煤基聚苯胺制掺N碳微纳米管的实验研究

doi:10.11949/0438-1157.20210007

化工学报 ›› 2021, Vol. 72 ›› Issue (9): 4950-4960.DOI: 10.11949/0438-1157.20210007

• 材料化学工程与纳米技术 • 上一篇下一篇

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.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

收稿日期:2021-01-04 修回日期:2021-05-27 出版日期:2021-09-05 发布日期:2021-09-05
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)

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

Shaoling CONG^1,²(),Jie ZHAO²,Yufei YANG^2,³,Changqing WU²,Fan HE²,Hua YUAN²,Xiaoqin WANG^1,²(),Shanxin XIONG^1,²,Yan WU¹,Anning ZHOU^1,²

^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

摘要/Abstract

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

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

中图分类号:

TM 53

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.

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.

图/表 8

图1 碳管生长装置示意图

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

表1 三种有机金属催化剂所长碳微纳米管的掺N量、收率及形态特征

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

图2 三种NCMNT的N 1s高分辨XPS谱图

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

图3 NCMNT-1的SEM图与TEM图

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

图4 NCMNT-2的SEM图与TEM图

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

图5 NCMNT-3的SEM、TEM图和管径分布

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

图6 三种催化剂所长碳微纳米管的XRD谱图与Raman谱图

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

图7 Pt/NCMNT和Pt/CNT催化剂的循环伏安曲线、计时电流曲线与TEM图

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

参考文献 39

1	Liu J H, Wu S Q, He C X, et al. Structure, property and application of carbon nanotubes and carbon microtubes[J]. Journal of Shenzhen University Science and Engineering, 2013, 30(1): 1-11.
2	Journet C, Maser W K, Bernier P, et al. Large-scale production of single-walled carbon nanotubes by the electric-arc technique[J]. Nature, 1997, 388(6644): 756-758.
3	李振涛, 董强, 刘红, 等. 以太西无烟煤为碳源制备单壁碳纳米管[J]. 化工学报, 2010, 61(4): 1040-1046.
	Li Z T, Dong Q, Liu H, et al. Preparation and characterization of single-walled carbon nanotubes from Taixi anthracite[J]. CIESC Journal, 2010, 61(4): 1040-1046.
4	Li Y F, Qiu J S, Zhao Z B, et al. Bamboo-shaped carbon tubes from coal[J]. Chemical Physics Letters, 2002, 366(5/6): 544-550.
5	邱介山, 韩红梅, 周颖, 等. 由二种烟煤制备碳纳米管的探索性研究[J]. 新型炭材料, 2001, 16(4): 1-6.
	Qiu J S, Han H M, Zhou Y, et al. Carbon nanotubes from two bituminous coals[J]. New Carbon Materials, 2001, 16(4): 1-6.
6	赵宗彬, 邱介山, 王同华, 等. 以煤为碳源直流电弧法制备单壁纳米碳管绳[J]. 新型炭材料, 2006, 21(1): 19-23.
	Zhao Z B, Qiu J S, Wang T H, et al. Fabrication of single-walled carbon nanotube ropes from coal by an arc discharge method[J]. New Carbon Materials, 2006, 21(1): 19-23.
7	Calderon Moreno J M, Yoshimura M. Hydrothermal processing of high-quality multiwall nanotubes from amorphous carbon[J]. Journal of the American Chemical Society, 2001, 123(4): 741-742.
8	Kumar M, Ando Y. Chemical vapor deposition of carbon nanotubes: a review on growth mechanism and mass production[J]. Journal of Nanoscience and Nanotechnology, 2010, 10(6): 3739-3758.
9	Wen G W, Yu H M, Huang X X. Synthesis of carbon microtube buckypaper by a gas pressure enhanced chemical vapor deposition method[J]. Carbon, 2011, 49(12): 4067-4069.
10	Ikegami T, Nakanishi F, Uchiyama M, et al. Optical measurement in carbon nanotubes formation by pulsed laser ablation[J]. Thin Solid Films, 2004, 457(1): 7-11.
11	Ghosh P, Afre R A, Soga T, et al. A simple method of producing single-walled carbon nanotubes from a natural precursor: eucalyptus oil[J]. Materials Letters, 2007, 61(17): 3768-3770.
12	Liu Q, Liu W, Cui Z M, et al. Synthesis and characterization of 3D double branched K junction carbon nanotubes and nanorods[J]. Carbon, 2007, 45(2): 268-273.
13	Jang J W, Lee C E, Lyu S C, et al. Structural study of nitrogen-doping effects in bamboo-shaped multiwalled carbon nanotubes[J]. Applied Physics Letters, 2004, 84(15): 2877-2879.
14	Qiu J S, An Y L, Zhao Z B, et al. Catalytic synthesis of single-walled carbon nanotubes from coal gas by chemical vapor deposition method[J]. Fuel Processing Technology, 2004, 85(8/9/10): 913-920.
15	Awasthi S, Awasthi K, Ghosh A K, et al. Formation of single and multi-walled carbon nanotubes and graphene from Indian bituminous coal[J]. Fuel, 2015, 147: 35-42.
