MIL-125-NH2固定化Pd在Suzuki-Miyaura反应中作为高效可回收金属-有机骨架的制备与表征

IF 2.7 3区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Journal of Organometallic Chemistry Pub Date : 2025-02-01 Epub Date: 2024-11-30 DOI:10.1016/j.jorganchem.2024.123466
Zeynab Sadati, Heshmatollah Alinezhad, Mahmood Tajbakhsh
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引用次数: 0

摘要

在本研究中,通过修饰MIL-125-NH2金属-有机骨架溴乙酰基溴和四乙基苯胺配体,制备了一种高效的非均相钯。然后将所得的修饰框架用作固定化Pd纳米颗粒(NPs)的平台,以生成Pd@MIL-125-NH-Ac-TEPA纳米复合材料。利用FT-IR、FESEM、EDS、TEM、CHN、TGA、XRD、ICP-OES等表征了纳米复合材料的结构。表征结果证实形成了分散良好的Pd纳米颗粒,尺寸分布在9 ~ 23 nm之间。负载率为2.97%的Pd@MIL-125-NH-Ac-TEPA纳米复合材料在芳基硼酸与含有电子供体和电子受体取代基的各种芳基和杂芳基卤化物(氯化物、溴化物和碘化物)的Suzuki-Miyaura偶联反应中表现出高效率。偶联产物以水/乙醇(1:1)为溶剂,在60℃条件下反应30 min,收率为70 - 99%。纳米催化剂可以很容易地回收,并且在至少连续五次运行中重复使用,而不会明显失去其活性。重复使用的纳米催化剂的钯浸出率小于1%。结果表明,引入的纳米催化剂具有其他有机转化的潜力。
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Preparation and characterization of Pd immobilized on the MIL-125-NH2 as an efficient recyclable metal-organic framework in the Suzuki–Miyaura reaction
In this study, an efficient heterogeneous palladium was developed by moifying the MIL-125-NH2 metal-organic framework bromoacetyl bromide and tetraethylenepentamine ligands. The resulting modified framework was then used as a platform for immobilizing Pd nanoparticles (NPs) to generate the Pd@MIL-125-NH-Ac-TEPA nanocomposite. FT-IR, FESEM, EDS, TEM, CHN, TGA, XRD, and ICP-OES were used to identify the structure of the nanocomposite. The characterization findings approve the formation of well-dispersed Pd nanoparticles with a size distribution of 9 to 23 nm. The Pd@MIL-125-NH-Ac-TEPA nanocomposite with 2.97 % loading of Pd exhibited high efficiency in the Suzuki-Miyaura coupling reaction of arylboronic acids with various aryl and heteroaryl halides (chlorides, bromides, and iodides) containing electron-donor and electron-acceptor substituents. The coupling products were obtained in water/ethanol mixture (1:1) as solvent at 60 °C for 30 min in 70–99 % yields. The nanocatalyst can be recovered easily and reused for at least five consecutive runs without losing its activity significantly. The palladium leaching of the reused nanocatalyst was less than 1 %. The results revealed that the introduced nanocatalyst has the potential for other organic transformations.
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来源期刊
Journal of Organometallic Chemistry
Journal of Organometallic Chemistry 化学-无机化学与核化学
CiteScore
4.40
自引率
8.70%
发文量
221
审稿时长
36 days
期刊介绍: The Journal of Organometallic Chemistry targets original papers dealing with theoretical aspects, structural chemistry, synthesis, physical and chemical properties (including reaction mechanisms), and practical applications of organometallic compounds. Organometallic compounds are defined as compounds that contain metal - carbon bonds. The term metal includes all alkali and alkaline earth metals, all transition metals and the lanthanides and actinides in the Periodic Table. Metalloids including the elements in Group 13 and the heavier members of the Groups 14 - 16 are also included. The term chemistry includes syntheses, characterizations and reaction chemistry of all such compounds. Research reports based on use of organometallic complexes in bioorganometallic chemistry, medicine, material sciences, homogeneous catalysis and energy conversion are also welcome. The scope of the journal has been enlarged to encompass important research on organometallic complexes in bioorganometallic chemistry and material sciences, and of heavier main group elements in organometallic chemistry. The journal also publishes review articles, short communications and notes.
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