Department of Chemical Engineering, Kansas State University, Manhattan, Kansas 66506, USA.
Nanoscale. 2016 Jul 21;8(27):13476-87. doi: 10.1039/c6nr03679a. Epub 2016 Jun 29.
Low-temperature chemical vapor deposition (CVD) growth of carbon nanotube (CNT) carpets from Fe and Fe-Cu catalysts using a gaseous product mixture from Fischer-Tropsch synthesis (FTS-GP) as a superior carbon feedstock is demonstrated. This growth approach addresses a persistent issue of obtaining thick CNT carpets on temperature-sensitive substrates at low temperatures using a non-plasma CVD approach without catalyst pretreatment and/or preheating of the carbon feedstock. The efficiency of the process is evidenced by the highly dense, vertically aligned CNT structures from both Fe and Fe-Cu catalysts even at temperatures as low as 400 °C - a record low growth temperature for CNT carpets obtained via conventional thermal CVD. The grown CNTs exhibit a straight morphology with hollow interior and parallel graphitic planes along the tube walls. The apparent activation energies for CNT carpet growth on Fe and Fe-Cu catalysts are 0.71 and 0.54 eV, respectively. The synergistic effect of Fe and Cu show a strong dependence on the growth temperature, with Cu being more influential at temperatures higher than 450 °C. The low activation energies and long catalyst lifetimes observed are rationalized based on the unique composition of FTS-GP and Gibbs free energies for the decomposition reactions of the hydrocarbon components. The use of FTS-GP facilitates low-temperature growth of CNT carpets on traditional (alumina film) and nontraditional substrates (aluminum foil) and has the potential of enhancing CNT quality, catalyst lifetime, and scalability.
采用费托合成(Fischer-Tropsch synthesis,FTS)气体产物混合物(FTS-GP)作为优质碳源,通过低温化学气相沉积(CVD)方法在 Fe 和 Fe-Cu 催化剂上生长碳纳米管(CNT)毯,证明了这一方法的可行性。该生长方法解决了一个长期存在的问题,即在低温下使用非等离子体 CVD 方法,无需对催化剂进行预处理和/或对碳源进行预热,在温度敏感的衬底上获得厚 CNT 毯。该过程的效率可从以下方面得到证明:即使在 400°C 的低温下,使用 Fe 和 Fe-Cu 催化剂都能获得高度密集、垂直排列的 CNT 结构,这是通过传统热 CVD 获得 CNT 毯的最低生长温度。生长的 CNT 具有直的形态,内部为空,管壁上的平行石墨层。在 Fe 和 Fe-Cu 催化剂上生长 CNT 毯的表观活化能分别为 0.71 和 0.54 eV。Fe 和 Cu 的协同效应强烈依赖于生长温度,在高于 450°C 的温度下 Cu 的影响更大。观察到的低活化能和长催化剂寿命可以根据 FTS-GP 的独特组成和烃类成分分解反应的吉布斯自由能来解释。使用 FTS-GP 可以促进 CNT 毯在传统(氧化铝膜)和非传统(铝箔)衬底上的低温生长,并有可能提高 CNT 的质量、催化剂的寿命和可扩展性。