基于碳基结构增敏型肥料中缩二脲检测的电化学传感器设计与评估

doi:10.12398/j.issn.2096-7217.2024.01.007

智能化农业装备学报（中英文） ›› 2024, Vol. 5 ›› Issue (1): 58-63.DOI: 10.12398/j.issn.2096-7217.2024.01.007

基于碳基结构增敏型肥料中缩二脲检测的电化学传感器设计与评估

王林江¹(), 王恒², 徐珊珊¹, 林则鑫¹, 郑阳¹, 张新爱³()

^1.连云港市质量技术综合检验检测中心，江苏连云港，222000
^2.连云港海关综合技术中心，江苏连云港，222042
^3.江苏大学食品与生物工程学院，江苏镇江，212013

收稿日期:2023-11-10 修回日期:2024-01-15 出版日期:2024-02-15 发布日期:2024-02-07
通讯作者: 张新爱
作者简介:王林江，男，1979年生，河南鹤壁人，硕士，高级工程师；研究方向为农用物资质量检验检测。E-mail： 1098401621@qq.com
基金资助:
江苏省市场监督管理局科技计划项目(KJ2022084);连云港市重点研发计划（社会发展）项目(SF2349)

Design and evaluation of electrochemical sensors for biuret detection in fertilizers sensitized with carbon-based structure

WANG Linjiang¹(), WANG Heng², XU Shanshan¹, LIN Zexin¹, ZHENG Yang¹, ZHANG Xin'ai³()

^1.Lianyungang Comprehensive Inspection and Testing Center for Quality and Technology，Lianyungang 222000，China
^2.Lianyungang Customs Integrated Technology Center，Lianyungang 222042，China
^3.School of Food and Biological Engineering，Jiangsu University，Zhenjiang 212013，China

Received:2023-11-10 Revised:2024-01-15 Online:2024-02-15 Published:2024-02-07
Contact: ZHANG Xin'ai

摘要/Abstract

摘要：

肥料通过调控植物生长发育而直接影响农作物产量，是推动现代集约化农业实现作物高产优质的重要因素；然而，尿素、含尿素复合肥生产过程中极易产生副产物缩二脲，目前由于肥料中缩二脲含量过高造成农田作物毒害问题不容忽视。建立高效的肥料中缩二脲检测方法对保障肥料生产安全、促进我国农业绿色高质量发展具有现实意义。本研究立足于我国现代农业发展对优质肥料的迫切需求，构建基于碳基结构材料敏感响应的电化学传感界面，实现肥料中缩二脲的在线快速评估，有效克服液相色谱法、紫外分光光度法存在的样品预处理繁琐、分析成本高、样品浊度干扰大等不足。首先，制备了兼具碳基结构表面特性和纳米金优良导电性质的石墨烯—纳米金复合物，并将其作为传感界面修饰材料固定于电极表面；其次，利用缩二脲对铜离子电化学信号的抑制作用，建立了铜离子响应电流随缩二脲浓度变化的线性回归方程，借助智能手机获取信号，进而实现缩二脲的电化学快速分析。实验结果表明，铜离子产生的响应电流与缩二脲浓度在1~80 mmol/L范围内呈良好的线性关系，检出限为0.50 mmol/L（S/N=3）；利用该电化学传感体系用于肥料样品中缩二脲的分析，检测结果与高效液相色谱法分析结果相对误差不超过6.9%。该电化学分析方法应用于肥料中缩二脲的在线检测便携程度高、可靠性好、准确度高，为肥料中缩二脲快速评估提供了新方法，科技创新赋能农作物高产优质。

关键词: 电化学传感, 肥料, 缩二脲, 碳基结构, 在线监测

Abstract:

