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通过金属有机框架的缓慢化学还原制备金属纳米颗粒复合材料

Fabrication of Metal Nanoparticle Composites by Slow Chemical Reduction of Metal-Organic Frameworks.

作者信息

Fu Yu, Zhai Xu, Wang Sha, Shao Lei, Bai Xiao-Jue, Su Ze-Shun, Liu Yun-Ling, Zhang Li-Ying, Chen Jun-Yi

机构信息

Department of Chemistry, College of Sciences, Northeastern University, Shenyang 110819, China.

State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, China.

出版信息

Inorg Chem. 2021 Nov 1;60(21):16447-16454. doi: 10.1021/acs.inorgchem.1c02277. Epub 2021 Oct 17.

Abstract

Constructing metal nanoparticle (MNP) composites from metal-organic framework (MOF) precursors has attracted extensive attention as the MOF precursors provide an excellent porous matrix for the generation of MNP composites, which enables the direct fabrication of well-dispersed MNP composites. In this work, a novel strategy is proposed to fabricate MNP composites by slow chemical reduction (SCR) of MOF precursors at room temperature. The reduction process is skillfully slowed via using ethanol as the solvent, and the formation of MNP composites is then realized by the SCR process. Briefly, BH slowly diffuses into an MOF precursor and in situ reduces metal ions to well-dispersed nanoscale MNP composites. Meanwhile, this SCR process breaks the coordination bonds from MOF precursors, leading to the generation of porous structures for the resulting composites. Interestingly, the composites inherit the morphology of MOF precursors well. Besides, this SCR strategy allows construction of MNP composites from different types of MOF precursors. The resulting Cu@HK-3 composites possess well-dispersed nanoscale Cu NPs and a porous architecture, which exhibit superior catalytic performance and stability in the Ullmann coupling reaction. This strategy provides a feasible, convenient, and energy-saving route to prepare MNP composites from MOF precursors with customizable morphology and well-dispersed MNPs.

摘要

由金属有机框架(MOF)前驱体制备金属纳米颗粒(MNP)复合材料已引起广泛关注,因为MOF前驱体为MNP复合材料的生成提供了优异的多孔基质,从而能够直接制备出分散良好的MNP复合材料。在这项工作中,提出了一种通过在室温下对MOF前驱体进行缓慢化学还原(SCR)来制备MNP复合材料的新策略。通过使用乙醇作为溶剂巧妙地减缓了还原过程,然后通过SCR过程实现了MNP复合材料的形成。简而言之,硼氢化钠(BH)缓慢扩散到MOF前驱体中,并将金属离子原位还原为分散良好的纳米级MNP复合材料。同时,这种SCR过程打破了MOF前驱体的配位键,导致所得复合材料产生多孔结构。有趣的是,复合材料很好地继承了MOF前驱体的形态。此外,这种SCR策略允许由不同类型的MOF前驱体制备MNP复合材料。所得的Cu@HK-3复合材料具有分散良好的纳米级铜纳米颗粒(Cu NPs)和多孔结构,在乌尔曼偶联反应中表现出优异的催化性能和稳定性。该策略提供了一种可行、便捷且节能的途径,可从具有可定制形态和分散良好的MNPs的MOF前驱体制备MNP复合材料。

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