CIESC Journal ›› 2021, Vol. 72 ›› Issue (9): 4950-4960.DOI: 10.11949/0438-1157.20210007

• Material science and engineering, nanotechnology • Previous Articles     Next Articles

Synthesis of N-doped carbon micro-nanotubes using coal-based polyaniline as a carbon and nitrogen source

Shaoling CONG1,2(),Jie ZHAO2,Yufei YANG2,3,Changqing WU2,Fan HE2,Hua YUAN2,Xiaoqin WANG1,2(),Shanxin XIONG1,2,Yan WU1,Anning ZHOU1,2   

  1. 1.Key Laboratory of Coal Resources Exploration and Comprehensive Utilization,Ministry of Natural Resources, Xi’an 710021, Shaanxi, China
    2.School of Chemistry and Chemical Engineering, Xi’an University of Science and Technology, Xi’an 710054, Shaanxi, China
    3.Department of Chemical Engineering and Power Engineering, Shenmu Vocational & Technical College, Shenmu 719300, Shaanxi, China
  • Received:2021-01-04 Revised:2021-05-27 Online:2021-09-05 Published:2021-09-05
  • Contact: Xiaoqin WANG

煤基聚苯胺制掺N碳微纳米管的实验研究

从少领1,2(),赵捷2,杨玉飞2,3,吴长清2,贺凡2,袁华2,汪晓芹1,2(),熊善新1,2,吴燕1,周安宁1,2   

  1. 1.自然资源部煤炭资源勘查与综合利用重点实验室,陕西 西安 710021
    2.西安科技大学化学与化工学院,陕西 西安 710054
    3.神木职业技术学院化工-电力工程系,陕西 神木 719300
  • 通讯作者: 汪晓芹
  • 作者简介:从少领(1996—),女,硕士研究生,1489178496@qq.com
  • 基金资助:
    陕西省自然科学基金项目(2020JM-518);煤炭资源勘查与综合利用重点实验室开放课题(KF2020-11);碑林区科技计划项目(GX2030)

Abstract:

China is rich in coal resources. Using coal as a raw material to prepare carbon nanotubes can achieve efficient utilization of coal resources, reduce environmental pollution, and provide a new way for the development of the coal industry.Three N-doped carbon micro-nanotubes with high graphitization degree were successfully synthesized by an approach coupling catalytic pyrolysis with chemical vapor deposition, using home-made coal-based polyaniline as a carbon and nitrogen source, selecting nickel acetate or ferric citrate as a pyrolysis catalyst and choosing nickelocene, nickel acetate or ferrocene as a catalyst for the growth of carbon tubes. The results of SEM, TEM, XRD, Raman and XPS tests showed that three carbon micro-nanotubes exhibited various morphologies including erect tubes, curved tubes and bamboo-like tubes. Nickelocene and ferrocene catalyst were suitable for growing long and upright tubes, and nickel acetate catalyst was beneficial for growing short and curved tubes. The yield of carbon micro-nanotubes grown by nickelocene catalyst was closed to that of nickel acetate catalyst and they were approx 5.8%(mass). In contrast, the yield of carbon micro-nanotubes grown by ferrocene catalyst was higher to 21.2%(mass). Furthermore, the as-doped N element mostly existed in three carbon micro-nanotubes with the chemical state of graphitic N. The carbon micro-nanotubes grown by nickel acetate catalyst had the highest N-doping content, up to 1.17%(mass), which was a suitable support for MOR electrocatalysts.

Key words: coal, pyrolysis, catalyst, chemical vapor deposition, carbon micro-nanotubes, nitrogen doping

摘要:

我国煤炭资源丰富,以煤为原料制备碳纳米管,可以实现煤炭资源的高效利用,减少环境污染,为煤炭行业的发展提供新途径。以煤基聚苯胺为碳氮源,分别以乙酸镍或柠檬酸铁为碳源热解催化剂,以二茂镍、乙酸镍或二茂铁为碳管生长催化剂,采用催化热解-化学气相沉积耦合法成功制备出了三种高石墨化程度的掺N碳微纳米管。并对其进行了SEM、TEM、XRD、Raman、XPS等结构测试和甲醇氧化电催化剂载体应用测试,结果发现:三种掺N碳微纳米管的微观形态多样,有直立管、弯曲管、竹节状管等。二茂镍和二茂铁适合生长长而直的碳管,乙酸镍适合生长短而弯的碳管。二茂镍和乙酸镍所长碳管收率相当,约为5.8%(质量);二茂铁所长碳管收率较高,为21.2%(质量)。N元素主要以石墨型N掺入三种碳微纳米管中,乙酸镍所长碳管的掺N量最高,为1.17%(质量),且表现出良好的电催化剂载体性能。

关键词: 煤, 热解, 催化剂, 化学气相沉积法, 碳微纳米管, N掺杂

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