Chen Yuan, Wei Li, Wang Bo, Lim Sangyun, Ciuparu Dragos, Zheng Ming, Chen Jia, Zoican Codruta, Yang Yanhui, Haller Gary L, Pfefferle Lisa D
Department of Chemical Engineering, Yale University, New Haven, CT 06520, USA.
ACS Nano. 2007 Nov;1(4):327-36. doi: 10.1021/nn700106c.
A mild, four-step purification procedure using NaOH reflux, HCl wash, and oxidation by 4 mol % molecular oxygen at 500 degrees C was developed to purify single-walled carbon nanotubes (SWCNTs) with narrow semiconducting (n,m) distribution produced from cobalt-incorporated MCM-41 (Co-MCM-41) in order to obtain bulk low-defect-density nanotubes. Three key features of Co-MCM-41 allow this mild purification technique: (1) ultrathin silica walls versus dense silica or other crystalline oxide supports are soluble in dilute NaOH aqueous solution, which avoids the damage to SWCNTs usually caused by using HF treatment to remove catalytic supports; (2) the small metallic particles are easily dissolved in HCl, a significantly milder chemical treatment compared to HF or HNO(3); (3) the high selectivity to SWCNTs with negligible multiwalled carbon nanotubes or graphite, which facilitates the removal of undesired carbon species by selective oxidation. The effectiveness of this purification procedure was evaluated by high-resolution transmission electron microscopy, scanning electron microscopy, Raman, UV-vis-NIR, and fluorescence spectroscopy, solution redox chemistry on fractionated (6,5) tubes, and SWCNT-based field effect transistor device performance. The results demonstrate that Co-MCM-41 catalyst not only provides tubes with narrow semiconducting (n,m) distribution but also allows a mild purification procedure and, therefore, produces SWCNTs with fewer defects.
开发了一种温和的四步纯化程序,该程序使用氢氧化钠回流、盐酸洗涤以及在500℃下用4摩尔%的分子氧进行氧化,以纯化由钴掺杂的MCM-41(Co-MCM-41)制备的具有窄半导体(n,m)分布的单壁碳纳米管(SWCNT),从而获得大量低缺陷密度的纳米管。Co-MCM-41的三个关键特性使得这种温和的纯化技术成为可能:(1)与致密二氧化硅或其他结晶氧化物载体相比,超薄二氧化硅壁可溶于稀氢氧化钠水溶液,这避免了通常因使用氢氟酸处理去除催化载体而对SWCNT造成的损害;(2)小金属颗粒很容易溶解在盐酸中,与氢氟酸或硝酸相比,这是一种温和得多的化学处理方法;(3)对单壁碳纳米管具有高选择性,而多壁碳纳米管或石墨可以忽略不计,这有利于通过选择性氧化去除不需要的碳物种。通过高分辨率透射电子显微镜、扫描电子显微镜、拉曼光谱、紫外-可见-近红外光谱和荧光光谱、分级(6,5)管上的溶液氧化还原化学以及基于SWCNT的场效应晶体管器件性能对该纯化程序的有效性进行了评估。结果表明,Co-MCM-41催化剂不仅提供具有窄半导体(n,m)分布的管,而且允许采用温和的纯化程序,因此产生的SWCNT缺陷更少。