Ni-CuO/ITO电极对乙醇电催化氧化及检测的研究

引用本文: 曹厚勇, 曹猛, 毕怡, 于乃森, 郎明非, 孙晶. Ni-CuO/ITO电极对乙醇电催化氧化及检测的研究[J]. 分析化学, 2021, 49(10): 1722-1732. doi: 10.19756/j.issn.0253-3820.210565 shu

Citation: CAO Hou-Yong, CAO Meng, BI Yi, YU Nai-Sen, LANG Ming-Fei, SUN Jing. Ni-CuO/ITO Electrode for Electrooxidation and Detection of Ethanol[J]. Chinese Journal of Analytical Chemistry, 2021, 49(10): 1722-1732. doi: 10.19756/j.issn.0253-3820.210565 shu

Ni-CuO/ITO电极对乙醇电催化氧化及检测的研究

曹厚勇 ^1, ,
曹猛 ^1, ,
毕怡 ^1, ,
于乃森 ^{3,4,
,} ,
郎明非 ^{2,
,} ,
孙晶 ^{1,
,}

1.
大连大学环境与化学工程学院, 大连 116622;
2.
大连大学医学院, 大连 116622;
3.
大连民族大学物理与材料工程学院, 大连 116600;
4.
桂林电子科技大学广西精密导航技术与应用重点实验室, 桂林 541004

通讯作者: 于乃森,E-mail:yunaisen@dlnu.edu.cn; 郎明非,E-mail:langmingfei@dlu.edu.cn; 孙晶,E-mail:sunjing@dlu.edu.cn

基金项目:
辽宁省-沈阳材料科学国家研究中心联合研发基金项目（Nos.2019JH3/30100006，2019010281-JH3/301）、辽宁省自然科学基金项目（No.2021JH6/10500143）和广西精密导航技术与应用重点实验室开放基金项目（No.DH2020015）资助。

摘要: 以氧化铟锡（ITO）导电玻璃为基底，依次电沉积Ni和CuO，制备Ni-CuO/ITO电极。扫描电子显微镜（SEM）表征结果显示，Ni-CuO呈纳米花状结构，均匀分布在ITO基底上，X射线衍射（XRD）结果显示，Ni-CuO主要成分为Ni、NiSO₄和CuO。分别研究了不同电极在碱性条件（1 mol/L KOH）下对乙醇（100 mmol/L）的电化学催化性能，ITO和CuO/ITO电极未显示乙醇催化活性，而Ni-CuO/ITO电极的催化能力可达到氧化峰电流密度20.90 mA/cm²，为Ni/ITO电极的1.7倍。进一步研究了Ni-CuO/ITO电极在不同扫描速度（20~100 mV/s）与不同浓度（10~500 mmol/L）乙醇溶液中电化学响应信号的变化。考察了Ni和CuO的沉积量对Ni-CuO/ITO电极乙醇电催化氧化活性的影响，发现以恒电位法沉积Ni 300 s、循环伏安法沉积CuO两圈时，Ni-CuO/ITO电极对乙醇电催化氧化具有最高的催化活性。以计时电流法测量10000 s后剩余的氧化峰电流密度为初始值的54.39%，显示了电极优异的长期稳定性。氧化峰电流与乙醇浓度在0.1~15 mmol/L范围内呈良好的线性关系，灵敏度为150 μA/（cm²（mmol/L）），检出限为0.047 μmol/L （S/N=3），乙醇的回收率为95.2%~104.1%，并且NaCl、KCl、Na₂HPO₄、山梨酸和柠檬酸等物质对乙醇的检测无明显干扰，表明Ni-CuO/ITO电极具有潜在的应用前景。

关键词:

English

Ni-CuO/ITO Electrode for Electrooxidation and Detection of Ethanol

CAO Hou-Yong ^1, ,
CAO Meng ^1, ,
BI Yi ^1, ,
YU Nai-Sen ^{3,4,
,} ,
LANG Ming-Fei ^{2,
,} ,
SUN Jing ^{1,
,}

