将单壁碳纳米管分散到溶有光引发剂2-羟基-2-甲基-1-苯基-1-丙醇的四氢呋喃溶液中,在紫外光辐照下,光引发剂裂解生成2-羟基异丙基自由基.通过自由基的偶合反应,2-羟基异丙基自由基偶合到碳纳米管表面.用UV-Vis光谱、FTIR、拉曼光谱、TGA-MS 及HRTEM等表征方法,证实在单壁碳纳米管表面引入了羟基.UV-Vis光谱上范霍夫吸收峰的消失表明碳纳米管表面被功能化.羟基化的SWCNTs样品在FTIR光谱中出现的3420cm-1(O-H键)、2930 和 2859cm-1(烷基C-H键)峰进一步证实了碳纳米管的功能化.拉曼光谱显示, 随着SWCNTs的功能化,其切向模式吸收带与杂碳原子吸收带的相对比值(IG/ID)下降.TGA-MS的m/z 59峰(400℃)揭示了SWCNTs上存在着异丙醇基团.HRTEM和溶解数据表明,光解改性有助于碳纳米管管束间缠结的解开,进而提高了其在有机溶剂中的溶解性,并且在一定程度上保持了碳纳米管的结构.
Single-walled carbon nanotubes (SWCNTs) were functionalized by the covalent attachment of 2-propanol-2-yl radicals to their surface. These radicals were generated by photolysis of 2-hydroxy-2-methyl-1-phenyl-1-propanone under ultraviolet (UV) light. Pristine SWCNTs were dispersed in a tetrahydrofuran solution, and then free radicals were attached to their surface when the solution was subjected to UV irradiation. The functionalization of SWCNTs was evidenced by UV/visible spectroscopy, Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, thermal gravimetric analysis-mass spectrometry (TGA-MS) and high resolution transmission electron microscopy (HRTEM). UV/visible results indicated a loss of Van Hove singularities because of the covalent functionalization. The modification was further proved by FTIR. Raman spectra showed that the intensity ratio of the G band and D band (IG/ID) decreased for the functionalized SWCNTs. TGA-MS also showed a 2-propanol-2-yl groups. HRTEM and solubility data proved that the sidewall functionalization dissociated the bundle structure, improved the solubility in common organic solvents and retained the original electronic structure of the SWCNTs without severe modification that damages the nanotubes.
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