高等学校化学学报 ›› 2020, Vol. 41 ›› Issue (11): 2503-2510.doi: 10.7503/cjcu20200342

• 物理化学 • 上一篇    下一篇

氮掺杂碳纳米管的合成及活化过一硫酸盐的性能与机理

闫松, 张成武, 袁芳, 秦传玉()   

  1. 吉林大学新能源与环境学院, 地下水资源与环境教育部重点实验室, 石油化工污染场地控制与修复技术国家联合工程实验室, 长春 130012
  • 收稿日期:2020-06-10 出版日期:2020-11-10 发布日期:2020-11-06
  • 通讯作者: 秦传玉 E-mail:qincyu@jlu.edu.cn
  • 基金资助:
    国家重点研发计划项目(2018YFC1802503)

Synthesis of Nitrogen-doped Carbon Nanotubes and the Performance and Mechanism of PMS Activation

YAN Song, ZHANG Chengwu, YUAN Fang, QIN Chuanyu()   

  1. School of New Energy and Environment,Key Laboratory of Groundwater Resources and Environment,Ministry of Education,National and Local Joint Engineering Laboratory for Petrochemical Contaminated Site Control and Remediation Technology,Jilin University,Changchun 130012,China
  • Received:2020-06-10 Online:2020-11-10 Published:2020-11-06
  • Contact: QIN Chuanyu E-mail:qincyu@jlu.edu.cn
  • Supported by:
    Supported by the National Key R&D Program of China(2018YFC1802503)

摘要:

以多壁碳纳米管(MWCNT)为原材料, 三聚氰胺为氮前体, 采用高温煅烧法制得了含氮量约3.33%(摩尔分数)的氮掺杂碳纳米管(N-CNT-700), 该纳米管为一维材料. N-CNT-700活化过一硫酸盐(PMS)体系60 min内对苯酚的降解效率可达100%, 总有机碳(TOC)去除率可达61.6%, 体系的活化能为35.4 kJ/mol. 通过电子顺磁共振(EPR)检测、 掩蔽实验及PMS浓度测定等方式确定了体系降解机制为自由基(·OH, SO4·-)与非自由基共同作用, 除去9%的吸附去除外, 91%的氧化降解中自由基作用占比约49%, 单线态氧(1O2)作用占比约18%, 活性中间体作用占比约24%. N-CNT-700的反应活性随着重复利用次数的增加而降低, 高温处理可以恢复其高反应活性. 煅烧温度影响材料中的氮含量及种类, N-CNT的反应活性与氮含量成正比, 且与石墨氮含量密切相关.

关键词: 碳纳米管, 氮掺杂, 过一硫酸盐, 苯酚, 反应活性

Abstract:

Using multi-wall carbon nanotubes(MWCNT) as raw materials and melamine as a nitrogen precursor, a nitrogen-doped carbon nanotube(N-CNT-700) with a nitrogen content of about 3.33%(molar fraction) was prepared by high-temperature calcination. N-CNT-700 is a one-dimensional tubular nanomaterial, the de-gradation efficiency of phenol can reach 100%, and the total organic carbon(TOC) removal rate can reach 61.6%, and the activation energy of the system is 35.4 kJ/mol within 60 min in N-CNT-700 activated PMS system. Through electron paramagnetic resonance(EPR) detection, quenching experiment and PMS concentration determination, the degradation mechanism of the system was determined to be free radicals(·OH, SO4·-) and non-free radicals, in addition to 9% adsorption removal, in the 91% oxidative degradation, free radicals account for about 49%, 1O2 for about 18%, and active intermediates for about 24%. The reactivity of N-CNT-700 decreases as the number of reuses increases, and high temperature treatment can restore its high reactivity. The calcination temperature affects the nitrogen content and types of the material. The reactivity of N-CNT is proportional to the nitrogen content and is closely related to the nitrogen content of graphite.

Key words: Carbon nanotubes, Nitrogen doping, Peroxymonosulfate, Phenol, Reactivity

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