Bergman环化反应在碳纳米管制备中的应用
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摘要
本文通过有机合成方法制备设计结构的烯二炔化合物,以无机介孔硅材料SBA-15作为模板,通过烯二炔结构化合物的自组装在SBA-15纳米孔道内形成单分子层,并经过热引发使其发生Bergman环化反应,从而在介孔材料孔道内形成聚芳烃交联网状结构,再经过高温热解使聚芳烃交联网状结构脱除杂原子,使所得碳材料进一步完善,最后刻蚀除去无机模板得到预定尺寸的结构均一的单壁碳纳米管有序序列。TEM测试结果表明,通过该制备方法得到了尺寸均一的单壁碳纳米管有序序列,所得碳纳米管由于无机模板中存在微孔桥结构使各个孔道相连而呈簇状排列。Raman测试结果表明,通过该制备方法得到的碳纳米管有序序列具有一定的石墨化程度。BET测试结果表明,通过该制备方法得到的碳纳米管有序序列具有优异的吸附能力。
本文所报道的利用无机介孔材料作为模板,通过烯二炔结构化合物的自组装形成单分子层,并经过高温处理制备碳纳米管的方法,是在碳纳米材料制备中首次应用分子组装技术,将功能化的分子在分子尺度范围内通过化学方法聚集成有序体系。这种自下而上(Bottom-up)的合成方法在碳纳米材料制备领域内是一种崭新的合成思路,该法所得碳纳米材料具有结构可设计、可调控的优点,并且为构造各种新型的纳米结构、制备各种纳米尺度的碳材料,如碳纳米管及其序列、碳纳米球、碳纳米胶囊、石墨烯等开拓了新的发展空间。
In this work, a bottom-up synthesis of carbon nanotube arrays was developed through Bergman cyclization of enediyne containing compounds immobilized inside of SBA-15 nano-channels and followed by pyrolysis. Raman spectroscopy confirmed the occurrence of thermal Bergman cyclization inside the channels. Further heating under elevated temperature produced nanotube arrays in good yield. TEM images revealed the formation of nanotube arrays due to the micro-tunnels of template. Raman spectra showed moderate degree of graphitization. Formation of enediyne self-assembled monolayers (SAMs) on a template followed by the processing sequence developed in this work is promising to construct carbon materials with various nanoscopic morphology, such as carbon nanotube, graphene and buckyball.
本文所报道的利用无机介孔材料作为模板,通过烯二炔结构化合物的自组装形成单分子层,并经过高温处理制备碳纳米管的方法,是在碳纳米材料制备中首次应用分子组装技术,将功能化的分子在分子尺度范围内通过化学方法聚集成有序体系。这种自下而上(Bottom-up)的合成方法在碳纳米材料制备领域内是一种崭新的合成思路,该法所得碳纳米材料具有结构可设计、可调控的优点,并且为构造各种新型的纳米结构、制备各种纳米尺度的碳材料,如碳纳米管及其序列、碳纳米球、碳纳米胶囊、石墨烯等开拓了新的发展空间。
In this work, a bottom-up synthesis of carbon nanotube arrays was developed through Bergman cyclization of enediyne containing compounds immobilized inside of SBA-15 nano-channels and followed by pyrolysis. Raman spectroscopy confirmed the occurrence of thermal Bergman cyclization inside the channels. Further heating under elevated temperature produced nanotube arrays in good yield. TEM images revealed the formation of nanotube arrays due to the micro-tunnels of template. Raman spectra showed moderate degree of graphitization. Formation of enediyne self-assembled monolayers (SAMs) on a template followed by the processing sequence developed in this work is promising to construct carbon materials with various nanoscopic morphology, such as carbon nanotube, graphene and buckyball.
引文
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