i-Lab, CAS Center for Excellence in Nanoscience, Suzhou Institute of Nano-Tech and Nano-Bionics (SINANO), Chinese Academy of Sciences , Suzhou 215123, China.
Division of Advanced Materials, SINANO, Chinese Academy of Sciences , Suzhou 215123, China.
Nano Lett. 2016 Oct 12;16(10):6541-6547. doi: 10.1021/acs.nanolett.6b03184. Epub 2016 Sep 26.
Carbon nanotubes (CNTs) have long been regarded as an efficient free radical scavenger because of the large-conjugation system in their electronic structures. Hence, despite abundant reports on CNT reacting with incoming free radical species, current research has not seen CNT itself displaying the chemical reactivity of free radicals. Here we show that reactive free radicals can in fact be generated on carbon nanotubes via reductive defluorination of highly fluorinated single-walled carbon nanotubes (FSWNTs). This finding not only enriches the current understanding of carbon nanotube chemical reactivity but also opens up new opportunities in CNT-based material design. For example, spacer-free direct intertube cross-linking of carbon nanotubes was previously achieved only under extremely high temperature and pressure or electron/ion beam irradiation. With the free radicals on defluorinated FSWNTs, the nanotubes containing multiple radicals on the sidewall can directly cross-link with each other under ambient temperature through intertube radical recombination. It is demonstrated that carbon nanotube fibers reinforced via direct cross-linking displays much improved mechanical properties.
碳纳米管(CNTs)因其电子结构中的大共轭体系,长期以来一直被认为是一种有效的自由基清除剂。因此,尽管有大量关于 CNT 与进入的自由基反应的报道,但目前的研究尚未看到 CNT 本身表现出自由基的化学反应性。在这里,我们表明,通过对高度氟化的单壁碳纳米管(FSWNTs)进行还原脱氟反应,实际上可以在碳纳米管上生成反应性自由基。这一发现不仅丰富了对碳纳米管化学反应性的现有认识,而且为基于 CNT 的材料设计开辟了新的机会。例如,以前只有在极高的温度和压力下或电子/离子束辐照下,才能实现无间隔剂的碳纳米管的直接管间交联。在脱氟 FSWNTs 上的自由基作用下,含有侧壁上多个自由基的纳米管可以在室温下通过管间自由基重组直接交联。实验证明,通过直接交联增强的碳纳米管纤维显示出了显著改善的机械性能。