Amorphous alloy electrode for electrochemical glucose detection sensing

By using Ni60+xMo20-xP16B4 amorphous alloy electrode material to conduct electrochemical glucose detection in the three-electrode working system, the problems of insufficient glucose detection sensitivity and high equipment cost in the prior art are solved, and high sensitivity, non-invasive, fast and accurate glucose monitoring effects are achieved.

CN120028401AActive Publication Date: 2025-05-23NANJING UNIV OF SCI & TECH
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Patent Information

Application Number
CN202311565620.5
Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Filing Date
2023-11-22
Publication Date
2025-05-23
Estimated Expiration
2043-11-22

AI Technical Summary

Technical Problem

The prior art has problems such as insufficient sensitivity, high equipment cost, large error in test results and high requirements for enzyme stability in glucose detection, making it difficult to achieve non-invasive, fast and accurate blood sugar monitoring.

Method used

Using Ni60+xMo20-xP16B4 amorphous alloy electrode material, electrochemical glucose detection is carried out in the three-electrode working system, and combined with the microelectrode system and signal processing unit to achieve continuous monitoring of glucose.

Benefits of technology

It realizes high sensitivity glucose detection, with a detection sensitivity of 2.503mAcm-2mM-1, simplifying the preparation process of electrode materials, improving stability and storage convenience, and having non-invasive, fast and accurate detection capabilities.

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Abstract

The invention discloses an amorphous alloy electrode for electrochemical glucose detection sensing. The electrode material is an amorphous alloy, the chemical composition expression of the electrode material is Ni < 60 + x > Mo < 20-x > P16B4, and x is equal to 0-8. The preparation method comprises the following steps: firstly, obtaining a Ni < 60 + x > Mo < 20-x > P16B4 alloy cast ingot through induction melting, then preparing an amorphous alloy strip from the alloy cast ingot through a single-roller rotary quenching method, and finally preparing the sensing electrode for electrochemical glucose detection through a connecting copper sheet or a screen printing electrode. The amorphous alloy electrode provided by the invention can realize visual detection of glucose in a strong alkali or strong acid electrolyte solution.
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Description

Technical Field

[0001] The invention belongs to the technical field of electrochemical glucose sensing and relates to an amorphous alloy electrode for electrochemical glucose detection sensing. Background Art

[0002] With the development of the economy and society, diabetes has become one of the most common chronic diseases in modern life. According to the data from the International Diabetes Federation (IDF) on December 6, 2021, the latest "IDF World Diabetes Atlas (10th Edition)" shows that as of 2021, 67 million people worldwide have lost their lives due to diabetes. IDF pointed out that among adults aged 20 to 79 years old worldwide, one in every 10 people has diabetes, and the total number of people with diabetes worldwide is as high as 537 million; and IDF also pointed out that in developing countries, 3 out of every 4 people have diabetes. Real-time monitoring of blood glucose concentration may be an effective way to solve this problem, so the development of sensors that can quickly and accurately detect glucose concentration levels in the blood and visualize the results is of great significance for the prevention and treatment of diabetes.

[0003] The current mainstream sensor is the enzyme glucose sensor, which has very important research value in glucose detection due to its high sensitivity and selectivity. At present, the commercial method of human blood glucose detection is still through the needle tip blood sampling-enzyme test paper method. This method not only brings physical pain to patients but also increases the risk of infection; but on the one hand, the enzyme is easily affected by environmental factors and inactivated, such as pH value, temperature, humidity, and the process of fixing the enzyme is very complicated, and its chemical stability is not good; on the other hand, although there are some non-invasive blood glucose monitoring equipment, the existing non-invasive blood glucose detector indirectly tests the concentration of glucose in the blood through infrared, electromagnetic, thermal capacity, ultrasound and other methods. The equipment is expensive and the test results have large errors. Therefore, there is an urgent need to develop a low-cost and non-invasive, fast and accurate continuous glucose monitoring sensor. Summary of the invention

[0004] The purpose of the present invention is to provide an amorphous alloy electrode material for electrochemical glucose detection sensing. In a three-electrode working system, when a glucose solution is added dropwise to an alkaline electrolyte, it exhibits ultra-high sensitivity; at the same time, an attempt is made to use a microelectrode system to connect a signal processing unit to achieve continuous glucose monitoring, providing a reference for exploring a new generation of wearable non-invasive blood glucose visualization monitoring equipment.

