化学镀制备纳米银-石墨烯复合材料及其电化学性能

doi:10.11868/j.issn.1001-4381.2020.000903

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摘要

以葡萄糖为还原剂，采用化学镀原位合成纳米银-石墨烯复合材料（Ag/GR），通过X射线衍射（XRD）、X射线能量色散谱（EDS）、X射线光电子能谱（XPS）、扫描电子显微镜（SEM）和傅里叶红外光谱（FTIR）等方法对材料的结构形态进行表征分析。结果表明，石墨烯表面银的负载形态为预期的单质状态，AgNPs平均粒径约为21 nm。同时，利用循环伏安法（CV）、交流阻抗谱（EIS）、线性伏安扫描法（LSV）和差分脉冲伏安法（DPV）对抗坏血酸（AA）在Ag/GR/GCE电化学传感器上的电化学响应进行研究。电化学测试结果表明，Ag/GR复合材料具有最高的响应电化学信号212.9 μA和最低的电荷转移电阻90.5 Ω，峰值电流约为石墨烯电极（110 μA）的2倍和玻碳电极（42.5 μA）的5倍，AgNPs与石墨烯具有良好的协同作用，对AA具有明显的电催化活性。AA的阳极峰电流在5~120 μmol/L浓度范围内线性增加。然而，AA的阳极峰电流与浓度范围为50~120 μmol/L的自然对数高度相关，检测限为0.06 μmol/L。

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	李金磊
	邓凌峰
	张淑娴
	谭洁慧
	覃榕荣
	王壮

关键词 ：化学镀, 银纳米粒子, 石墨烯, 抗坏血酸

Abstract：

Using glucose as the reducing agent, the nano-silver-graphene composite material (Ag/GR) was synthesized in situ by electroless plating, the structural morphology of the material was characterized and analyzed by X-ray diffraction (XRD), X-ray energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM) and Fourier infrared spectrometry (FTIR). The results show that the loading morphology of silver on the graphene surface is the single state that meets the expectation. The average particle size of AgNPs is about 21 nm. At the same time, the electrochemical response of ascorbic acid (AA) on Ag/GR/GCE electrochemical sensors was studied using the electrochemical test methods of cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), linear sweep voltammetry (LSV) and differential pulse voltammetry (DPV). The electrochemical test results show that the Ag/GR composite has the highest response electrochemical signal of 212.9 μA and the lowest resistance of charge transfer of 90.5 Ω. The peak current is about twice that of the graphene electrode (110 μA) and about five times that of the glassy carbon electrode (42.5 μA). Due to the good synergistic effect of AgNPs and graphene, it has obvious electrocatalytic activity for AA. And the anode peak current and concentration show positive correlation linear change trend in the range of 5-120 μmol/L. However, the anode peak current of AA is highly correlated with the natural logarithm of the concentration range from 50 μmol/L to 120 μmol/L. The low limits of detection is 0.06 μmol/L.

Key words： electroless plating silver nanoparticle graphene ascorbic acid

收稿日期: 2020-09-24 出版日期: 2021-08-12

中图分类号:

TQ13

基金资助:国家自然科学基金重点资助项目(31530009);湖南省科研创新资助项目(CX2018B458)

通讯作者: 邓凌峰 E-mail: denglingfeng168@126.com

作者简介: 邓凌峰(1970-), 男, 副教授, 博士, 主要从事能源材料的研究, 联系地址: 湖南省长沙市天心区韶山南498号中南林业科技大学研究生院(410004), E-mail: denglingfeng168@126.com

引用本文:

李金磊, 邓凌峰, 张淑娴, 谭洁慧, 覃榕荣, 王壮. 化学镀制备纳米银-石墨烯复合材料及其电化学性能[J]. 材料工程, 2021, 49(8): 127-138.
Jin-lei LI, Ling-feng DENG, Shu-xian ZHANG, Jie-hui TAN, Rong-rong QIN, Zhuang WANG. Preparation and electrochemical performance of nano-silver-graphene composite by electroless plating. Journal of Materials Engineering, 2021, 49(8): 127-138.

链接本文:

http://jme.biam.ac.cn/CN/10.11868/j.issn.1001-4381.2020.000903 或 http://jme.biam.ac.cn/CN/Y2021/V49/I8/127

Fig.1 Ag/GR的制备工艺流程

Fig.2 Ag/GR复合材料的XRD图

Fig.3 Ag/GR复合材料SEM照片(a)和EDS图谱(b)

Fig.4 Ag/GR-7和石墨烯的XPS全谱及其C，O和Ag元素的精细谱
(a)Ag/GR-7全谱；(b)石墨烯全谱；(c)Ag/GR-7 C1s光谱；(d)石墨烯C1s能谱；(e)Ag/GR-7 O1 s光谱；(f)Ag/GR-7和石墨烯的Ag3d光谱

Fig.5 不同银负载量下Ag/GR复合材料的SEM微观形貌
(a)5 g/L；(b)6 g/L；(c)7 g/L；(d)8 g/L；(e)9 g/L

Fig.6 GO，GR和Ag/GR的FTIR图

Fig.7 不同电化学传感器在[Fe(CN)₆]^3-/4-和KCl溶液中的CV图

Fig.8 银负载量不同Ag/GR修饰电极的电化学阻抗谱
(a)Nyquist图；(b)高频区的放大

Fig.9 AA在Ag/GR-5(a)，Ag/GR-6(b)，Ag/GR-7(c)，Ag/GR-8(d)，Ag/GR-9(e)上的CV曲线

Fig.10 负载量与阳极峰值电流、阴极峰值电流和电荷转移电阻的关系

Fig.11 扫描速率对抗坏血酸传感的影响
(a)AA在Ag/GR-9/GCE上的CV图；(b)I_pa和I_pc与v的关系；(c)I_pa和I_pc与v^1/2的关系；(d)lgI_p与lgv的关系

Fig.12 AA氧化还原的电化学机理

Fig.13 AA在Ag/GR修饰电极上的电化学行为
(a)AA的LSV曲线；(b)E_pa与v的关系；(c)I_pa与v^1/2的关系；(d)lgI_pa与lgv的线性关系

Fig.14 Ag/GR-8/GCE在含不同浓度AA醋酸缓冲液中的差分脉冲伏安图
(a)总DPV曲线；(b)5~50 μmol/L的DPV曲线；(c)I_pa与lnc的关系；(d)50~120 μmol/L的DPV曲线；(e)I_pa与lnc的关系

Table 1 纳米银-石墨烯复合材料修饰电极(Ag/GR/GCE)与其他修饰电极在抗坏血酸电化学测定中的效率比较

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