阅读说明：本技术 一种多孔血糖电极材料及其制备方法 (Porous blood sugar electrode material and preparation method thereof ) 是由 张智祺 于 2021-07-05 设计创作，主要内容包括：本发明公开一种多孔血糖电极材料,该功能电极材料由网状空心Cu/C复合集流体和其上原位生长的花状铜氧化物组成,制备流程包括以下步骤：第一步,配置自还原铜导电墨水；第二步,将碳布浸泡入自还原导电墨水中；第三步,将碳布取出烘干；第四步,将碳布置于马弗炉中进行热处理,获得多孔血糖电极。本发明中集流体为网状空心结构,可以提高单位空间内与待测样本的接触面积,原位生成的花状铜氧化物,不仅结合牢固,且具有多活性位点,信号响应迅速的优势。(The invention discloses a porous blood sugar electrode material, which consists of a reticular hollow Cu/C composite current collector and flower-shaped copper oxide growing on the current collector in situ, and the preparation process comprises the following steps: firstly, preparing self-reduction copper conductive ink; secondly, soaking the carbon cloth into self-reduction conductive ink; thirdly, taking out the carbon cloth and drying; and fourthly, placing the carbon cloth in a muffle furnace for heat treatment to obtain the porous blood sugar electrode. The current collector has a net-shaped hollow structure, so that the contact area between the current collector and a sample to be detected in a unit space can be increased, and the flower-shaped copper oxide generated in situ not only is firmly combined, but also has the advantages of multiple active sites and rapid signal response.)

1. A porous blood sugar electrode material is characterized in that the functional electrode material consists of a reticular hollow Cu/C composite current collector and flower-shaped copper oxide growing on the reticular hollow Cu/C composite current collector in situ.

2. The porous blood glucose electrode material of claim 1, wherein the diameter of the mesh wire in the mesh-shaped hollow Cu/C composite current collector is 0.1-1000 μm, and the central pore diameter of the mesh wire is 0.01-500 μm.

3. The porous blood glucose electrode material of claim 1, wherein the flower-like copper oxide is composed of flake copper oxide and/or cuprous oxide with a thickness of 10-100 nm.

4. A preparation method of a porous blood sugar electrode material is characterized by comprising the following steps:

firstly, preparing self-reduction copper conductive ink;

secondly, soaking the carbon cloth into self-reduction conductive ink;

thirdly, taking out the carbon cloth and drying;

and fourthly, placing the carbon cloth in a muffle furnace for heat treatment to obtain the porous blood sugar electrode.

5. The method according to claim 4, wherein the self-reduced copper conductive ink in the first step contains Cu in an amount of 2-40% by mass, and the solvent includes but is not limited to one or more selected from ethanol, water, ethylene glycol, acetone, and glycerol.

6. The method for preparing the porous blood sugar electrode material according to claim 4, wherein the carbon cloth in the second step is soaked for 1-60 minutes at a temperature of 20-60 ℃.

7. The method for preparing a porous blood sugar electrode material according to claim 4, wherein the drying temperature in the third step is 40-200 ℃ for 1-48 hours.

8. The method for preparing a porous blood sugar electrode material according to claim 4, wherein the heat treatment temperature in the fourth step is 400 to 500 ℃, the atmosphere is air or oxygen atmosphere, and the time is 1 to 6 hours.

Technical Field

The invention is applied to the field of biosensors, and relates to a porous blood glucose electrode material with high specific surface, multiple active sites, high sensitivity and flexibility and a preparation method thereof.

Background

With the increase of national economic strength and the improvement of living standard of people, more and more patients with diabetes (called as 'rich disease') exist. According to the international diabetes union (IDF) survey, it is estimated that from 1.51 hundred million in 2000 to date, there has been a dramatic increase, reaching 4.63 hundred million in 2019. However, the method for detecting the blood sugar content is still simple, the current household blood sugar meter usually detects the blood sugar content by extracting fingertip blood, and the extracted venous blood adopted by hospitals is blood which is more dependent on high-content glucose, and the extracted blood has certain harm and pain to human bodies. Therefore, the traditional blood glucose meter is difficult to meet the increasing concern of people on self health nowadays no matter from the aspects of non-invasive detection, sensitivity and the like. Glucose in sweat is closely related to blood sugar, and noninvasive detection can be well realized by combining analysis of body temperature, heart rate and other physical signs. However, the concentration of sweat is usually only a few tens to a few hundredths of the blood glucose concentration, which is well below the detection limit of conventional blood glucose electrodes, and becomes a key limiting the application of such technologies.

The invention discloses a porous blood sugar electrode material and a preparation method thereof, which can obviously reduce the detection limit of an electrode and realize accurate detection of sweat by improving the specific surface area of the electrode and the associativity of a current collector and a functional semiconductor.

Disclosure of Invention

The invention aims to solve the technical problem of insufficient sensitivity of the existing blood sugar electrode and provides a porous blood sugar electrode material and a preparation method thereof.

In order to solve the technical problems, the functional electrode material of the porous blood sugar electrode material consists of a reticular hollow Cu/C composite current collector and flower-shaped copper oxide growing on the reticular hollow Cu/C composite current collector in situ.

In a possible embodiment, the diameter of a mesh wire in the reticular hollow Cu/C composite current collector is 0.1-1000 μm, the central pore diameter of the mesh wire is 0.01-500 μm, and the flower-shaped copper oxide is composed of flake copper oxide and/or cuprous oxide with the thickness of 10-100 nm.

A preparation method of a porous blood sugar electrode material comprises the following steps:

firstly, preparing self-reduction copper conductive ink;

secondly, soaking the carbon cloth into self-reduction conductive ink;

thirdly, taking out the carbon cloth and drying;

and fourthly, placing the carbon cloth in a muffle furnace for heat treatment to obtain the porous blood sugar electrode.

As a possible implementation manner, further, the self-reduced copper conductive ink in the first step contains 2 to 40% by mass of Cu, and the solvent includes but is not limited to one or a mixture of several of ethanol, water, ethylene glycol, acetone, and glycerol.

As a possible implementation manner, further, the carbon cloth in the second step is soaked for 1 to 60 minutes at a temperature of 20 to 60 ℃.

As a possible implementation manner, further, the drying temperature in the third step is 40 to 200 ℃ and the time is 1 to 48 hours.

As a possible implementation manner, further, the heat treatment temperature in the first step is 400 to 500 ℃, the atmosphere is air or oxygen atmosphere, and the time is 1 to 6 hours

By adopting the technical scheme, the invention has the following beneficial effects:

(1) compared with the existing commercial blood sugar electrode, the invention does not use biological enzyme, but adopts inorganic material as catalyst, so that the dependence of sensitivity on temperature and humidity is obviously reduced, and the requirement on storage environment is obviously reduced.

(2) The Cu/C current collector and the flower-shaped copper oxide are generated in situ by the self-reduction conductive ink, and the interface between the current collector and the copper oxide catalyst layer is fresh, so that the electronic transmission is facilitated, and the sensitivity is improved.

(3) According to the invention, the carbon cloth is used as a carrier to prepare the electrode, and in the heat treatment process, the carbon cloth is removed by thermal decomposition to form a porous network wire, so that the weight of the electrode is reduced, the specific surface area of the electrode can be increased, more active sites are provided, and the sensitivity of the electrode is improved.

Drawings

The invention is described in further detail below with reference to the following figures and embodiments:

fig. 1 is a schematic structural diagram of a porous blood glucose electrode material of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be described in detail and completely with reference to the accompanying drawings.

The invention provides a porous blood sugar electrode material, wherein the functional electrode material consists of a reticular hollow Cu/C composite current collector and a flower-shaped copper oxide growing on the reticular hollow Cu/C composite current collector in situ.

In a possible embodiment, the diameter of a mesh wire in the reticular hollow Cu/C composite current collector is 0.1-1000 μm, the central pore diameter of the mesh wire is 0.01-500 μm, and the flower-shaped copper oxide is composed of flake copper oxide and/or cuprous oxide with the thickness of 10-100 nm.

A preparation method of a porous blood sugar electrode material comprises the following steps:

firstly, preparing self-reduction copper conductive ink;

secondly, soaking the carbon cloth into self-reduction conductive ink;

thirdly, taking out the carbon cloth and drying;

and fourthly, placing the carbon cloth in a muffle furnace for heat treatment to obtain the porous blood sugar electrode.

As a possible implementation manner, further, the self-reducing copper conductive ink in the first step contains 2 to 40% by mass of Cu, and the solvent includes but is not limited to one or a mixture of several of ethanol, water, ethylene glycol, acetone, glycerol, and erythritol.

As a possible implementation manner, further, the carbon cloth in the second step is soaked for 1 to 60 minutes at a temperature of 20 to 60 ℃.

As a possible implementation manner, further, the drying temperature in the third step is 40 to 200 ℃ and the time is 1 to 48 hours.

As a possible implementation mode, further, the heat treatment temperature in the first step is 400-500 ℃, the atmosphere is air or oxygen atmosphere, and the time is 1-6 hours.

Example 1

Preparing a porous blood sugar electrode material which consists of a reticular hollow Cu/C composite current collector and flower-shaped copper oxide growing on the reticular hollow Cu/C composite current collector in situ. Wherein the diameter of a mesh wire in the reticular hollow Cu/C composite current collector is 0.1 mu m, the central aperture of the mesh wire is 0.01 mu m, and the flower-shaped copper oxide is composed of flaky copper oxide with the thickness of 10 nm.

A preparation method of a porous blood sugar electrode material comprises the following steps:

firstly, preparing self-reduction copper conductive ink containing 40% of Cu by mass and ethanol as a solvent;

secondly, soaking the carbon cloth in the self-reduction conductive ink for 60 minutes at the temperature of 60 ℃;

thirdly, taking out the carbon cloth and drying the carbon cloth at the temperature of 120 ℃ for 6 hours;

and fourthly, placing the carbon cloth in a muffle furnace for heat treatment at 400 ℃, wherein the atmosphere is an oxygen atmosphere for 1 hour, and obtaining the porous blood sugar electrode.

The detection limit of the electrode was 0.5. mu. mol/L.

Example 2

Preparing a porous blood sugar electrode material which consists of a reticular hollow Cu/C composite current collector and flower-shaped copper oxide growing on the reticular hollow Cu/C composite current collector in situ. Wherein the diameter of a mesh wire in the reticular hollow Cu/C composite current collector is 20 mu m, the central aperture of the mesh wire is 10 mu m, and the flower-shaped copper oxide is composed of flaky cuprous oxide with the thickness of 40 nm.

A preparation method of a porous blood sugar electrode material comprises the following steps:

firstly, preparing self-reduction copper conductive ink containing 20% of Cu by mass and 20% of ethanol as a solvent;

secondly, soaking the carbon cloth in the self-reduction conductive ink for 10 minutes at the temperature of 40 ℃;

thirdly, taking out the carbon cloth and drying the carbon cloth at 40 ℃ for 48 hours;

and fourthly, placing the carbon cloth in a muffle furnace for heat treatment at the temperature of 420 ℃, wherein the atmosphere is air atmosphere and the time is 26 hours, and obtaining the porous blood sugar electrode.

The electrode sensitivity was 1.2. mu. mol/L.

Example 3

Preparing a porous blood sugar electrode material which consists of a reticular hollow Cu/C composite current collector and flower-shaped copper oxide growing on the reticular hollow Cu/C composite current collector in situ. Wherein the diameter of a mesh wire in the reticular hollow Cu/C composite current collector is 800 mu m, the central aperture of the mesh wire is 200 mu m, and the flower-shaped copper oxide is formed by mixing 20 percent of flake copper oxide with the thickness of 100 nm and 80 percent of cuprous oxide with the thickness of 80 nm.

A preparation method of a porous blood sugar electrode material comprises the following steps:

firstly, preparing self-reduction copper conductive ink containing 5% of Cu by mass and ethylene glycol as a solvent;

secondly, soaking the carbon cloth in self-reduction conductive ink for 30 minutes at 50 ℃;

thirdly, taking out the carbon cloth and drying the carbon cloth at the temperature of 200 ℃ for 25 hours;

and fourthly, placing the carbon cloth in a muffle furnace for heat treatment at 4500 ℃ in an air atmosphere for 3 hours to obtain the porous blood sugar electrode.