[0005] The technical solution adopted by the present invention is as follows:

[0006] An amorphous alloy electrode material for electrochemical glucose detection sensing, the electrode material is an amorphous alloy, and its chemical composition expression is Ni 60+xMo 20-x P 16 B 4, x=0-8, preferably x=4-6, and x is more preferably 4.

[0007] The method for preparing the above electrode material comprises the following steps:

[0008] Step 1, according to the chemical composition of the electrode material, using induction melting and arc melting methods to prepare alloy ingots;

[0009] Step 2, preparing an amorphous alloy strip by a vacuum single-roll spinning method using the obtained alloy ingot;

[0010] Step 3, cutting the obtained strip into sheets of required size as electrode material.

[0011] Preferably, in step 1, the induction melting current is 20A and the arc melting current is 160A.

[0012] Preferably, in step 2, when the amorphous alloy strip is prepared by vacuum single-roll spinning method, the diameter of the quartz tube injection nozzle is 0.7-0.9 mm, and optimally 0.8 mm.

[0013] Preferably, in step 2, when preparing the amorphous alloy strip by vacuum single-roll spinning method, the rotation speed of the copper roller is above 5000 rpm. If the rotation speed is too low, the cooling rate of the molten alloy liquid will be insufficient, resulting in failure to form an amorphous alloy.

[0014] The present invention also provides an amorphous alloy electrode for electrochemical glucose detection sensing prepared by the above method, and the specific steps are: applying a conductive silver paste on one surface of a clean copper sheet or a central circular area of ​​a commercial Poten-TC201 type screen-printed electrode, and after drying, placing the thin sheet, i.e., the electrode material, on the conductive silver paste to fully contact and press it, and insulating the area except the thin sheet.

[0015] The present invention also provides use of the amorphous alloy electrode in detecting glucose.

[0016] Furthermore, the glucose includes glucose in blood sugar.

[0017] Compared with the prior art, the present invention has the following advantages:

[0018] The present invention is the first to use Ni 60+x Mo 20-x P 16 B 4The electrode made of amorphous alloy strips performs electrochemical sensitivity detection of glucose in 0.1M NaOH solution. Compared with conventional enzyme glucose sensors, the electrode material of the present invention has a simple preparation process, high stability and is easier to store. At the same time, it shows a sensitivity of up to 2.503mAcm in glucose electrochemical detection. -2 mM -1 detection sensitivity. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 Ni in Example 1 60 Mo 20 P 16 B 4 Characterization of amorphous alloy electrode structure and electrochemical detection of glucose, where a is the XRD spectrum, b is the IT curve of glucose detection, c is the linear fitting result of the linear part in b, and the slope is the glucose detection sensitivity of the sensor.

[0020] Figure 2 Ni in Example 2 64 Mo 16 P 16 B 4 Characterization of amorphous alloy electrode structure and electrochemical detection of glucose, where a is the XRD spectrum, b is the IT curve of glucose detection, c is the linear fitting result of the linear part in b, and the slope is the glucose detection sensitivity of the sensor.

[0021] Figure 3 Ni in Example 3 66 Mo 14 P 16 B 4 Characterization of amorphous alloy electrode structure and electrochemical detection of glucose, where a is the XRD spectrum, b is the IT curve of glucose detection, c is the linear fitting result of the linear part in b, and the slope is the glucose detection sensitivity of the sensor.

[0022] Figure 4 Ni in Example 4 68 Mo 12 P 16 B 4 Characterization of amorphous alloy electrode structure and electrochemical detection of glucose, where a is the XRD spectrum, b is the IT curve of glucose detection, c is the linear fitting result of the linear part in b, and the slope is the glucose detection sensitivity of the sensor.

[0023] Figure 5 Ni in Example 5 64 Mo 16 P 16 B 4 Actual test photo of the amorphous alloy strip micro-sensing system.

[0024] Figure 6 Ni constructed in Example 5 64 Mo 16 P 16 B 4 IT curve of glucose detection of amorphous alloy strip microsensing system.