1.
College of Environmental and Chemical Engineering, Dalian University, Dalian 116622, China;
2.
Medical College, Dalian University, Dalian 116622, China;
3.
School of Physics and Materials Engineering, Dalian Minzu University, Dalian 116600, China;
4.
Guangxi Key Laboratory of Precision Navigation Technology and Application, Guilin University of Electronic Technology, Guilin 541004, China

Corresponding author: YU Nai-Sen, ; LANG Ming-Fei, ; SUN Jing,

Received Date: 13 June 2021
Revised Date: 21 July 2021
Fund Project:
Supported by the Liaoning Province-Shenyang National Laboratory for Materials Science Joint Research and Development Fund (Nos.2019010274-JH3/301, 2019010281-JH3/301), the Natural Science Foundation of Liaoning Province, China(No.2021JH6/10500143) and the Open Fund Projects of Guangxi Key Laboratory of Precision Navigation Technology and Application (No.XLYC1807004).

Abstract: Ni-CuO/ITO electrode was prepared by sequential electrodeposition of Ni and CuO onto indium tin oxide (ITO) substrate. Scanning electron microscopy (SEM) demonstrated uniform distribution of Ni-CuO nanoflowers on the ITO substrate. X-ray diffraction (XRD) characterization showed that the Ni-CuO was mainly composed of Ni, NiSO₄ and CuO. The electrochemical catalysis of different electrodes for ethanol (100 mmol/L) oxidation was studied in alkaline solution (1 mol/L KOH). ITO and CuO/ITO electrodes had negligible electrochemical activity, while the Ni-CuO electrode had high electrochemical activity, exhibiting oxidative peak current density of 20.90 mA/cm², 1.7 times as high as that of the Ni/ITO. Furthermore, the electrochemical responses of the Ni-CuO electrode at different scan rates (20-100 mV/s) and toward different concentrations (10-500 mmol/L) of ethanol were inspected. By investigating the relationship between the amount of Ni and CuO deposition and the electrochemical catalysis of ethanol, the highest catalytic activity was achieved with potentiostatic Ni deposition for 300 s and CuO deposition for two cyclic voltammetry (CV) cycles. The Ni-CuO/ITO electrode retained 54.39% of its initial oxidative peak current density over a 10000-s stability test by chronoamperometry, exhibiting high long-term stability. A linear relationship was obtained between the oxidative peak current densities of the Ni-CuO/ITO electrode and the ethanol concentrations ranging from 0.1 mmol/L to 15 mmol/L, with an ethanol detection sensitivity of 150 μA/(cm² (mmol/L)), a detection limit of 0.047 μmol/L (S/N=3) and recoveries of 95.2%-104.1%. In addition, excellent anti-interference was found when NaCl, KCl, disodium hydrogen phosphate, sorbic acid, and citric acid were added as interference species during the ethanol detection. These results suggested that the Ni-CuO/ITO electrode had potential practical applications in detection of ethanol.

Key words:

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通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Ni-CuO/ITO电极对乙醇电催化氧化及检测的研究

通讯作者: 于乃森,E-mail:yunaisen@dlnu.edu.cn; 郎明非,E-mail:langmingfei@dlu.edu.cn; 孙晶,E-mail:sunjing@dlu.edu.cn

English

Ni-CuO/ITO Electrode for Electrooxidation and Detection of Ethanol

Corresponding author: YU Nai-Sen, ; LANG Ming-Fei, ; SUN Jing,

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

Ni-CuO/ITO电极对乙醇电催化氧化及检测的研究

通讯作者: 于乃森,E-mail:yunaisen@dlnu.edu.cn; 郎明非,E-mail:langmingfei@dlu.edu.cn; 孙晶,E-mail:sunjing@dlu.edu.cn

English

Ni-CuO/ITO Electrode for Electrooxidation and Detection of Ethanol

Corresponding author: YU Nai-Sen, ; LANG Ming-Fei, ; SUN Jing,

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs