CN103076375A - Preparation method and application of coaxial solid/nanoporous gold/Co3O4 composite electrode material - Google Patents

Preparation method and application of coaxial solid/nanoporous gold/Co3O4 composite electrode material Download PDF

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CN103076375A
CN103076375A CN2012105630164A CN201210563016A CN103076375A CN 103076375 A CN103076375 A CN 103076375A CN 2012105630164 A CN2012105630164 A CN 2012105630164A CN 201210563016 A CN201210563016 A CN 201210563016A CN 103076375 A CN103076375 A CN 103076375A
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gold
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electrode material
glucose
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郎兴友
付红颖
姚丽君
文子
杨萍
朱永福
赵明
李建忱
蒋青
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Jilin University
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Abstract

本发明涉及一种共轴实体/纳米多孔金/Co3O4复合电极材料的制备方法及应用,利用电化学合金化/去合金化原位刻蚀技术制备自支持共轴实体/纳米多孔金电极材料,并在该材料的外层多孔金上通过水热合成的方式修饰Co3O4纳米颗粒作为一种新型生物传感器的金属/氧化物复合电极的制备方法和应用。本发明是基于三电极电化学体系,在金线上通过电化学合金化/去合金化制备自支持共轴实体/纳米多孔金电极材料,该材料在硝酸钴和十六烷基三甲基溴化铵溶液通过水热合成过程后制得自支持的共轴实体/纳米多孔金/Co3O4的复合纳米结构,并将该材料用于葡萄糖的电化学检测。结果表明由于Au和Co3O4的交互作用和特有的微观结构共同效应,该材料对葡萄糖具有极高敏感度。

Figure 201210563016

The invention relates to a preparation method and application of a coaxial solid/nanoporous gold/Co 3 O 4 composite electrode material, which uses electrochemical alloying/dealloying in-situ etching technology to prepare a self-supporting coaxial solid/nanoporous gold Electrode material, and Co 3 O 4 nanoparticles modified by hydrothermal synthesis on the outer porous gold of the material as a preparation method and application of a metal/oxide composite electrode for a new type of biosensor. The present invention is based on a three-electrode electrochemical system, and prepares a self-supporting coaxial entity/nanoporous gold electrode material by electrochemical alloying/dealloying on a gold wire. A self-supported coaxial entity/nanoporous gold/Co 3 O 4 composite nanostructure was fabricated from ammonium chloride solution through a hydrothermal synthesis process, and the material was used for the electrochemical detection of glucose. The results show that the material is highly sensitive to glucose due to the interaction of Au and Co 3 O 4 and the common effect of the unique microstructure.

Figure 201210563016

Description

共轴实体/纳米多孔金/Co3O4复合电极材料的制备方法及应用Preparation method and application of coaxial solid/nanoporous gold/Co3O4 composite electrode material

技术领域: Technical field:

本发明涉及纳米金属/氧化物结构制备及化学分析检测技术领域。  The invention relates to the technical field of nanometer metal/oxide structure preparation and chemical analysis and detection. the

背景技术: Background technique:

用于葡萄糖检测的生物传感器需要具有灵敏度高、可靠性好、反应迅速、选择性良好以及成本低的特点。目前主要用于检测的方法有:光学方法、比色法、电化学法和电化学发光法。其中,电化学方法简单、灵敏度高、成本也很低而受到广泛关注。  Biosensors for glucose detection need to have the characteristics of high sensitivity, good reliability, rapid response, good selectivity and low cost. At present, the methods mainly used for detection are: optical method, colorimetric method, electrochemical method and electrochemiluminescence method. Among them, the electrochemical method is simple, high sensitivity, and low cost, and has attracted widespread attention. the

通常基于生物酶的葡萄糖电化学传感器利用生物催化剂葡萄糖脱氢酶(GDH)和葡萄糖氧化酶(GOx)。GDH基的葡萄糖生物传感器是通过GDH酶催化电化学氧化反应产生烟酰胺腺嘌呤二核苷酸(NADH),但由于NADH中电子迁移动力学缓慢,决定了其电化学氧化需要较高的电位0.7~1.0V(vs.SCE)。而GOx基的葡萄糖生物传感器是通过催化葡萄糖氧化生成H2O2,该过程也需要超过0.6V(vs.SCE)的高电位。在如此高的电位下,多种电化学活性种类在生物体液中是共存的,如抗坏血酸、微生物C、尿酸,等,也将被氧化,从而产生干扰信号。而且基于生物酶的传感器存在着如下的缺点:(1)缺乏长期稳定性,这是酶的固有特性;(2)酶,包括GOx在内,价格都非常昂贵,成本较高;(3)酶的活性极其容易受到温度,溶液PH值,湿度和其他杂质如贵金属的影响。而且葡萄糖氧化酶易溶于水,性质不稳定,并且酶的活性中心深埋在蛋白质内部,这些因素影响了葡萄糖生物传感器的灵敏度、稳定性及重现性,也限制了其产业化发展。  Typically, enzyme-based electrochemical sensors for glucose utilize the biocatalysts glucose dehydrogenase (GDH) and glucose oxidase (GOx). The GDH-based glucose biosensor produces nicotinamide adenine dinucleotide (NADH) through the electrochemical oxidation reaction catalyzed by the GDH enzyme, but due to the slow electron transfer kinetics in NADH, its electrochemical oxidation requires a higher potential of 0.7 ~1.0V (vs. SCE). The GOx-based glucose biosensor generates H 2 O 2 by catalyzing the oxidation of glucose, which also requires a high potential exceeding 0.6 V (vs. SCE). At such a high potential, a variety of electrochemically active species coexist in biological fluids, such as ascorbic acid, microbial C, uric acid, etc., will also be oxidized, thereby generating interference signals. Moreover, enzyme-based sensors have the following disadvantages: (1) lack of long-term stability, which is an inherent characteristic of enzymes; (2) enzymes, including GOx, are very expensive and costly; (3) enzymes Its activity is extremely susceptible to temperature, solution pH, humidity and other impurities such as precious metals. Moreover, glucose oxidase is easily soluble in water, unstable in nature, and the active center of the enzyme is deeply buried inside the protein. These factors affect the sensitivity, stability and reproducibility of the glucose biosensor, and also limit its industrial development.