[0025] Figure 7 The crystalline Ni in Comparative Example 1 64 Mo 16 P 16 B 4 Glucose electrochemical detection using alloy electrodes, where a is the XRD pattern, b is the IT curve for glucose detection, c is the linear fitting result of the linear part in b, and the slope is the glucose detection sensitivity of the sensor. DETAILED DESCRIPTION

[0026] The technical solution of the present invention is further described below with specific implementation methods. The following embodiments are all implemented on the premise of the technical solution of the present invention, and detailed implementation methods and specific operation processes are given, but the protection scope of the present invention is not limited to the following embodiments.

[0027] Based on the previous research on the composition of NiMo-based amorphous alloys, we have designed a fuel cell electrode material that can match the performance of Pt. Based on the design criteria for the composition of amorphous alloys, we believe that NiMoPB amorphous alloys with a suitable NiMo element ratio have good catalytic performance in electrochemical glucose detection.

[0028] Example 1

[0029] Step 1: Take high-purity Ni, Mo, P, and B (purity above 99.95%) and accurately weigh them according to the ingot composition ratio, and use induction melting and arc melting methods in turn to obtain Ni 60 Mo 20 P 16 B 4 Alloy ingots;

[0030] Step 2: Ni obtained in step 1 60 Mo 20 P 16 B 4 The alloy ingot was placed in a quartz tube with a casting port diameter of 0.8 mm and evacuated;

[0031] Step 3, after the vacuum environment is formed, high-purity argon gas is filled in as a protective gas, and the speed of the copper roller is set to 5000 rpm;

[0032] Step 4: Turn on the induction heating power supply and slowly increase it to 20A. 60 Mo20 P 16 B 4 The alloy ingot is heated to boiling state and maintained for 10 seconds;

[0033] Step 5: Ni 60 Mo 20 P 16 B 4 The alloy melt is spray-casted into an amorphous alloy strip and collected;

[0034] Step 6, coating the first surface of the clean copper sheet with conductive silver paste, placing the thin sheet obtained in step 5 on the first surface after drying to fully contact and press, and performing insulation treatment on the area other than the thin sheet;

[0035] Step 7, connect the three-electrode working system (the amorphous alloy electrode prepared in the present invention is the working electrode, the platinum sheet electrode is the counter electrode, and the Ag / AgCl is the reference electrode) to the electrochemical workstation, and perform electrochemical testing in a 0.1M NaOH solution as the electrolyte solution. Place the electrolytic cell on a magnetic stirring table with a rotation speed of 300 r / min and a temperature of 25°C.

[0036] Step 8, perform cyclic voltammetry test to activate the surface of the working electrode, set the voltage window to 0.15V to 0.65V, the scan rate to 50mV / s, and the number of scan segments to 20.

[0037] Step 9, set the chronoamperometric detection and set the potential to 0.5 V. Add glucose solutions of different concentrations to the electrolytic cell so that the glucose concentration in the electrolyte solution changes continuously from 10 μM to 1 mM.

[0038] To you 60 Mo 20 P 16 B 4 The amorphous alloy strip electrode was tested by XRD, with a scanning angle range (2θ) of 30° to 60° and a scanning step of 0.02°. The results showed that a diffuse peak different from the strong diffraction peak of the crystal appeared around 2θ of about 43°, proving its amorphous structure. Figure 1 As shown in a in .

[0039] The electrochemical sensitivity test was carried out. By statistically analyzing the current response in the IT curve under different glucose concentrations ( Figure 1 The electrochemical sensitivity of the electrode to glucose can be obtained by linear fitting. 60 Mo 20 P 16 B 4 The sensitivity of the amorphous alloy strip electrode to glucose is 0.96 mA cm -2 mM, such as Figure 1As shown in c.

[0040] Example 2

[0041] Step 1: Take high-purity Ni, Mo, P, and B (purity above 99.95%) and accurately weigh them according to the ingot composition ratio, and use induction melting and arc melting methods in turn to obtain Ni 64 Mo 16 P 16 B 4 Alloy ingots;

[0042] Step 2: Ni obtained in step 1 64 Mo 16 P 16 B 4 The alloy ingot was placed in a quartz tube with a casting port diameter of 0.8 mm and evacuated;

[0043] Step 3, after the vacuum environment is formed, high-purity argon gas is filled in as a protective gas, and the speed of the copper roller is set to 5000 rpm;

[0044] Step 4: Turn on the induction heating power supply and slowly increase it to 20A. 64 Mo 16 P 16 B 4 The alloy ingot is heated to boiling state and maintained for 10 seconds;

