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

doi:10.11949/0438-1157.20210007

Abstract

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

CLC Number:

TM 53

Shaoling CONG, Jie ZHAO, Yufei YANG, Changqing WU, Fan HE, Hua YUAN, Xiaoqin WANG, Shanxin XIONG, Yan WU, Anning ZHOU. Synthesis of N-doped carbon micro-nanotubes using coal-based polyaniline as a carbon and nitrogen source[J]. CIESC Journal, 2021, 72(9): 4950-4960.

从少领, 赵捷, 杨玉飞, 吴长清, 贺凡, 袁华, 汪晓芹, 熊善新, 吴燕, 周安宁. 煤基聚苯胺制掺N碳微纳米管的实验研究[J]. 化工学报, 2021, 72(9): 4950-4960.

Figures/Tables 8

Fig.1 Schematic diagram of the device for the carbon mico-nanotube growth

Table 1 The N-doping contents， yields and morphological features of carbon micro-nanotubes grown on three organometallic catalysts

生长催化剂	NCMNT
生长催化剂	掺N量/ %(质量)	收率 (碳管/生长催化剂/煤基聚苯胺的质量比)	形态特征
二茂镍	0.68	9.28/1/160	微米管和纳米管均较多；微米管大多为直立管，管径可达400 nm，壁厚约30 nm；纳米管大多为弯曲管，管径约60 nm，壁厚约10 nm；碳管中嵌有单质镍粒子。伴有竹节状管、糖葫芦串状碳
乙酸镍	1.17	9.36/1/160	管径在10~200 nm，以30~80 nm的纳米弯曲管居多，粗细较均匀；伴有竹节状管、糖葫芦串状碳
二茂铁	0.51	1.06/1/5	管径分布在23~128 nm，以35~75 nm的纳米管为主，壁厚约10 nm

Fig.2 The N 1s XPS spectra of three NCMNT partiles

Fig.3 SEM and TEM images of NCMNT-1 particles synthesized over nickelocene catalyst

Fig.4 SEM and TEM images of NCMNT-2 particles synthesized over nickel acetate catalyst

Fig.5 SEM, TEM images and diameter distribution of NCMNT-3 particles synthesized over ferrocene catalyst

Fig.6 XRD patterns and Raman spectra of carbon micro-nanotubes synthesized over three catalysts

Fig.7 Cyclic voltammograms curves, chronoamperometry curves and TEM image of Pt/NCMNT and Pt/CNT catalysts

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