二氧化铈掺杂中空碳纳米纤维的制备及电化学性能

doi:10.16085/j.issn.1000-6613.2018-1861

摘要/Abstract

摘要：

以葡萄糖为碳源，硝酸铈为铈源，去离子水做溶剂合成前体，使用实验室自制阳极氧化铝模板（anodized aluminum oxide，AAO）作为硬模板，采用真空压力诱导技术将前体注入到AAO的纳米孔道内，热分解合成二氧化铈纳米粒子（CeO₂-NPs）掺杂的中空碳纳米纤维（CeO₂/HCFs）。使用拉曼光谱、电感耦合等离子体质谱（ICP-MS）、透射电镜（TEM）、X射线衍射仪（XRD）、X射线光电子能谱（XPS）对样品进行表征，结果表明，CeO₂/HCFs具有平均直径约为200nm的中空管状结构，具有较好的碳化程度，CeO₂-NPs均匀分布在HCFs中，其晶型为面心立方晶系。通过循环伏安法（CV）与安倍电流-时间法（I-t曲线）技术，研究了支持电解质的pH对检测结果的影响以及CeO₂/HCFs对抗坏血酸的电化学催化性能，实验结果表明支持电解质在pH=4.18时具有最稳定的检测电流，CeO₂/HCFs对抗坏血酸有较高的电化学活性，修饰电极的灵敏度为505.4μA/(cm²·mmol)，检出限为0.55μmol/L，线性范围为2.5~8.4mmol/L，具有良好的选择性、稳定性和重现性。该方法快捷、灵敏、稳定、操作简便，具有较大的应用潜力。

关键词: 二氧化铈, 碳纳米纤维, 制备, 抗坏血酸, 电化学

Abstract:

Using glucose as carbon source, cerium nitrate as cerium source and deionized water as solvent, the precursors were synthesized. Homemade anodic alumina oxide (AAO) was used as hard templates. The precursors were injected into nanochannels of AAO templates via vacuum pressure induction method. The cerium oxide nanoparticles (CeO₂-NPs) doped hollow carbon nanofibers (CeO₂/HCFs) were synthesized by thermal decomposition. The synthesized CeO₂/HCFs were characterized in detail by Raman spectroscopy, inductively coupled plasma mass spectrometry (ICP-MS), transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results revealed that CeO₂/HCFs had the tubular structure with an average diameter of about 200nm with good graphitization degree. Moreover, CeO₂-NPs were uniformly distributed and highly dispersed in HCFs with face centered cubic lattice. Electrochemical activity of CeO₂/HCFs and the effect of supporting electrolyte pH on the detection were investigated by cyclic voltammetry (CV) and amperometric I-t curve. The ascorbic acid sensors displayed high electrochemical activity towards the oxidation of ascorbic acid and the most stable current can be detected when the pH of the supporting electrolyte was 4.18. The sensitivity of the modified electrode was 505.4μA/(cm²·mmol) with the detection limit of 0.55μmol/L. The linear range was 2.5—8.4mmol/L. Moreover, the experimental results demonstrated that CeO₂/HCFs had good stability, reproducibility and selectivity. This method was fast, sensitive, stable and easy to operate. The results suggested that CeO₂/HCFs could be a promising candidate for the construction of non-enzymatic sensor.

Key words: cerium, carbon nanofibers, preparation, ascorbic acid, electrochemistry

中图分类号:

O611.4

吕仁江, 蔡人浩, 李英杰, 高丽娣, 秦世丽. 二氧化铈掺杂中空碳纳米纤维的制备及电化学性能[J]. 化工进展, 2019, 38(06): 2854-2861.

Renjiang LÜ, Renhao CAI, Yingjie LI, Lidi GAO, Shili QIN. Preparation and electrochemical property of CeO₂ doped hollow carbon nanofibers[J]. Chemical Industry and Engineering Progress, 2019, 38(06): 2854-2861.

图/表 13

图1 葡萄糖与硝酸铈混合的前体TG曲线

图2 不同温度下制备的CeO2/HCFs 拉曼表征图

表1 不同掺杂质量硝酸铈样品中Ce的质量分数

样品	样品中Ce的质量分数/%
H-1	7.42
H-2	14.23
H-3	20.79
H-4	22.64

图3 H-3样品的 TEM 图片

图4 H-3样品的形成机理图

图5 H-3样品的CeO2/HCFs X射线衍射谱图

图6 CeO2/HCFs的XPS表征图

图7 支持电解质的pH与峰电流的关系曲线

图8 不同条件下CeO2/HCFs的CV对比曲线

图9 不同扫描速率与峰电流值的关系曲线

图10 AA浓度与峰电流值的关系曲线

图11 修饰电极在不同干扰物质存在下的选择性因素考察

表2 修饰电极的稳定性与重复性实验结果

实验次数	稳定性测试	重复性测试
1	1.996×10^-5	1.963×10^-5
2	1.965×10^-5	1.981×10^-5
3	1.921×10^-5	1.966×10^-5
4	1.816×10^-5	1.984×10^-5
5	1.807×10^-5	1.950×10^-5

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