多壁碳纳米管的改性及NO吸附—脱附研究
摘要
本文采用碱活化法(KOH)、环糊精非共价法对多壁碳纳米管进行改性,并制备了氮、硼掺杂的碳纳米管。采用SEM、TG-MS、XRD、XPS、FT-IR、Raman等对所制备和改性的碳纳米管进行了表征。结果表明碱活化后的碳纳米管其比表面积较碱活化前的碳纳米管明显增大,SEM图片显示碱活化后的碳纳米管变直变短;而经环糊精改性的碳纳米管表面被环糊精所包裹,XRD和Raman研究表明,碱活化法和环糊精改性的碳纳米管结构并没有发生变化。而氮硼掺杂改性的碳纳米管Raman谱图G峰峰位向波数大的方向偏移,表现出半导体的特性。
NO吸附-脱附研究结果发现:经碱活化和环糊精改性的碳纳米管,对NO吸附的能力明显增强。因为碱活化后的碳纳米管的比表面积增大,增强了碳纳米管对NO的吸附能力;而环糊精特有的空腔和多羟基结构对NO具有选择吸附性能。
用氮、硼掺杂改性的碳纳米管,制备碳纳米管修饰电极,进行NO在碳纳米管修饰电极上的电氧化研究。研究发现氮、硼掺杂改性的碳纳米管修饰电极NO电催化反应活性增加,反应的活化能降低,提高了NO电化学氧化反应的灵敏度。
In this article, muli-walled carbon nanotubes modified by KOH,β-Cyclodextrin , and doped with B or N have been synthesized. The samples are characterized by SEM, TG-MS, XRD, FT-IR, Raman and XPS. The results demonstrate that the BET surface area of MWCNTs activated by KOH is higher than those of unactivated MWCNTs. And SEM images show that MWCNTs activated by KOH becomes shorter and straighter. While MWCNTs were modified withβ-Cyclodextrin,β-Cyclodextrin enwrapped the surface of MWCNTs. MWCNTs activated by KOH and modified byβ-Cyclodextrin were characterized by the means of XRD and Raman, it was found the structure of the MWCNTs didn’t changed. The results of NO adsorption-desorption showed that the adsorption of NO of MWCNTs activated by KOH and modified byβ-Cyclodextrin are obviously higher than that of MWCNTs. Because of the larger BET surface area of MWCNTs activated by KOH, therefore the NO adsorption capability of MWCNTs activated by KOH was improved; andβ-Cyclodextrin that wrapped MWCNTs has unique cavum and NO can be adsorbed inside it, the adsorption amount of NO of MWCNTs modified byβ-Cyclodextrin increased comparison of MWCNTs. The Raman G bands of MWCNTs dopped with N and B happen to red shift, which show the characteristic of semiconductor obviously.
Electrocatalytic oxidation of nitric oxide (NO) at the modified electrodes of MWCNTs dopped with N and B were studied with cyclic voltammetric determination.
The activity of modified electrode of MWCNTs dopped with N and B were better than that of MWCNTs, MWCNTs activated by KOH and modified byβ-Cyclodextrin. The activation energy (anode potential of MWCNTs dopped with N and B) of NO oxidation decreased. The result demonstrates that sensitivity of NO electrocatalytic oxidation reaction of MWCNTs dopped with N and B was enhanced.
NO吸附-脱附研究结果发现:经碱活化和环糊精改性的碳纳米管,对NO吸附的能力明显增强。因为碱活化后的碳纳米管的比表面积增大,增强了碳纳米管对NO的吸附能力;而环糊精特有的空腔和多羟基结构对NO具有选择吸附性能。
用氮、硼掺杂改性的碳纳米管,制备碳纳米管修饰电极,进行NO在碳纳米管修饰电极上的电氧化研究。研究发现氮、硼掺杂改性的碳纳米管修饰电极NO电催化反应活性增加,反应的活化能降低,提高了NO电化学氧化反应的灵敏度。
In this article, muli-walled carbon nanotubes modified by KOH,β-Cyclodextrin , and doped with B or N have been synthesized. The samples are characterized by SEM, TG-MS, XRD, FT-IR, Raman and XPS. The results demonstrate that the BET surface area of MWCNTs activated by KOH is higher than those of unactivated MWCNTs. And SEM images show that MWCNTs activated by KOH becomes shorter and straighter. While MWCNTs were modified withβ-Cyclodextrin,β-Cyclodextrin enwrapped the surface of MWCNTs. MWCNTs activated by KOH and modified byβ-Cyclodextrin were characterized by the means of XRD and Raman, it was found the structure of the MWCNTs didn’t changed. The results of NO adsorption-desorption showed that the adsorption of NO of MWCNTs activated by KOH and modified byβ-Cyclodextrin are obviously higher than that of MWCNTs. Because of the larger BET surface area of MWCNTs activated by KOH, therefore the NO adsorption capability of MWCNTs activated by KOH was improved; andβ-Cyclodextrin that wrapped MWCNTs has unique cavum and NO can be adsorbed inside it, the adsorption amount of NO of MWCNTs modified byβ-Cyclodextrin increased comparison of MWCNTs. The Raman G bands of MWCNTs dopped with N and B happen to red shift, which show the characteristic of semiconductor obviously.
Electrocatalytic oxidation of nitric oxide (NO) at the modified electrodes of MWCNTs dopped with N and B were studied with cyclic voltammetric determination.
The activity of modified electrode of MWCNTs dopped with N and B were better than that of MWCNTs, MWCNTs activated by KOH and modified byβ-Cyclodextrin. The activation energy (anode potential of MWCNTs dopped with N and B) of NO oxidation decreased. The result demonstrates that sensitivity of NO electrocatalytic oxidation reaction of MWCNTs dopped with N and B was enhanced.
引文
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