[0045] Step 5: Ni 64 Mo 16 P 16 B 4 The alloy melt is spray-casted into an amorphous alloy strip and collected;

[0046] Step 6, coating the first surface of the clean copper sheet with conductive silver paste, placing the thin sheet obtained in step 5 on the first surface after drying to fully contact and press, and performing insulation treatment on the area other than the thin sheet;

[0047] Step 7, connect the three-electrode working system (the amorphous alloy electrode prepared in the present invention is the working electrode, the platinum sheet electrode is the counter electrode, and the Ag / AgCl is the reference electrode) to the electrochemical workstation, and perform electrochemical testing in a 0.1M NaOH solution as the electrolyte solution. Place the electrolytic cell on a magnetic stirring table with a rotation speed of 300 r / min and a temperature of 25°C.

[0048] Step 8, perform cyclic voltammetry test to activate the surface of the working electrode, set the voltage window to 0.15V to 0.65V, the scan rate to 50mV / s, and the number of scan segments to 20.

[0049] Step 9, set the chronoamperometric detection and set the potential to 0.5 V. Add glucose solutions of different concentrations to the electrolytic cell so that the glucose concentration in the electrolyte solution changes continuously from 10 μM to 1 mM.

[0050] To you 64 Mo 16 P 16 B 4 The amorphous alloy strip electrode was tested by XRD, with a scanning angle range (2θ) of 30° to 60° and a scanning step of 0.02°. The results showed that a diffuse peak different from the strong diffraction peak of the crystal appeared around 2θ of about 43°, proving its amorphous structure. Figure 2 As shown in a in .

[0051] The electrochemical sensitivity test was carried out. By statistically analyzing the current response in the IT curve under different glucose concentrations ( Figure 2 The electrochemical sensitivity of the electrode to glucose can be obtained by linear fitting. 64 Mo 16 P 16 B 4 The sensitivity of the amorphous alloy strip electrode to glucose is 2.503 mA cm -2 mM -1 ,like Figure 2 As shown in c.

[0052] Example 3

[0053] Step 1: Take high-purity Ni, Mo, P, and B (purity above 99.95%) and accurately weigh them according to the ingot composition ratio, and use induction melting and arc melting methods in turn to obtain Ni 66 Mo 14 P 16 B 4 Alloy ingots;

[0054] Step 2: Ni obtained in step 1 66 Mo 14 P 16 B 4 The alloy ingot was placed in a quartz tube with a casting port diameter of 0.8 mm and evacuated;

[0055] Step 3, after the vacuum environment is formed, high-purity argon gas is filled in as a protective gas, and the speed of the copper roller is set to 5000 rpm;

[0056] Step 4: Turn on the induction heating power supply and slowly increase it to 20A. 66 Mo 14 P 16 B 4 The alloy ingot is heated to boiling state and maintained for 10 seconds;

[0057] Step 5: Ni 66 Mo 14 P 16 B 4 The alloy melt is spray-casted into an amorphous alloy strip and collected;

[0058] Step 6, coating the first surface of the clean copper sheet with conductive silver paste, placing the thin sheet obtained in step 5 on the first surface after drying to fully contact and press, and performing insulation treatment on the area other than the thin sheet;

[0059] Step 7, connect the three-electrode working system (the amorphous alloy electrode prepared in the present invention is the working electrode, the platinum sheet electrode is the counter electrode, and the Ag / AgCl is the reference electrode) to the electrochemical workstation, and perform electrochemical testing in a 0.1M NaOH solution as the electrolyte solution. Place the electrolytic cell on a magnetic stirring table with a rotation speed of 300 r / min and a temperature of 25°C.

[0060] Step 8, perform cyclic voltammetry test to activate the surface of the working electrode, set the voltage window to 0.15V to 0.65V, the scan rate to 50mV / s, and the number of scan segments to 20.

[0061] Step 9, set the chronoamperometric detection and set the potential to 0.5 V. Add glucose solutions of different concentrations to the electrolytic cell so that the glucose concentration in the electrolyte solution changes continuously from 10 μM to 1 mM.

[0062] To you 66 Mo 14 P 16 B 4 The amorphous alloy strip electrode was tested by XRD, with a scanning angle range (2θ) of 30° to 60° and a scanning step of 0.02°. The results showed that a diffuse peak different from the strong diffraction peak of the crystal appeared around 2θ of about 43°, proving its amorphous structure. Figure 3 As shown in a in .

