English

Modulating the Diameter of Bulk Single-Walled Carbon Nanotubes Grown by FeCo/MgO Catalyst

• Zeyao Zhang ^{1, 2, 4, 5,} ,
• Yixi Yao ^{2, 3,} ,
• Yan Li ^{2, 3, 4, ,}

• 1.

  Peking University Shenzhen Institute, Shenzhen 518057, Guangdong Province, China

• 2.

  Beijing National Laboratory for Molecular Science, Key Laboratory for the Physics and Chemistry of Nanodevices, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China

• 3.

  Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871, China

• 4.

  PKU-HKUST ShenZhen-HongKong Institution, Shenzhen 518057, Guangdong Province, China

• 5.

  College of Engineering, Peking University, Beijing 100871, China

Corresponding author: Yan Li, Email: yanli@pku.edu.cn; Tel.: +86-10-62756773

• Received Date: 28 January 2021
  Accepted Date: 02 March 2021
  Revised Date: 02 March 2021
  Available Online: 15 August 2022
• Fund Project:

  the Shenzhen Basic Research Project 

  the Shenzhen KQTD Project 

  the National Science and Technology Major Project of the Ministry of Science and Technology of China 

  the National Natural Science Foundation of China 

  the Beijing National Laboratory for Molecular Sciences 

Abstract: The diameter-controlled growth of single-walled carbon nanotubes (SWNTs) is one of the key issues of SWNT synthesis and application. To guarantee that SWNTs grow with desired diameters, it is necessary to control catalyst size and modulate growth conditions. SWNTs with diameters of 0.9–1.2 nm are highly desirable for near-infrared fluorescence bioimaging and serving as effective single-photon sources for the development of quantum devices. Herein, we used an FeCo/MgO catalyst to grow bulk SWNTs with diameters in the range and studied the influence of catalysts and chemical vapor deposition (CVD) growth conditions on the diameter of SWNTs. The preparation of catalyst precursors is a key step in obtaining catalyst nanoparticles of small size. In the impregnation process, we used three different types of metal salts, namely, sulfates, acetates, and nitrates, to prepare the catalysts. The metal sulfates, which exhibit the weakest hydrolysis ability, were found to grow SWNTs with the smallest diameters. Lowering the immersion pH, which suppresses the hydrolysis of metal ions, was also favorable for growing smaller SWNTs. Moreover, the addition of complexing agent molecules such as ethylenediaminetetraacetic acid during the impregnation process, which inhibits the hydrolysis of metal ions as well, further confined the diameter distribution of the resultant SWNTs. During the solution drying process, metal salts hydrolyze into metal hydroxides and oxides. Under mild hydrolysis conditions, the produced hydroxide and oxide particles are smaller and more likely to be uniformly distributed on the surface of the supports. Therefore, it is more favorable to produce catalysts with controlled sizes under mild hydrolysis conditions, which are preferred for diameter control of the resultant SWNTs. In the CVD growth process, we used either ethanol or methane as the carbon source and found that, under our experimental conditions, the SWNTs grown from ethanol had smaller diameters than those from methane. The hydrogen content in the CVD process also affects diameter distribution of SWNTs. As the carbon-to-hydrogen ratio decreased, SWNTs with larger diameters disappeared, and the number of SWNTs with smaller diameters increased. During the CVD process, the carbon-to-hydrogen ratio determines the carbon feeding rate to the catalysts. At a low carbon feeding rate, catalysts of large sizes are underfed and unable to grow SWNTs, whereas smaller catalysts are in a favorable condition for growth. Therefore, the average diameter of the SWNTs decreased as the carbon-to-hydrogen ratio decreased.

Key words:
• Single-walled carbon nanotube
•  /  Chemical vapor deposition
•  /  Controlled growth
•  /  Diameter
•  /  Metal catalyst
•  /  Precursor
•  /  Nano particle

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