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费托合成的气态产物混合物作为低温 CVD 生长碳纳米管地毯的有效碳源。

Gaseous product mixture from Fischer-Tropsch synthesis as an efficient carbon feedstock for low temperature CVD growth of carbon nanotube carpets.

机构信息

Department of Chemical Engineering, Kansas State University, Manhattan, Kansas 66506, USA.

出版信息

Nanoscale. 2016 Jul 21;8(27):13476-87. doi: 10.1039/c6nr03679a. Epub 2016 Jun 29.

Abstract

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.

摘要

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。

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