The electrode sensitivity was 3.0. mu. mol/L.

Example 4

Preparing a porous blood sugar electrode material which consists of a reticular hollow Cu/C composite current collector and flower-shaped copper oxide growing on the reticular hollow Cu/C composite current collector in situ. Wherein the diameter of a mesh wire in the reticular hollow Cu/C composite current collector is 1000 mu m, the central aperture of the mesh wire is 500 mu m, and the flower-shaped copper oxide is formed by mixing 20 percent of flake copper oxide with the thickness of 70 nm and 80 percent of cuprous oxide with the thickness of 30 nm.

A preparation method of a porous blood sugar electrode material comprises the following steps:

firstly, preparing self-reduction copper conductive ink containing 15% of Cu by mass and acetone as a solvent;

secondly, soaking the carbon cloth in the self-reduction conductive ink for 40 minutes at the temperature of 20 ℃;

thirdly, taking out the carbon cloth and drying the carbon cloth at the temperature of 60 ℃ for 32 hours;

and fourthly, placing the carbon cloth in a muffle furnace for heat treatment at 460 ℃ for 2 hours in an oxygen atmosphere to obtain the porous blood sugar electrode.

The electrode sensitivity was 3.5. mu. mol/L.

Example 5

Preparing a porous blood sugar electrode material which consists of a reticular hollow Cu/C composite current collector and flower-shaped copper oxide growing on the reticular hollow Cu/C composite current collector in situ. Wherein the diameter of a mesh wire in the reticular hollow Cu/C composite current collector is 90 mu m, the central aperture of the mesh wire is 50 mu m, and the flower-shaped copper oxide is composed of flaky cuprous oxide with the thickness of 50 nm.

A preparation method of a porous blood sugar electrode material comprises the following steps:

firstly, preparing self-reduction copper conductive ink containing 2% of Cu by mass and 40% of ethanol in acetone solution;

secondly, soaking the carbon cloth in the self-reduction conductive ink for 1 minute at the temperature of 30 ℃;

thirdly, taking out the carbon cloth and drying the carbon cloth at the temperature of 150 ℃ for 2 hours;

and fourthly, placing the carbon cloth in a muffle furnace for heat treatment at 400 ℃, wherein the atmosphere is an oxygen atmosphere and the time is 4 hours, and obtaining the porous blood sugar electrode.

The electrode sensitivity was 1.5. mu. mol/L.

Example 6

Preparing a porous blood sugar electrode material which consists of a reticular hollow Cu/C composite current collector and flower-shaped copper oxide growing on the reticular hollow Cu/C composite current collector in situ. Wherein the diameter of a mesh wire in the reticular hollow Cu/C composite current collector is 400 mu m, the central aperture of the mesh wire is 200 mu m, and the flower-shaped copper oxide is composed of flaky copper oxide with the thickness of 60 nm.

A preparation method of a porous blood sugar electrode material comprises the following steps:

firstly, preparing self-reduction copper conductive ink containing 35% of Cu by mass and ethanol as a solvent;

secondly, soaking the carbon cloth in the self-reduction conductive ink for 20 minutes at the temperature of 20 ℃;

thirdly, taking out the carbon cloth and drying the carbon cloth at the temperature of 150 ℃ for 1 hour;

and fourthly, placing the carbon cloth in a muffle furnace for heat treatment at 400 ℃, wherein the atmosphere is air atmosphere and the time is 5 hours, and obtaining the porous blood sugar electrode.

The electrode sensitivity was 1.8. mu. mol/L.

Example 7

Preparing a porous blood sugar electrode material which consists of a reticular hollow Cu/C composite current collector and flower-shaped copper oxide growing on the reticular hollow Cu/C composite current collector in situ. Wherein the diameter of a mesh wire in the reticular hollow Cu/C composite current collector is 2 mu m, the central aperture of the mesh wire is 0.8 mu m, and the flower-shaped copper oxide is composed of flaky copper oxide with the thickness of 50 nm.

