaura coupling reaction between arylboronic acids and aryl bromides. On the basis of the synergistic effect, microporous InOF-1 nanorods afford a confined space for improving the selectivity of target products while Pd nanoparticles endow abundant active sites for catalysis. Herein, choosing the smallest size reactant with only one benzene ring gives the highest isolated yield of 90%, and if the size is larger, the yield is obviously reduced or even the target product could not be collected. Looking forward, this demonstrated study not only assembles a well-designed Pd@MOF composite with unique micro-nanostructures but also delivers an impressive option for cross-coupling reaction, which has implications for the further development of MOF hybrids for sustainable applications.

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Engineering functional group decorated ZIFs to high-performance Pd@ZIF-92 nanocatalysts for C(sp2)-C(sp2) couplings in aqueous medium

Cited by 10 publications

References 107 publications

Sonogashira Synthesis of New Porous Aromatic Framework-Entrapped Palladium Nanoparticles as Heterogeneous Catalysts for Suzuki–Miyaura Cross-Coupling

Sonogashira Synthesis of New Porous Aromatic Framework-Entrapped Palladium Nanoparticles as Heterogeneous Catalysts for Suzuki–Miyaura Cross-Coupling

Plasmonic metal‐organic frameworks

Size-Selective Suzuki–Miyaura Coupling Reaction over Ultrafine Pd Nanocatalysts in a Water-Stable Indium–Organic Framework

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