Metathesis Strategy for the Immobilization of Copper(II) onto Carboxymethylcellulose/Fe3O4 Nanohybrid Supports: Efficient and Recoverable Magnetic Catalyst for the CuAAC Reaction

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• 作者：Zhuan Zhang ; Ping Song ; Junbin Zhou ; Yang Chen ; Bijin Lin ; Yiqun Li
• 刊名：Industrial & Engineering Chemistry Research
• 出版年：2016
• 出版时间：December 7, 2016
• 年：2016
• 卷：55
• 期：48
• 页码：12301-12308
• 全文大小：626K
• ISSN：1520-5045

文摘

To overcome the inherent obstacles facing the traditional surface modification of Fe₃O₄ magnetic nanoparticles with appropriate capping agents to anchor the catalytically active complexes, a novel retrievable copper(II) catalyst immobilized on carboxymethylcellulose/Fe₃O₄ nanoparticles (Cu^II–CMC–Fe₃O₄) magnetic hybrid materials was successfully prepared through three steps of sequential metathesis and one step of oxidation. First, ferrous carboxymethylcellulose (CMC–Fe^II) was prepared by ionic exchange of ferrous chloride and sodium carboxymethylcellulose (CMC–Na). Second, the resulting CMC–Fe^II was treated with NaOH solution to form the corresponding hybrid material Na–CMC–Fe(OH)₂, which proceeded to be exposed to the air to afford the Na–CMC–Fe₃O₄. Finally, the as-prepared Na–CMC–Fe₃O₄ was immersed in copper sulfate solution to self-assembly-fabricate the Cu^II–CMC–Fe₃O₄ hybrid catalyst by ionic exchange of Cu(II) with Na–CMC–Fe₃O₄. The morphology and structural feature of the catalyst were characterized by different microscopic and spectroscopic techniques such as FT-IR, ICP-AES, XRD, SEM, EDS, TEM, TGA, and DSC. The ensuring catalyst has been successfully applied in the CuAAC reaction of benzyl halides, sodium azide, and terminal alkynes to the synthesis of 1,2,3-triazoles. Furthermore, the Cu^II–CMC–Fe₃O₄ could be easily isolated and recovered by magnetic decantation and reused for five consecutive cycles without much loss in activity.