针对上述生物酶催化剂所面临的问题,非酶催化剂在葡萄糖检测应用上有着巨大的发展空间。最近,纳米结构的金属氧化物由于其价格低廉,高生物兼容性和电催化活性,以及增强的电子转移和吸附能力而受到广泛的关注,将具有高催化活性的纳米结构金属氧化物作为一种新的电极材料被引入了传感器的应用当中,为改良非酶类葡萄糖生物传感器提供了新机会。然而,金属氧化物纳米结构超低的导电性能,例如室温的Co3O4的电导率仅为10-5S m-1,严重的局限他们在高敏感和可靠性、快速反应的电化学生物传感器中的广泛应用。增强在电化学生物传感其中电子传输能力的方法之一是设计具有高催化活性物质与高导电性的复合物材料。虽然目前研究主要基于零维、一维或二维纳米结构碳材料或金属纳米颗粒,并取得了初步的进展。但这些低维纳米结构内电子传输距离有限,各结构间和与集流器的集成均会 产生高的接触电阻。因此由这些低维纳米结构所组装成的整体电极的导电性能改性仍然很有限,限制其在高灵敏度、低检测浓度极限和快速反应的电化学传感器中的广泛应用。  In view of the problems faced by the above-mentioned biological enzyme catalysts, non-enzyme catalysts have a huge development space in the application of glucose detection. Recently, nanostructured metal oxides have attracted extensive attention due to their low price, high biocompatibility and electrocatalytic activity, as well as enhanced electron transfer and adsorption capabilities. New electrode materials were introduced for sensor applications, providing new opportunities for improving non-enzymatic glucose biosensors. However, the ultra-low conductivity of metal oxide nanostructures, for example, the conductivity of Co 3 O 4 at room temperature is only 10 -5 S m -1 , severely limits their application in highly sensitive and reliable, fast-response electrochemical biological Wide range of applications in sensors. One of the approaches to enhance the electron transport capability in electrochemical biosensing is to design composite materials with high catalytic activity and high conductivity. Although the current research is mainly based on zero-dimensional, one-dimensional or two-dimensional nanostructured carbon materials or metal nanoparticles, preliminary progress has been made. However, the electron transmission distance in these low-dimensional nanostructures is limited, and the integration between each structure and the current collector will generate high contact resistance. Therefore, the modification of the electrical conductivity of monolithic electrodes assembled from these low-dimensional nanostructures is still limited, limiting their wide application in electrochemical sensors with high sensitivity, low detection concentration limit, and fast response.

发明内容: Invention content:

本发明的目的是提供一种具有高机械稳定性、自支持的共轴实体/纳米多孔金/Co3O4复合电极材料的制备方法及应用,特别是在痕量葡萄糖检测中的应用。该发明通过原位电化学合金化/去合金化与水热合成相结合的方式将金属氧化物复合于三维纳米多孔结构的金属孔道内、并将该纳米多孔结构集成于集流器,实现提高电催化活性的同时最小化活性物质与集流器接触电阻。该复合纳米结构具有特有的双连接纳米孔道和金属韧带,能同时增强了分析物和电子的传输,并且纳米多孔结构所提供的超高比表面积能有效地、充分地利用金属/氧化物复合材料增强的电催化活性。  The purpose of the present invention is to provide a preparation method and application of a self-supporting coaxial solid/nanoporous gold/Co 3 O 4 composite electrode material with high mechanical stability, especially in the detection of trace glucose. The invention combines metal oxides in the metal channels of the three-dimensional nanoporous structure by combining in-situ electrochemical alloying/dealloying with hydrothermal synthesis, and integrates the nanoporous structure into the current collector to achieve improved Electrocatalytic activity while minimizing the contact resistance between the active material and the current collector. The composite nanostructure has unique double-connected nanopores and metal ligaments, which can simultaneously enhance the transport of analytes and electrons, and the ultra-high specific surface area provided by the nanoporous structure can effectively and fully utilize metal/oxide composites Enhanced electrocatalytic activity.

