氮掺杂多孔碳负载铜钴纳米复合材料的制备及其电催化性能

doi:10.11868/j.issn.1001-4381.2021.000267

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先以ZIF-8作为前驱体采用简单的高温炭化法制备出氮掺杂多孔碳纳米多面体(NPC), 再通过一步化学还原法将铜和钴颗粒负载到多孔碳上, 成功制备出Cu@Co/NPC纳米复合材料。运用X射线粉末衍射仪、透射电子显微镜和X射线光电子能谱等手段对复合材料进行表征, 将该复合材料修饰到玻碳电极表面上, 研究其对肼的电化学响应。结果表明, Cu@Co/NPC纳米复合材料发挥出协同作用, 从而对肼展现出比单一组分修饰电极更优异的电催化作用。在优化的实验条件下, 复合材料修饰电极与肼的浓度在5~1850 μmol/L范围内呈良好的线性关系, 检测限达0.08 μmol/L。此外, 该复合材料修饰电极测定肼的稳定性、重现性以及选择性均较好, 已被成功用于环境水样中肼的检测, 结果令人满意。

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关键词 ： Cu@Co, 氮掺杂多孔碳, 纳米复合材料, 肼, 电化学测定

Abstract：

Nitrogen doped porous carbon nanopolyhedra (NPC) derived from ZIF-8 was firstly prepared by high temperature carbonization. Subsequently, copper and cobalt were decorated on NPC to form novel nanocomposite by one-step chemical reduction method. Cu@Co/NPC hybrid material was characterized using X-ray powder diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy. The composite was modified on the surface of glassy carbon electrode to study its electrochemical response to hydrazine. The results show that Cu@Co /NPC nanocomposites play a synergistic role, which shows better electrocatalytic effect on hydrazine than single component modified electrode. Under the optimum conditions, the concentration of composite modified electrode and hydrazine in the range of 5-1850 μmol/L exhibits good linear relationship, and the detection limit is 0.08 μmol/L. In addition, the composite modified electrode has good stability, reproducibility and selectivity for the determination of hydrazine. It has been successfully used for the determination of hydrazine in environmental water samples with satisfactory results.

Key words： Cu@Co N-doped porous carbon nanocomposite hydrazine electrochemical detection

收稿日期: 2021-03-26 出版日期: 2022-04-18

中图分类号:

O657.1

基金资助:国家自然科学基金(21771003);安徽省自然科学基金(1808085MB36)

通讯作者: 吴芳辉 E-mail: wfhwfh@ahut.edu.cn

作者简介: 吴芳辉(1975—)，女，教授，博士，研究方向为功能碳材料制备与应用，联系地址：安徽省马鞍山市安徽工业大学化工学院(243000)，E-mail：wfhwfh@ahut.edu.cn

引用本文:

任美娟, 王淼, 吴芳辉, 贾虎, 叶明富, 文国强. 氮掺杂多孔碳负载铜钴纳米复合材料的制备及其电催化性能[J]. 材料工程, 2022, 50(4): 104-111.
Meijuan REN, Miao WANG, Fanghui WU, Hu JIA, Mingfu YE, Guoqiang WEN. Preparation and electrocatalytic properties of nitrogen doped porous carbon loaded copper and cobalt nanocomposite. Journal of Materials Engineering, 2022, 50(4): 104-111.

链接本文:

http://jme.biam.ac.cn/CN/10.11868/j.issn.1001-4381.2021.000267 或 http://jme.biam.ac.cn/CN/Y2022/V50/I4/104

Fig.1 ZIF-8, NPC, Cu/NPC, Co/NPC和Cu@Co/NPC的XRD图

Fig.2 ZIF-8(a), NPC(b), Cu@Co(c)和Cu@Co/NPC(d)的TEM照片

Fig.3 Cu@Co/NPC复合材料的XPS全谱(a)和Cu2p(b), Co2p(c)及N1s(d)的高分辨谱图

Fig.4 0.1 mol/L PBS (pH= 7.0)缓冲溶液中1.0 mmol/L N₂H₄在各电极上的循环伏安图(扫速为50 mV/s)

Fig.5 各电极在含有5 mmol/L [Fe(CN)₆]^4-/3- (1∶1) 的0.1 mol/L KCl溶液中的交流阻抗图(扫速为50 mV/s)

Fig.6 扫速对Cu/Co(1∶1)@NPC修饰电极响应电流的影响
(a)含2 mmol/L N₂H₄的0.1 mol/L PBS (pH=7.0)缓冲溶液中修饰电极在不同扫速下的循环伏安图；(b)扫速平方根与峰电流之间的线性关系图

Fig.7 Cu@Co/NPC复合材料的制备及对肼电化学响应示意图

Fig.8 Cu/Co(1∶1)@NPC修饰电极对不同浓度肼的响应
(a)0.1 mol/L PBS (pH=7.0)中连续添加不同浓度肼的安培曲线；(b)肼的催化电流和浓度之间的线性关系图

Table 1 各种肼电化学传感器的性能比较

Table 2 不同实际水样中肼的测定结果(n=6)

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