16	Ren Z F, Huang Z P, Xu J W, et al. Synthesis of large arrays of well-aligned carbon nanotubes on glass[J]. Science, 1998, 282(5391): 1105-1107.
17	吴霞, 王鲁香, 刘浪, 等. 新疆煤基碳纳米管的调控制备[J]. 无机化学学报, 2013, 29(9): 1842-1848.
	Wu X, Wang L X, Liu L, et al. Controllable preparation of carbon nanotubes from Xinjiang coal[J]. Chinese Journal of Inorganic Chemistry, 2013, 29(9): 1842-1848.
18	Wang X F, Liu X Q, Lai L F, et al. Syntheses, properties and electrochemical activity of carbon microtubes modified with amino groups[J]. Advanced Functional Materials, 2008, 18(12): 1809-1823.
19	Libera J, Gogotsi Y. Hydrothermal synthesis of graphite tubes using Ni catalyst[J]. Carbon, 2001, 39(9): 1307-1318.
20	于洪明. 碳微米管的合成及其性能研究[D]. 哈尔滨: 哈尔滨工业大学, 2011.
	Yu H M. Synthesis and properties of carbon microtubes[D]. Harbin: Harbin Institute of Technology, 2011.
21	Li L X, Liu Y C, Geng X, et al. Synthesis and electrochemical performance of nitrogen-doped carbon nanotubes[J]. Acta Physico-Chimica Sinica, 2011, 27(2): 443-448.
22	Zhao G Q, Tang Y L, Wan G P, et al. High-performance and flexible all-solid-state hybrid supercapacitor constructed by NiCoP/CNT and N-doped carbon coated CNT nanoarrays[J]. Journal of Colloid and Interface Science, 2020, 572: 151-159.
23	Wang X Q, Li Q Q, Zhang Y, et al. Synthesis and capacitance properties of N-doped porous carbon/NiO nanosheet composites using coal-based polyaniline as carbon and nitrogen source[J]. Applied Surface Science, 2018, 442: 565-574.
24	Wu B H, Zhu J J, Li X, et al. PtRu nanoparticles supported on p-phenylenediamine-functionalized multiwalled carbon nanotubes: enhanced activity and stability for methanol oxidation[J]. Ionics, 2019, 25(1): 181-189.
25	Su D S, Chen X W, Liu X, et al. Mount-etna-lava-supported nanocarbons for oxidative dehydrogenation reactions[J]. Advanced Materials, 2008, 20(19): 3597-3600.
26	Lin J, Yang Y H, Zhang H A, et al. Optimization of CNTs growth on TiB₂-based composite powders by CVD with Fe as catalyst[J]. Ceramics International, 2020, 46(3): 3837-3843.
27	Lin J, Yang Y H, Zhang H A, et al. Preparation of CNT-Co@TiB₂ by catalytic CVD: effects of synthesis temperature and growth time[J]. Diamond and Related Materials, 2020, 106: 107830.
28	Escobar M, Rubiolo G, Candal R, et al. Effect of catalyst preparation on the yield of carbon nanotube growth[J]. Physica B: Condensed Matter, 2009, 404(18): 2795-2798.
29	Paraknowitsch J P, Thomas A, Antonietti M. A detailed view on the polycondensation of ionic liquid monomers towards nitrogen doped carbon materials[J]. Journal of Materials Chemistry, 2010, 20(32): 6746.
30	Ashok A, Kumar A, Ponraj J, et al. Synthesis and growth mechanism of bamboo like N-doped CNT/graphene nanostructure incorporated with hybrid metal nanoparticles for overall water splitting[J]. Carbon, 2020, 170: 452-463.
31	Deng H J, Li Q, Liu J J, et al. Active sites for oxygen reduction reaction on nitrogen-doped carbon nanotubes derived from polyaniline[J]. Carbon, 2017, 112: 219-229.
32	丁佩. 碳氮纳米管的制备、表征及场致电子发射特性研究[D]. 郑州: 郑州大学, 2003.
	Ding P. Preparation, characterization and field electron emission properties of CN_x nanotubes[D]. Zhengzhou: Zhengzhou University, 2003.
33	杨永哲. 掺氮碳纳米管的制备及其催化硝基苯加氢性能研究[D]. 湘潭: 湘潭大学, 2018.
	Yang Y Z. Nitrogen-doped carbon nanotubes preparation and their catalytic performance in nitrobenzene hydrogenation reaction[D]. Xiangtan: Xiangtan University, 2018.
34	Yin X F, He L M, Syed-Hassan S S A, et al. One-step preparation of a N-CNTs@Ni foam electrode material with the co-production of H₂ by catalytic reforming of N-containing compound of biomass tar[J]. Fuel, 2020, 280: 118601.
35	Ha Y, Shi L X, Yan X X, et al. Multifunctional electrocatalysis on a porous N-doped NiCo₂O₄@C nanonetwork[J]. ACS Applied Materials & Interfaces, 2019, 11(49): 45546-45553.
36	Arrigo R, Hävecker M, Schlögl R, et al. Dynamic surface rearrangement and thermal stability of nitrogen functional groups on carbon nanotubes[J]. Chemical Communications, 2008, (40): 4891-4893.
37	Baker R T K. Catalytic growth of carbon filaments[J]. Carbon, 1989, 27(3): 315-323.
38	Kunadian I, Andrews R, Qian D L, et al. Growth kinetics of MWCNTs synthesized by a continuous-feed CVD method[J]. Carbon, 2009, 47(2): 384-395.
39	Zhu C Y, Xie Z L, Guo K M. Growth mechanism of carbon nanotubes in floating catalyst system[J]. Journal of Functional Materials, 2005, 36(11): 1789-1793, 1797.

[1]	何松, 刘乔迈, 谢广烁, 王斯民, 肖娟. 高浓度水煤浆管道气膜减阻两相流模拟及代理辅助优化[J]. 化工学报, 2023, 74(9): 3766-3774.
[2]	陈杰, 林永胜, 肖恺, 杨臣, 邱挺. 胆碱基碱性离子液体催化合成仲丁醇性能研究[J]. 化工学报, 2023, 74(9): 3716-3730.
[3]	吴雷, 刘姣, 李长聪, 周军, 叶干, 刘田田, 朱瑞玉, 张秋利, 宋永辉. 低阶粉煤催化微波热解制备含碳纳米管的高附加值改性兰炭末[J]. 化工学报, 2023, 74(9): 3956-3967.
[4]	陈哲文, 魏俊杰, 张玉明. 超临界水煤气化耦合SOFC发电系统集成及其能量转化机制[J]. 化工学报, 2023, 74(9): 3888-3902.
[5]	杨学金, 杨金涛, 宁平, 王访, 宋晓双, 贾丽娟, 冯嘉予. 剧毒气体PH₃的干法净化技术研究进展[J]. 化工学报, 2023, 74(9): 3742-3755.
[6]	赵佳佳, 田世祥, 李鹏, 谢洪高. SiO₂-H₂O纳米流体强化煤尘润湿性的微观机理研究[J]. 化工学报, 2023, 74(9): 3931-3945.
[7]	李艺彤, 郭航, 陈浩, 叶芳. 催化剂非均匀分布的质子交换膜燃料电池操作条件研究[J]. 化工学报, 2023, 74(9): 3831-3840.
[8]	韩晨, 司徒友珉, 朱斌, 许建良, 郭晓镭, 刘海峰. 协同处理废液的多喷嘴粉煤气化炉内反应流动研究[J]. 化工学报, 2023, 74(8): 3266-3278.
[9]	倪文翔, 赵京, 李博, 魏小林, 吴东垠, 刘迪, 王强. 转炉煤气全干法显热回收工艺中余热锅炉积灰特性研究[J]. 化工学报, 2023, 74(8): 3485-3493.
[10]	杨菲菲, 赵世熙, 周维, 倪中海. Sn掺杂的In₂O₃催化CO₂选择性加氢制甲醇[J]. 化工学报, 2023, 74(8): 3366-3374.
[11]	李凯旋, 谭伟, 张曼玉, 徐志豪, 王旭裕, 纪红兵. 富含零价钴活性位点的钴氮碳/活性炭设计及甲醛催化氧化应用研究[J]. 化工学报, 2023, 74(8): 3342-3352.
[12]	杨欣, 彭啸, 薛凯茹, 苏梦威, 吴燕. 分子印迹-TiO₂光电催化降解增溶PHE废水性能研究[J]. 化工学报, 2023, 74(8): 3564-3571.
[13]	余娅洁, 李静茹, 周树锋, 李清彪, 詹国武. 基于天然生物模板构建纳米材料及集成催化剂研究进展[J]. 化工学报, 2023, 74(7): 2735-2752.
[14]	涂玉明, 邵高燕, 陈健杰, 刘凤, 田世超, 周智勇, 任钟旗. 钙基催化剂的设计合成及应用研究进展[J]. 化工学报, 2023, 74(7): 2717-2734.
[15]	张琦钰, 高利军, 苏宇航, 马晓博, 王翊丞, 张亚婷, 胡超. 碳基催化材料在电化学还原二氧化碳中的研究进展[J]. 化工学报, 2023, 74(7): 2753-2772.

煤基聚苯胺制掺N碳微纳米管的实验研究

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

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 8

参考文献 39

相关文章 15

编辑推荐

Metrics

本文评价