State Key Laboratory of Optoelectronic Materials and Technologies, School of Physics and Engineering, Sun Yat-Sen University, Guangzhou 510275, China.
ACS Nano. 2013 Apr 23;7(4):3095-103. doi: 10.1021/nn305180g. Epub 2013 Mar 18.
We propose a unique experimental technique in which isotopically labeled ethanol, e.g., 12CH3-13CH2-OH, is used to trace the carbon atoms during the formation of single-walled carbon nanotubes (SWNTs) by chemical vapor deposition (CVD). The proportion of 13C is determined from Raman spectra of the obtained SWNTs, yielding the respective contribution of ethanol's two different carbon atoms to SWNT formation. Surprisingly, the carbon away from the hydroxyl group is preferably incorporated into the SWNT structure, and this preference is significantly affected by growth temperature, presence of secondary catalyst metal species such as Mo, and even by the substrate material. These experiments provide solid evidence confirming that the active carbon source is not limited to products of gas-phase decomposition such as ethylene and acetylene, but ethanol itself is arriving at and reacting with the metal catalyst particles. Furthermore, even the substrate or other catalytically inactive species directly influences the formation of SWNTs, possibly by changing the local environment around the catalyst or even the reaction pathway of SWNT formation. These unexpected effects, which are inaccessible by conventional techniques, paint a clearer picture regarding the decomposition and bond breaking process of the ethanol precursor during the entire CVD process and how this might influence the quality of the obtained SWNTs.
我们提出了一种独特的实验技术,即在化学气相沉积(CVD)过程中通过使用同位素标记的乙醇,例如 12CH3-13CH2-OH,来追踪单壁碳纳米管(SWNTs)形成过程中的碳原子。通过对所获得的 SWNTs 的拉曼光谱确定 13C 的比例,从而确定乙醇的两个不同碳原子对 SWNT 形成的各自贡献。令人惊讶的是,远离羟基的碳原子更倾向于掺入 SWNT 结构中,这种偏好受生长温度、存在如 Mo 等二次催化剂金属物种,甚至受基底材料的显著影响。这些实验提供了确凿的证据,证实活性碳源不仅限于气相分解产物,如乙烯和乙炔,而是乙醇本身到达并与金属催化剂颗粒发生反应。此外,即使是基底或其他非催化活性物质也会直接影响 SWNTs 的形成,可能通过改变催化剂周围的局部环境,甚至改变 SWNT 形成的反应途径。这些通过传统技术无法获得的意外影响,更清晰地描绘了整个 CVD 过程中乙醇前体的分解和键断裂过程,以及这如何影响所获得的 SWNTs 的质量。