Fertilizer directly affects crop yield by regulating plant growth and development， and it is an important factor in promoting modern intensive agriculture for high yield and quality of crops. However， urea and urea containing compound fertilizers are prone to produce byproducts such as biuret. Currently， the high content of biuret in fertilizers causes crop toxicity in farmland， which cannot be ignored. Therefore， it is of practical significance to establish an efficient method for detecting biuret in fertilizers， ensuring the safety of fertilizer production and promoting the green and high-quality development of agriculture in China. This research is based on the urgent demand for high-quality fertilizers in the development of modern agriculture in China， and a sensitive electrochemical sensing interface based on carbon-based structural materials is constructed to achieve online and rapid evaluation of biuret in fertilizers and effectively overcomes the shortcomings of liquid chromatography and UV spectrophotometry， such as cumbersome sample pretreatment， high analysis cost， and large sample turbidity interference. During the electrochemical assay， a graphene-nanogold composite is firstly prepared as a sensing interface modification material， which combines the surface characteristics of carbon-based structure with the excellent conductivity of nanogold； Secondly， based on the inhibitory effect of biuret on electrochemical signal of copper ions， a linear regression equation is established for the response current of copper ions with the variation of biuret concentration. With the help of a smartphone obtaining electrochemical signal， rapid electrochemical analysis of biuret is achieved. The experimental results demonstrate that there is a good linear relationship between the response current generated by copper ions and the concentration of biuret in the range of 1-80 mmol/L， with a detection limit of 0.50 mmol/L （S/N=3）； The electrochemical sensing system is used for the analysis of biuret in fertilizer samples， and the relative errors between the detection results and those by high-performance liquid chromatography do not exceed 6.9%. Overall， this electrochemical method is applied to the online detection of biuret in fertilizers with high portability， reliability， and accuracy， aiming for technological innovation empowering crops with high yield and quality.

Key words: electrochemical sensing, fertilizer, biuret, carbon-based structure, online monitoring

中图分类号:

王林江, 王恒, 徐珊珊, 林则鑫, 郑阳, 张新爱. 基于碳基结构增敏型肥料中缩二脲检测的电化学传感器设计与评估[J]. 智能化农业装备学报（中英文）, 2024, 5(1): 58-63.

WANG Linjiang, WANG Heng, XU Shanshan, LIN Zexin, ZHENG Yang, ZHANG Xin'ai. Design and evaluation of electrochemical sensors for biuret detection in fertilizers sensitized with carbon-based structure[J]. Journal of Intelligent Agricultural Mechanization, 2024, 5(1): 58-63.

图/表 7

图1 丝网印刷三电极体系作为电化学传感界面

Figure 1 Electrochemical sensing interface using screen printing three-electrode system

图2 基于智能手机获取信号的电化学传感方法用于肥料中缩二脲快速评估

Figure 2 Schematic diagram of electrochemical sensing toward biuret in fertilizer using smartphone

图3 采用透射电镜技术表征不同纳米结构材料的形貌特征

Figure 3 Morphological characteristics of TEM images for nanostructures

图4 不同扫速下的循环伏安曲线及峰电流注：ipa为阳极峰电流，ipc为阴极峰电流。

Figure 4 Cyclic voltammetry curves at different scan rates for calculating surface area of sensing interface

图5 缩二脲用量100 mmol/L时，电流信号随铜离子用量增加的变化图

Figure 5 The variation of current response with increasing Cu2+ amount under 100 mmol/L biuret

图6 电化学传感器用于检测不同浓度的缩二脲

Figure 6 Electrochemical sensing toward biuret at different concentrations

表1 肥料中缩二脲的测定（n=5）

Table 1 Detection results for biuret in fertilizer

样品序号	高效液相色谱法 /（mmol·L^-1）	本方法 /（mmol·L^-1）	相对误差/%
1	13.6	14.3	5.15
2	5.8	5.5	5.17
3	60	63.4	5.67
4	7.6	10.8	4.21
5	68	65.4	3.82
6	2.9	3.1	6.90

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基于碳基结构增敏型肥料中缩二脲检测的电化学传感器设计与评估

Design and evaluation of electrochemical sensors for biuret detection in fertilizers sensitized with carbon-based structure

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