A preparation method of a porous blood sugar electrode material comprises the following steps:

firstly, preparing self-reduction copper conductive ink containing 2% of Cu by mass and acetone as a solvent;

secondly, soaking the carbon cloth in the self-reduction conductive ink for 10 minutes at the temperature of 20 ℃;

thirdly, taking out the carbon cloth and drying the carbon cloth at the temperature of 50 ℃ for 1 hour;

and fourthly, placing the carbon cloth in a muffle furnace for heat treatment at 480 ℃, wherein the atmosphere is air atmosphere and the time is 3 hours, and obtaining the porous blood sugar electrode.

The electrode sensitivity was 0.2. mu. mol/L.

Example 8

Preparing a porous blood sugar electrode material which consists of a reticular hollow Cu/C composite current collector and flower-shaped copper oxide growing on the reticular hollow Cu/C composite current collector in situ. Wherein the diameter of a mesh wire in the reticular hollow Cu/C composite current collector is 8 mu m, the central aperture of the mesh wire is 0.01 mu m, and the flower-shaped copper oxide is composed of flaky cuprous oxide with the thickness of 30 nm.

A preparation method of a porous blood sugar electrode material comprises the following steps:

firstly, preparing self-reduction copper conductive ink containing 5% of Cu by mass and water as a solvent;

secondly, soaking the carbon cloth in the self-reduction conductive ink for 10 minutes at the temperature of 60 ℃;

thirdly, taking out the carbon cloth and drying the carbon cloth at the temperature of 200 ℃ for 48 hours;

and fourthly, placing the carbon cloth in a muffle furnace for heat treatment at the temperature of 500 ℃, wherein the atmosphere is an oxygen atmosphere and the time is 6 hours, and obtaining the porous blood sugar electrode.

The electrode sensitivity was 1.8. mu. mol/L.

Example 9

Preparing a porous blood sugar electrode material which consists of a reticular hollow Cu/C composite current collector and flower-shaped copper oxide growing on the reticular hollow Cu/C composite current collector in situ. Wherein the diameter of a mesh wire in the reticular hollow Cu/C composite current collector is 0.5 mu m, the central aperture of the mesh wire is 0.01 mu m, and the flower-shaped copper oxide is formed by mixing 90 percent of sheet-shaped copper oxide with the thickness of 10nm and 10 percent of cuprous oxide with the thickness of 30 nm.

A preparation method of a porous blood sugar electrode material comprises the following steps:

firstly, preparing self-reduction copper conductive ink containing 8 mass percent of Cu and 40 percent of glycerol in ethanol solution;

secondly, soaking the carbon cloth in self-reduction conductive ink for 50 minutes at 40 ℃;

thirdly, taking out the carbon cloth and drying the carbon cloth at 160 ℃ for 12 hours;

and fourthly, placing the carbon cloth in a muffle furnace for heat treatment at the temperature of 500 ℃, wherein the atmosphere is air atmosphere and the time is 3 hours, and obtaining the porous blood sugar electrode.

The electrode sensitivity was 0.8. mu. mol/L.

Example 10

Preparing a porous blood sugar electrode material which consists of a reticular hollow Cu/C composite current collector and flower-shaped copper oxide growing on the reticular hollow Cu/C composite current collector in situ. Wherein the diameter of a mesh wire in the reticular hollow Cu/C composite current collector is 300 mu m, the central aperture of the mesh wire is 100 mu m, and the flower-shaped copper oxide is composed of flaky cuprous oxide with the thickness of 90 nm.

A preparation method of a porous blood sugar electrode material comprises the following steps:

firstly, preparing self-reduction copper conductive ink containing 15% of Cu by mass and ethanol as a solvent;

secondly, soaking the carbon cloth in self-reduction conductive ink for 5 minutes at 50 ℃;

thirdly, taking out the carbon cloth and drying the carbon cloth at the temperature of 150 ℃ for 40 hours;

and fourthly, placing the carbon cloth in a muffle furnace for heat treatment at the temperature of 500 ℃, wherein the atmosphere is an oxygen atmosphere and the time is 5 hours, and obtaining the porous blood sugar electrode.

The electrode sensitivity was 2.8. mu. mol/L.