本发明通过哟西额技术方案实现:  The present invention realizes through the technical scheme of yoxi amount:

一种共轴实体/纳米多孔金/Co3O4复合电极材料的制备方法,包括以下步骤:  A method for preparing a coaxial solid/nanoporous gold/Co 3 O 4 composite electrode material, comprising the following steps:

a、在60℃水浴中,将纯度99.9%的无水ZnCl2经过磁子搅拌充分溶解在苯甲醇(BA99%)中得到ZnCl2/BA电解液,电解液浓度为1~2M;  a. In a water bath at 60°C, fully dissolve anhydrous ZnCl2 with a purity of 99.9% in benzyl alcohol (BA99%) through magnetic stirring to obtain a ZnCl2 /BA electrolyte with a concentration of 1-2M;

b、将直径为0.01~0.2mm的金线作为工作电极,Zn板作为对电极,Zn线作为参比电极,组装成三电极电化学体系,以上混合有机溶液为电解液体在油浴中加热并维持在100~120℃;  b. A gold wire with a diameter of 0.01 to 0.2 mm is used as the working electrode, a Zn plate is used as the counter electrode, and a Zn wire is used as the reference electrode to assemble a three-electrode electrochemical system. The above mixed organic solution is used as the electrolytic liquid, heated in an oil bath and Maintain at 100~120℃;

c、在-0.8~1.9V的范围内以电化学扫描速率为5~50mV/s扫描循环,经过20~50次合金/去合金循环过程后,得到自支持的共轴实体/纳米多孔结构的金电极材料。  c. In the range of -0.8 to 1.9V, the electrochemical scanning rate is 5 to 50mV/s scanning cycle, and after 20 to 50 alloying/dealloying cycles, a self-supporting coaxial entity/nanoporous structure is obtained gold electrode material. the

所述的一种共轴实体/纳米多孔金/Co3O4复合电极材料的制备方法,所述步骤b中的金线经抛光后,依次利用丙酮、乙醇和高纯水清洗,最后烘干,作为工作电极。  In the preparation method of a coaxial entity/nanoporous gold/Co 3 O 4 composite electrode material, after the gold wire in the step b is polished, it is washed with acetone, ethanol and high-purity water in sequence, and finally dried, as working electrode.

所述的一种共轴实体/纳米多孔金/Co3O4复合电极材料的制备方法制备自支持的共轴实体/纳米多孔结构,制作出自支持的共轴实体/纳米多孔金/Co3O4复合电极材料,包括以下步骤:  The preparation method of a coaxial solid/nanoporous gold/Co 3 O 4 composite electrode material prepares a self-supporting coaxial solid/nanoporous structure, and produces a self-supporting coaxial solid/nanoporous gold/Co 3 O 4 Composite electrode materials, comprising the following steps:

a、将浓度比例为3:1的Co(NO3)2和CTAB(十六烷基三甲基溴化铵)放在比例为6:1的乙醇和水中充分搅拌均匀;  a. Put Co(NO 3 ) 2 and CTAB (cetyltrimethylammonium bromide) with a concentration ratio of 3:1 in ethanol and water with a ratio of 6:1 and stir well;

b、将权利要求1的样品即共轴实体/纳米多孔结构的金电极材料用支撑夹夹起直立在配置溶液中央,使其四周都能充分接触溶液;  B, the sample of claim 1, that is, the gold electrode material of coaxial solid/nanoporous structure is clamped and erected in the center of the configuration solution with support clips, so that it can fully contact the solution around it;

c、将准备好的样品和溶液放在反应釜中,温度设置为180℃,60~120min后得到自支持的共轴实体/纳米多孔金/Co3O4复合电极材料。  c. Put the prepared sample and solution in the reaction kettle, set the temperature at 180° C., and obtain a self-supporting coaxial solid/nanoporous gold/Co 3 O 4 composite electrode material after 60 to 120 minutes.

所述的一种自支持的共轴实体/纳米多孔金/Co3O4复合电极材料直接用于对葡萄糖浓度 的电化学测试,包括以下步骤:  Described a kind of self-supporting coaxial entity/nanoporous gold/Co 3 O The composite electrode material is directly used in the electrochemical test to glucose concentration, comprises the following steps:

a、将所述样品作为工作电极,Pt作为对电极,Ag/AgCl作为参比电极,组成三电极系统;  a, using the sample as a working electrode, Pt as a counter electrode, and Ag/AgCl as a reference electrode to form a three-electrode system;

b、用所述样品作为工作电极电化学测定时,将循环伏安特性曲线的范围定为-0.8~0.6V进行循环伏安法扫描;将电流-时间曲线的电压设定为0.26V,当背景电流达到稳态后(1~2min),记录时间电流曲线段(1~2min),并用微量进样器添加葡萄糖溶液样品同时进行搅拌(1~2min),将在不同葡萄糖溶液浓度下测量得到的传感器对葡萄糖的电流响应值,在5nM~70mM范围内,得到电流与葡萄糖浓度的线性关系;  b. When using the sample as the working electrode for electrochemical measurement, the range of the cyclic voltammetry characteristic curve is determined as -0.8~0.6V for cyclic voltammetry scanning; the voltage of the current-time curve is set as 0.26V, when After the background current reaches a steady state (1-2min), record the time-current curve segment (1-2min), and use a micro-sampler to add glucose solution samples while stirring (1-2min), and measure at different glucose solution concentrations to obtain The current response value of the sensor to glucose is within the range of 5nM to 70mM, and the linear relationship between current and glucose concentration is obtained;

c、所述样品作为工作电极的电流与葡萄糖浓度的线性关系随浓度的不同线性的斜率发生变化。  c. The linear relationship between the current of the sample used as the working electrode and the glucose concentration changes with different concentrations. the

本发明的结构作为电极当作一种新型的电化学葡萄糖传感器,直接用于葡萄糖的快速超低浓度电化学测定,自支持的共轴实体/纳米多孔金/Co3O4纳米颗粒复合电极材料作为电极具有催化性能高、稳定性好、抗干扰性强等优点,并且对葡萄糖的检测效率高,准确度高。  The structure of the present invention is used as an electrode as a new type of electrochemical glucose sensor, which is directly used for fast ultra-low concentration electrochemical determination of glucose, self-supporting coaxial solid/nanoporous gold/Co 3 O 4 nanoparticle composite electrode material As an electrode, it has the advantages of high catalytic performance, good stability, strong anti-interference, etc., and has high detection efficiency and high accuracy for glucose.

附图说明: Description of drawings:

图1、自支持的共轴实体/纳米多孔金/Co3O4纳米颗粒复合电极材料的制作过程示意图,其中:  Figure 1. Schematic diagram of the fabrication process of a self-supporting coaxial solid/nanoporous gold/Co 3 O 4 nanoparticle composite electrode material, in which:

(a)实体金线;  (a) physical gold wire;

(b)共轴实体/纳米多孔金线;  (b) coaxial solid/nanoporous gold wire;

(c)共轴实体/纳米多孔/氧化钴复合结构。  (c) Coaxial solid/nanoporous/cobalt oxide composite structure. the

图2、自支持的共轴实体/纳米多孔金线的扫描电镜(SEM)表征图,其中:  Figure 2. Scanning electron microscope (SEM) characterization of self-supporting coaxial solid/nanoporous gold wires, where:

(a)共轴实体/纳米多孔金线低倍SEM表征图;  (a) Low-magnification SEM characterization of coaxial solid/nanoporous gold wire;

(b)共轴实体/纳米多孔金线横截断面SEM表征图;  (b) SEM characterization diagram of the cross-section of the coaxial solid/nanoporous gold wire;

(c)共轴实体/纳米多孔金线顶视SEM表征图。  (c) Top-view SEM characterization of coaxial solid/nanoporous gold wires. the

图3、自支持的共轴实体/纳米多孔金/Co3O4纳米颗粒复合电极材料的扫描电镜(SEM)表征图。  Fig. 3. Scanning electron microscopy (SEM) characterization of self-supporting coaxial solid/nanoporous gold/Co 3 O 4 nanoparticle composite electrode materials.

图4、自支持的共轴实体/纳米多孔金/Co3O4纳米颗粒复合电极材料的透射电镜(TEM)表征图。  Fig. 4. Transmission electron microscopy (TEM) characterization of self-supporting coaxial solid/nanoporous gold/Co 3 O 4 nanoparticle composite electrode materials.

图5、自支持的共轴实体/纳米多孔金/Co3O4纳米颗粒复合电极材料的拉曼光谱图。  Fig. 5. Raman spectra of the self-supporting coaxial solid/nanoporous gold/Co 3 O 4 nanoparticle composite electrode material.

图6、自支持的共轴实体/纳米多孔金/Co3O4纳米颗粒复合电极材料的XRD光谱图。  Fig. 6. XRD spectrum of self-supporting coaxial solid/nanoporous gold/Co 3 O 4 nanoparticle composite electrode material.

图7、自支持的共轴实体/纳米多孔金/Co3O4纳米颗粒复合电极材料与20μm厚的多孔金韧性实验对比图片,其中:  Figure 7. Comparison of self-supporting coaxial solid/nanoporous gold/Co 3 O 4 nanoparticle composite electrode materials and 20 μm thick porous gold toughness experiments, in which:

(a)纯纳米多孔金;  (a) pure nanoporous gold;

(b)共轴实体/纳米多孔金。  (b) Coaxial solid/nanoporous gold. the

图8、自支持的共轴实体/纳米多孔金/Co3O4纳米颗粒复合电极材料为电极在0.5M的KOH溶液(a)含有(b)不含有10mM葡萄糖中的循环伏安特性曲线,其中:  Figure 8. Cyclic voltammetry characteristic curves of the self-supporting coaxial solid/nanoporous gold/Co 3 O 4 nanoparticle composite electrode material in 0.5M KOH solution (a) containing (b) excluding 10mM glucose, in:

(a)含有(b)不含有10mM葡萄糖中的循环伏安特性曲线;  (a) contains (b) does not contain the cyclic voltammetry characteristic curve in 10mM glucose;

(b)不含有10mM葡萄糖中的循环伏安特性曲线。  (b) Cyclic voltammetry curve without 10 mM glucose. the

图9、自支持的共轴实体/纳米多孔金/Co3O4纳米颗粒复合电极材料作为电极对葡萄糖探测的快速响应曲线,其中:  Figure 9. The self-supporting coaxial solid/nanoporous gold/Co 3 O 4 nanoparticle composite electrode material as the fast response curve of the electrode for glucose detection, where:

(a)快速响应曲线,  (a) Fast response curve,

(b)标准曲线。  (b) Standard curve. the

图10、自支持的共轴实体/纳米多孔金/Co3O4纳米颗粒复合电极材料作为电极的探测极限和抗干扰性,其中:  Figure 10. The detection limit and anti-interference performance of the self-supporting coaxial solid/nanoporous gold/ Co3O4 nanoparticle composite electrode material as an electrode, where:

(a)电极的探测极限,  (a) the detection limit of the electrode,

(b)电极的抗干扰性。  (b) Anti-interference of electrodes. the

具体实施方式: Detailed ways:

以下结合实施例进一步说明本发明的具体内容及实施方式。  The specific content and implementation mode of the present invention will be further described below in conjunction with the examples. the

实施例  Example

本实施例中的制备过程和步骤如下:  The preparation process and steps in this embodiment are as follows:

(1)在60℃水浴中,将纯度为99.9%ZnCl2经过磁子搅拌充分溶解在苯甲醇(BA99%)中得到ZnCl2/BA电解液,电解液浓度为1.5M,将直径为0.2mm,长1.5cm的金线进行抛光,然后依次利用丙酮、乙醇和高纯水清洗,最后烘干,作为工作电极待用。将宽1mm长4cm的锌线作为参比电极,将宽为5mm长4cm的锌板作为对电极。三个电极放在上述制备溶液中,无需设置盐桥连接,在120℃下利用三电极系统在金电极上扫描循环进行电化学合金化/去合金化过程。扫描的电压范围为-0.72~1.88V(vs.Zn),多次循环的扫描速率选定为10mV/S,经过循环50圈后,将金电极依次在苯甲醇、乙醇和去离子水中依次序清洗。  (1) In a water bath at 60°C, fully dissolve ZnCl 2 with a purity of 99.9% in benzyl alcohol (BA99%) through magnetic stirring to obtain a ZnCl 2 /BA electrolyte with a concentration of 1.5M and a diameter of 0.2mm , a gold wire with a length of 1.5 cm was polished, then washed with acetone, ethanol and high-purity water in sequence, and finally dried, and used as a working electrode. A zinc wire with a width of 1 mm and a length of 4 cm is used as a reference electrode, and a zinc plate with a width of 5 mm and a length of 4 cm is used as a counter electrode. The three electrodes are placed in the above-mentioned preparation solution without setting a salt bridge connection, and the electrochemical alloying/dealloying process is carried out by using a three-electrode system to scan and cycle on the gold electrode at 120°C. The scanning voltage range is -0.72 ~ 1.88V (vs. Zn), and the scanning rate of multiple cycles is selected as 10mV/S. After 50 cycles, the gold electrode is sequentially placed in benzyl alcohol, ethanol and deionized water. cleaning.

(2)将6mM的Co(NO3)2和2mM的CTAB(十六烷基三甲基溴化铵)放在30mL乙醇和5mL水中充分搅拌均匀;将多孔金包裹的金线用支撑夹夹起直立在配置溶液中央,使自支持多孔金包裹金线结构四周都能充分接触溶液,将准备好样品和溶液放在反应釜中,温度设置为180℃,反应90min得到自支持的共轴实体/纳米多孔金/Co3O4纳米颗粒复合电极材料。  (2) Put 6mM Co(NO 3 ) 2 and 2mM CTAB (cetyltrimethylammonium bromide) in 30mL ethanol and 5mL water and stir well; clamp the porous gold-wrapped gold wire with a support clamp Stand upright in the center of the configuration solution, so that the surroundings of the self-supporting porous gold-wrapped gold wire structure can fully contact the solution, put the prepared sample and solution in the reaction kettle, set the temperature at 180°C, and react for 90 minutes to obtain a self-supporting coaxial entity /Nanoporous gold/Co 3 O 4 nanoparticle composite electrode material.

(3)电化学测定时,将循环伏安特性曲线的范围定为-0.8~0.6V进行循环伏安法扫描,将电流-时间曲线的电压设定为0.26V,当背景电流达到稳态后(2min),记录时间电流曲线 段(2min),并用微量进样器加葡萄糖溶液样品同时进行搅拌(2min),将在不同葡萄糖溶液浓度下测量得到的传感器对葡萄糖的电流响应值,在5nM~70mM范围内,得到电流与葡萄糖浓度的线性关系;电流与葡萄糖浓度的线性关系随浓度的不同线性的斜率发生变化;将干扰物质UA(尿酸),AP(醋氨酚),AA(抗坏血酸)加入到三电极测试系统中进行干扰探测,与葡萄糖探测步骤相同,最后滴入葡萄糖进行抗干扰性对比。  (3) During electrochemical measurement, set the range of the cyclic voltammetry characteristic curve to -0.8~0.6V for cyclic voltammetry scanning, set the voltage of the current-time curve to 0.26V, when the background current reaches a steady state (2min), record the time current curve segment (2min), and add the glucose solution sample with a micro-injector and stir simultaneously (2min), the current response value of the sensor measured under different glucose solution concentrations to glucose, in 5nM~ In the range of 70mM, the linear relationship between the current and the glucose concentration is obtained; the linear relationship between the current and the glucose concentration changes with the different linear slopes of the concentration; the interfering substances UA (uric acid), AP (acetaminophen), and AA (ascorbic acid) are added Go to the three-electrode test system for interference detection, which is the same as the glucose detection step, and finally drop glucose for anti-interference comparison. the

一种作为葡萄糖传感器的自支持的共轴实体/纳米多孔金/Co3O4纳米颗粒复合电极材料作为电极的用途及方法,其用途是直接用于葡萄糖浓度的电化学测定;使用方法如下:电化学测定时,将循环伏安特性曲线的范围定为-0.8~0.6V进行循环伏安法扫描,将电流-时间曲线的电压设定为0.26V,当背景电流达到稳态后(1~2min),记录时间电流曲线段(1~2min),并用微量进样器加葡萄糖溶液样品同时进行搅拌(1~2min),将在不同葡萄糖溶液浓度下测量得到的传感器对葡萄糖的电流响应值,在5nM~70mM范围内,得到电流与葡萄糖浓度的线性关系;电流与葡萄糖浓度的线性关系随浓度的不同线性的斜率发生变化  A self-supporting coaxial entity/nanoporous gold/Co 3 O 4 nanoparticle composite electrode material as a glucose sensor uses and method as an electrode, and its use is directly used for the electrochemical determination of glucose concentration; the use method is as follows: During the electrochemical measurement, the range of the cyclic voltammetry characteristic curve was set as -0.8~0.6V for cyclic voltammetry scanning, and the voltage of the current-time curve was set as 0.26V. When the background current reached a steady state (1~ 2min), record the time-current curve segment (1-2min), and add the glucose solution sample with a micro-sampler while stirring (1-2min), and measure the current response value of the sensor to glucose under different glucose solution concentrations, In the range of 5nM to 70mM, the linear relationship between the current and the glucose concentration is obtained; the linear relationship between the current and the glucose concentration changes with the different concentration of the linear slope

作为葡萄糖传感器的自支持的共轴实体/纳米多孔金/Co3O4纳米颗粒复合电极材料的表征:  Characterization of a self-supporting coaxial solid/nanoporous gold/ Co3O4 nanoparticle composite electrode material as a glucose sensor :

通过扫描电镜(SEM)观察到自支持的共轴实体/纳米多孔金/Co3O4纳米颗粒复合电极材料的表面形态,参阅图2和图3。从图中可以看出,共轴实体/纳米多孔金线表面的三维双连续的多孔结构均匀,有效的提高了材料的比表面积,自支持的共轴实体/纳米多孔金/Co3O4纳米颗粒复合电极材料表面被Co3O4纳米颗粒均匀覆盖包裹,在导电性很大的情况下,更加增大了该复合结构的比表面积,同时可以有效发挥Co3O4颗粒的特性,从而导致传感器产生高敏感的电流响应。参阅图5和图6,自支持多孔金包裹金线及自支持多孔金包裹金线被Co3O4颗粒再包裹的一种核壳结构进行了XRD和DES的表征,证明该结构制备过程的产物确为Co3O4颗粒。  The surface morphology of the self-supporting coaxial solid/nanoporous gold/Co 3 O 4 nanoparticle composite electrode material was observed by scanning electron microscopy (SEM), see Fig. 2 and Fig. 3 . It can be seen from the figure that the three-dimensional bicontinuous porous structure on the surface of the coaxial solid/nanoporous gold wire is uniform, which effectively improves the specific surface area of the material, and the self-supporting coaxial solid/nanoporous gold/Co 3 O 4 nano The surface of the particle composite electrode material is evenly covered and wrapped by Co 3 O 4 nanoparticles. In the case of high conductivity, the specific surface area of the composite structure is further increased, and at the same time, the characteristics of Co 3 O 4 particles can be effectively utilized, resulting in The sensor produces a highly sensitive current response. Referring to Figures 5 and 6, a core-shell structure in which self-supporting porous gold-wrapped gold wires and self-supporting porous gold-wrapped gold wires are rewrapped by Co 3 O 4 particles has been characterized by XRD and DES, proving that the preparation process of the structure is accurate. The product is indeed Co 3 O 4 particles.

