基于Au/rGO/FeOOH的新型电化学传感器一步检测亚硝酸盐

doi:10.13208/j.electrochem.211019

摘要/Abstract

摘要：

亚硝酸盐是一种广泛存在的原料,长期食用会对人体健康不利甚至致癌。因此,简单、灵敏的亚硝酸盐检测方法的开发具有非常重要的意义。本文合成了金/还原氧化石墨烯/羟基氧化铁(Au/rGO/FeOOH)复合材料,并通过SEM、 XRD和EDX等测试进行了材料表征。将合成的复合材料滴涂在氧化氟锡(FTO)电极表面,利用它们的协同催化氧化性能,成功构建了一步检测亚硝酸盐(NO₂^-)的新型电化学传感器。在最佳优化实验条件下, 通过差分脉冲伏安法实现NO₂^-的定量检测, 其线性范围为0.001 ~ 5 mmol·L^-1, 检出限为0.8 μmol·L^-1(S/N = 3), 且响应时间小于2 s。同时, 所制备的传感器表现出良好的选择性和重现性, 也能用于实际样品的测定。

关键词: 亚硝酸盐, Au/rGO/FeOOH, 电化学传感器, 一步检测

Abstract:

Nitrite, a widespread raw material, is harmful to human health for long-term consumption. At present, the detection methods of nitrite mainly include chemical analysis, fluorescence, ultraviolet spectrophotometry and chromatography. These methods have ideal sensitivity and selectivity, but also have some characteristics: cumbersome operation, expensive equipment and professional personnel. Therefore, the development of a simple and sensitive nitrite assay is of great significance. In this paper, the Au/rGO/FeOOH composite materials, which revealed good synergistic catalytic performance among the three elements in the composite, were prepared by simple hydrothermal method and reduction method for the first time with large specific surface area and good electrical conductivity. A one-step electrochemical sensor was constructed by using a traditional three-electrode system for detecting NO₂^-. Of course, the Au/rGO/FeOOH composite modified FTO was regarded as the working electrode. When the target NO₂^- existed, the current increased because the material on the electrode could electro-catalyze NO₂^- to NO₃^-. When the NO₂^- was oxidized, the electron was transferred from NO₂^- to the Au/rGO/FeOOH composite. And the rGO with a large specific surface area and good conductivity in the composite would rapidly transfer electrons to the FTO electrode, thus, enhancing the current signal. Quantitative analysis of NO₂^- could be obtained according to the current intensity which is positively correlated with the concentration of the target. Under the optimal experimental conditions, nitrite was quantitatively detected by differential pulse voltammetry with a linear range of 0.001 ~ 5 mmol·L^-1 and a detection limit of 0.8 μmol·L^-1 (S/N = 3), and the response time was less than 2s. Moreover, the sensor exhibited good selectivity and reproducibility, and could be applied to actual samples. The excellent sensitivity for rapid detection of NO₂^- may be derived from two aspects: 1. the unique structure of rGO FeOOH expands the surface area of the electrode, and further speeds up electron transfer during electrochemical reactions; 2. the composite material has synergistic electrocatalytic oxidation performance among Au, rGO and FeOOH. More importantly, the one-step determination of NO₂^- could be realized accompanying with the simple fabrication of electrode and quick response (~ 2s). It also provides a new idea for the application of metal-organic framework materials in electrochemical field.

Key words: nitrite, Au/rGO/FeOOH, electrochemical sensor, one-step detection

罗大娟, 刘冰倩, 覃蒙颜, 高荣, 苏丽霞, 苏永欢. 基于Au/rGO/FeOOH的新型电化学传感器一步检测亚硝酸盐[J]. 电化学（中英文）, 2022, 28(8): 2110191.

Da-Juan Luo, Bing-Qian Liu, Meng-Yan Qin, Rong Gao, Li-Xia Su, Yong-Huan Su. A Novel Electrochemical Sensor Based on Au/rGO/FeOOH for One-Step Detection of Nitrite[J]. Journal of Electrochemistry, 2022, 28(8): 2110191.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.211019

https://electrochem.xmu.edu.cn/CN/Y2022/V28/I8/2110191

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Method	Linear range (mmol·L^-1)	Detected limit (μmol·L^-1)	Ref.
HPLC	0.001 ~ 0.8	0.075	[16]
Colorimetric method	0.05 ~ 1	25	[17]
Fluorescent assay	0.01 ~ 0.225	3.4	[18]
Spectrophotometric method	0.01 ~ 0.84	0.39	[19]
Differential pulse voltammetry	0.005 ~ 0.8	1.5	[20]
Amperometric method	0.0049 ~ 1.184	3.3	[21]
Cyclic voltammetry	0 ~ 1.38×10⁴	1.39	[22]
Differential pulse voltammetry	0.0025 ~ 1.25	0.15	[23]
Amperometric method	0.002 ~ 0.425	0.7	[24]
Amperometric method	0.001 ~ 1	0.018	[25]
Differential pulse voltammetry	12 ~ 1.2×10³	11.4	[26]
Electrochemical sensor	0.001 ~ 5	0.8	This work

Sample No.	Added (mmol·L^-1)	Found (mmol·L^-1)	Recovery (%)	RSD (%, n = 3)
1	0	0.16	-	1.18
2	0.001	0.0011	110.01	2.42
3	0.01	0.0082	82.51	0.62
4	0.1	0.0888	88.83	3.15
5	1.0	0.8225	82.25	2.42