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

作　　者：从少领 赵捷[2] 杨玉飞 吴长清 贺凡 袁华 汪晓芹 熊善新[1,2] 吴燕 周安宁[1,2] CONG Shaoling;ZHAO Jie;YANG Yufei;WU Changqing;HE Fan;YUAN Hua;WANG Xiaoqin;XIONG Shanxin;WU Yan;ZHOU Anning(Key Laboratory of Coal Resources Exploration and Comprehensive Utilization,Ministry of Natural Resources,Xi’an 710021,Shaanxi,China;School of Chemistry and Chemical Engineering,Xi’an University of Science and Technology,Xi’an 710054,Shaanxi,China;Department of Chemical Engineering and Power Engineering,Shenmu Vocational&Technical College,Shenmu 719300,Shaanxi,China)

机构地区：[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

出　　处：《化工学报》2021年第9期4950-4960,共11页CIESC Journal

基　　金：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)。

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。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.

关 键 词：煤 热解 催化剂 化学气相沉积法 碳微纳米管 N掺杂 

分 类 号：TM53[电气工程—电器]