封装银纳米颗粒的纤维状一维共价有机框架实现4-硝基苯酚还原

Silver nanoparticles encapsulated in one-dimensional fibrous covalent organic frameworks for reduction of 4-nitrophenol

摘要

金属纳米颗粒(nanoparticles, NPs)是多相催化领域中最重要的催化剂之一,然而小尺寸的金属 NPs往往会在制备和应用过程中由于自身较大的表面能而团聚失活。一维共价有机框架(one dimensional covalent organic framework, 1D COF)因其稳定的框架结构、可调的孔径尺寸、丰富的活性位点等结构优点,为可控生长金属纳米颗粒提供了绝佳的平台。使用4,4',4″,4‴-(芘-1,3,6,8-四基)四苯胺和5-乙炔基间苯二甲醛作为构筑单元,采用溶剂热法合成新型纤维状1D COF材料(COF-EP)。利用粉末X 射线衍射、红外光谱、固体核磁共振碳谱、X 射线光电子能谱、热重分析、氮气吸附-脱附等技术对 COF-EP材料进行了详细表征。进一步地,利用其结构中的末端炔基与银离子之间的配位作用,将银纳米颗粒(AgNPs)封装于 COF-EP纳米纤维间,从而得到 AgNPs@COF-EP材料。该催化剂对4-硝基苯酚(4-NP)还原表现出良好的催化活性和可循环性,连续7次运行后,4-NP在6 min内被完全还原。该研究不仅为合成1D COF提供了一种简便策略,而且为高效催化降解环境污染物提供了一种新思路。

Abstract

Metal nanoparticles (NPs) are one of the most important classes of catalysts in heterogeneous catalysis. However, small metal NPs are prone to inactivation by aggregation during the preparation and application due to their high surface energy. One-dimensional covalent organic framework (1D COF) offers an excellent platform for controllable growth of metal NPs owing to their intrinsic characteristics, such as robust skeleton, tunable pore sizes, and abundant active sites. A novel fibrous 1D COF, namely COF-EP, was successfully synthesized by reacting 5-ethynylisophthalaldehyde with 4,4',4″,4‴-(pyrene-1,3,6,8-tetrayl)tetraaniline under solvothermal conditions. The as-synthesized COF-EP was characterized in detail using various characterization techniques including powder X-ray diffraction, Fourier transform infrared spectroscopy, solid-state carbon nuclear magnetic resonance spectroscopy, X-ray photoelectron spectroscopy, thermogravimetric analysis, and nitrogen adsorption-desorption methods. Furthermore, leveraging the coordination interactions between terminal alkyne groups and silver ions, we report a facile strategy to encapsulate silver nanoparticles (AgNPs) within the COF nanofibers, yielding the AgNPs@COF-EP composite. The as-prepared AgNPs@COF-EP exhibited excellent catalytic activity and good recyclability with the complete reduction of 4-nitrophenol (4-NP) within 6 min after 7 successive runs. This work provides not only a simple strategy for the synthesis of 1D COF but also a new idea for the efficient catalytic degradation of environmental pollutants.

关键词

共价有机框架 / 银纳米颗粒 / 纤维形貌 / 对硝基苯酚 / 一维

Key words

covalent organic frameworks / silver nanoparticles / fibrous morphology / 4-nitrophenol / one-dimensional

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基金资助

国家自然科学基金青年科学基金(52203006)