韧性测定:  Toughness measurement:

将本发明的电极材料和20um厚的多孔金分别做韧性测试,并实时跟踪其最大弯折度,发现本发明的自支持的共轴实体/纳米多孔金/Co3O4纳米颗粒复合电极材料任意弯折成任何形状而不折断。  The electrode material of the present invention and the porous gold with a thickness of 20um were respectively tested for toughness, and the maximum bending degree was tracked in real time, and it was found that the self-supporting coaxial entity/nanoporous gold/Co 3 O 4 nanoparticle composite electrode material of the present invention It can be bent into any shape without breaking.

电化学测定:  Electrochemical determination:

在最佳测试条件下,自支持的共轴实体/纳米多孔金/Co3O4纳米颗粒复合电极材料对葡萄糖的循环伏安和计时电流的响应参阅图8所示。该电极材料在比自支持共轴实体/纳米多孔金线有更大的电流密度,并且参阅图10其探测葡萄糖时电流响应时间非常短,这主要是因为通过本方法制备的自支持的共轴实体/纳米多孔金/Co3O4纳米颗粒复合电极材料具有良好的生物相容性、多孔性及超高的导电性。图9显示的是随着葡萄糖浓度的增加,传感器对葡 萄糖的响应逐渐增大,并且电流与葡萄糖浓度成线性关系。  Under the optimal test conditions, the cyclic voltammetry and chronoamperometric responses of the self-supporting coaxial solid/nanoporous gold/Co 3 O 4 nanoparticle composite electrode material to glucose are shown in Fig. 8 . This electrode material has a higher current density than the self-supporting coaxial solid/nanoporous gold wire, and see Figure 10 for its very short current response time when detecting glucose, which is mainly due to the self-supporting coaxial The solid/nanoporous gold/Co 3 O 4 nanoparticle composite electrode material has good biocompatibility, porosity and ultrahigh conductivity. Figure 9 shows that as the glucose concentration increases, the sensor's response to glucose gradually increases, and the current has a linear relationship with the glucose concentration.

本发明制备的电极,参阅图10其探测葡萄糖时电流响应时间非常短,小于1s。对葡萄糖探测的敏感性高,探测最小葡萄糖浓度为5nM,对干扰物质UA(尿酸),AP(醋氨酚),AA(抗坏血酸)抵抗性高。  The electrode prepared by the present invention, referring to Fig. 10, has a very short current response time when detecting glucose, less than 1 s. The sensitivity to glucose detection is high, the minimum glucose concentration for detection is 5nM, and the resistance to interfering substances UA (uric acid), AP (acetaminophen) and AA (ascorbic acid) is high. the

Claims (4)

1. coaxial entity/nano-porous gold/Co 3O 4The preparation method of combination electrode material may further comprise the steps:
A, in 60 ℃ of water-baths, with the anhydrous ZnCl of purity 99.9% 2Stirring fully is dissolved in the phenmethylol (BA99%) and obtains ZnCl through magneton 2/ BA electrolytic solution, concentration of electrolyte are 1~2M;
B, with diameter be the gold thread of 0.01~0.2mm as working electrode, the Zn plate is as to electrode, the Zn line is assembled into the three-electrode electro Chemical system as contrast electrode, above mixed organic solvents is that electrolyte heats in oil bath and maintains 100~120 ℃;
C, in the scope of-0.8~1.9V take Electrochemical Scanning speed as 5~50mV/s scan cycle, through behind 20~50 alloys/go the alloy cyclic process, obtain the gold electrode material of the coaxial entity/nano-porous structure of self-supporting.
2. according to a kind of coaxial entity/nano-porous gold claimed in claim 1/Co 3O 4The preparation method of combination electrode material, the gold thread among the described step b utilizes acetone, ethanol and high purity water to clean after polishing successively, and at last oven dry is as working electrode.
3. according to a kind of coaxial entity/nano-porous gold claimed in claim 1/Co 3O 4The preparation method of combination electrode material prepares the coaxial entity/nano-porous structure of self-supporting, produces the coaxial entity/nano-porous gold of self-supporting/Co 3O 4Combination electrode material may further comprise the steps:
A, be the Co (NO of 3:1 with concentration ratio 3) 2And CTAB (cetyl trimethyl ammonium bromide) ratio of being placed on is to stir in the second alcohol and water of 6:1;
B, be that the gold electrode material of coaxial entity/nano-porous structure picks up with propclip and stands upright on configuration solution central authorities with the sample of claim 1, can both fully contact solution around making it;
C, ready sample and solution are placed in the reactor, temperature setting is set to 180 ℃, obtains the coaxial entity/nano-porous gold of self-supporting/Co behind 60~120min 3O 4Combination electrode material.
4. according to the coaxial entity/nano-porous gold of a kind of self-supporting claimed in claim 3/Co 3O 4Combination electrode material is directly used in the electro-chemical test to concentration of glucose, may further comprise the steps:
A, with described sample as working electrode, Pt is as to electrode, Ag/AgCl forms three-electrode system as contrast electrode;
B,, the characteristic scope of cyclic voltammetric is decided to be during as the working electrode electrochemical gaging with described sample-0.8~0.6V carries out cyclic voltammetry scanning; The voltage of electric current-time curve is set as 0.26V, after background current reaches stable state (1~2min), writing time, the current curve section (1~2min), and add the glucose solution sample with microsyringe and stir simultaneously (1~2min), the sensor that will measure under different glucose solution concentration is to the current-responsive value of glucose, in 5nM~70mM scope, obtain the linear relationship of electric current and concentration of glucose;
C, described sample change as the linear relationship of the electric current of working electrode and the concentration of glucose slope with the not collinearity of concentration.
CN2012105630164A 2012-12-21 2012-12-21 Preparation method and application of coaxial solid/nanoporous gold/Co3O4 composite electrode material Pending CN103076375A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103359796A (en) * 2013-07-12 2013-10-23 上海大学 Preparation method of supercapacitor cobaltous oxide electrode material
CN104383938A (en) * 2014-09-25 2015-03-04 北京科技大学 Glucose oxidation electrocatalyst and preparation method thereof
CN105506726A (en) * 2016-03-02 2016-04-20 沈阳建筑大学 In-situ electrochemical preparation method for silver nanometer thin films
CN105680010A (en) * 2016-01-18 2016-06-15 吉林大学 Method and application of improving discharge capacity and high rate discharge performance of hydrogen storage alloy by in-situ compounding Co3O4
CN105734643A (en) * 2016-03-02 2016-07-06 沈阳建筑大学 In-situ electrochemical preparation method of nanometer silver oxide film
CN106770567A (en) * 2016-11-25 2017-05-31 江苏丰格测控技术有限公司 A kind of Platinum Nanoparticles cobalt/porous gold/graphene composite material and preparation method thereof
CN108593729A (en) * 2018-06-27 2018-09-28 中山大学 A kind of preparation method of the porous golden blood glucose micropin electrochemical sensor module of no proteins carry enzyme
CN109239151A (en) * 2018-08-10 2019-01-18 广州钰芯传感科技有限公司 A kind of pair of modification microneedle electrodes and preparation method thereof and blood glucose micropin electrochemical sensor electrodes
CN111239217A (en) * 2020-02-07 2020-06-05 中国人民解放军军事科学院军事医学研究院 N-doped carbon-wrapped Co @ Co3O4Core-shell particle polyhedron and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102583582A (en) * 2012-03-06 2012-07-18 南京大学 Co3O4 nanocrystal, its preparation method, application and enzyme-free hydrogen peroxide sensor
CN102621208A (en) * 2012-03-21 2012-08-01 南京邮电大学 Preparation method and application of three-dimensional graphene electrode for electrochemical biosensor

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102583582A (en) * 2012-03-06 2012-07-18 南京大学 Co3O4 nanocrystal, its preparation method, application and enzyme-free hydrogen peroxide sensor
CN102621208A (en) * 2012-03-21 2012-08-01 南京邮电大学 Preparation method and application of three-dimensional graphene electrode for electrochemical biosensor

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHUANFANG YU ET AL.: "Direct Oxidation of Methanol on Self-Supported Nanoporous Gold Film Electrodes with High Catalytic Activity and Stability", 《CHEM.MATER.》 *
JING-FANG HUANG ET AL.: "Fabrication and Surface Functionalization of Nanoporous Gold by Electrochemical Alloying/Dealloying of Au±Zn in an Ionic Liquid,and the Self-Assembly of L-Cysteine Monolayers", 《ADV.FUNCT.MATER.》 *
XIAO-CHEN DONG ET AL.: "3D Graphene Cobalt Oxide Electrode for High-Performance Supercapacitor and Enzymeless Glucose Detection", 《ACSNANO》 *

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CN104383938A (en) * 2014-09-25 2015-03-04 北京科技大学 Glucose oxidation electrocatalyst and preparation method thereof
CN105680010A (en) * 2016-01-18 2016-06-15 吉林大学 Method and application of improving discharge capacity and high rate discharge performance of hydrogen storage alloy by in-situ compounding Co3O4
CN105506726A (en) * 2016-03-02 2016-04-20 沈阳建筑大学 In-situ electrochemical preparation method for silver nanometer thin films
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CN105506726B (en) * 2016-03-02 2017-12-19 沈阳建筑大学 A kind of in-situ electrochemistry preparation of silver-colored nano thin-film
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CN108593729A (en) * 2018-06-27 2018-09-28 中山大学 A kind of preparation method of the porous golden blood glucose micropin electrochemical sensor module of no proteins carry enzyme
CN109239151A (en) * 2018-08-10 2019-01-18 广州钰芯传感科技有限公司 A kind of pair of modification microneedle electrodes and preparation method thereof and blood glucose micropin electrochemical sensor electrodes
CN111239217A (en) * 2020-02-07 2020-06-05 中国人民解放军军事科学院军事医学研究院 N-doped carbon-wrapped Co @ Co3O4Core-shell particle polyhedron and preparation method and application thereof

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