[0063] The electrochemical sensitivity test was carried out. By statistically analyzing the current response in the IT curve under different glucose concentrations ( Figure 3 The electrochemical sensitivity of the electrode to glucose can be obtained by linear fitting. 66 Mo 14 P 16 B 4 The sensitivity of the amorphous alloy strip electrode to glucose is 1.671 mA cm -2 mM -1 ,like Figure 3 As shown in c.

[0064] Example 4

[0065] Step 1: Take high-purity Ni, Mo, P, and B (purity above 99.95%) and accurately weigh them according to the ingot composition ratio, and use induction melting and arc melting methods in turn to obtain Ni 68 Mo 12 P 16 B 4 Alloy ingots;

[0066] Step 2: Ni obtained in step 1 68 Mo 12 P 16 B 4 The alloy ingot was placed in a quartz tube with a casting port diameter of 0.8 mm and evacuated;

[0067] Step 3, after the vacuum environment is formed, high-purity argon gas is filled in as a protective gas, and the speed of the copper roller is set to 5000 rpm;

[0068] Step 4: Turn on the induction heating power supply and slowly increase it to 20A. 68 Mo 12 P 16 B 4 The alloy ingot is heated to boiling state and maintained for 10 seconds;

[0069] Step 5: Ni 68 Mo 12 P 16 B 4 The alloy melt is spray-casted into an amorphous alloy strip and collected;

[0070] Step 6, coating the first surface of the clean copper sheet with conductive silver paste, placing the thin sheet obtained in step 5 on the first surface after drying to fully contact and press, and performing insulation treatment on the area other than the thin sheet;

[0071] Step 7, connect the three-electrode working system (the amorphous alloy electrode prepared in the present invention is the working electrode, the platinum sheet electrode is the counter electrode, and the Ag / AgCl is the reference electrode) to the electrochemical workstation, and perform electrochemical testing in a 0.1M NaOH solution as the electrolyte solution. Place the electrolytic cell on a magnetic stirring table with a rotation speed of 300 r / min and a temperature of 25°C.

[0072] Step 8, perform cyclic voltammetry test to activate the surface of the working electrode, set the voltage window to 0.15V to 0.65V, the scan rate to 50mV / s, and the number of scan segments to 20.

[0073] Step 9, set the chronoamperometric detection and set the potential to 0.5 V. Add glucose solutions of different concentrations to the electrolytic cell so that the glucose concentration in the electrolyte solution changes continuously from 10 μM to 1 mM.

[0074] To you68 Mo 12 P 16 B 4 The amorphous alloy strip electrode was tested by XRD, with a scanning angle range (2θ) of 30° to 60° and a scanning step of 0.02°. The results showed that a diffuse peak different from the strong diffraction peak of the crystal appeared around 2θ of about 43°, proving its amorphous structure. Figure 4 As shown in a in .

[0075] The electrochemical sensitivity test was carried out. By statistically analyzing the current response in the IT curve under different glucose concentrations ( Figure 4 The electrochemical sensitivity of the electrode to glucose can be obtained by linear fitting. 68 Mo 12 P 16 B 4 The sensitivity of the amorphous alloy strip electrode to glucose is 1.56 mA cm -2 mM, such as Figure 4 As shown in c.

[0076] Example 5

[0077] Step 1: Take high-purity Ni, Mo, P, and B (purity above 99.95%) and accurately weigh them according to the ingot composition ratio, and use induction melting and arc melting methods in turn to obtain Ni 64 Mo 16 P 16 B 4 Alloy ingots;

[0078] Step 2: Ni obtained in step 1 64 Mo 16 P 16 B 4 The alloy ingot was placed in a quartz tube with a casting port diameter of 0.8 mm and evacuated;

[0079] Step 3, after the vacuum environment is formed, high-purity argon gas is filled in as a protective gas, and the speed of the copper roller is set to 5000 rpm;

[0080] Step 4: Turn on the induction heating power supply and slowly increase it to 20A. 64 Mo 16 P 16 B 4 The alloy ingot is heated to boiling state and maintained for 10 seconds;

[0081] Step 5: Ni 64 Mo 16 P 16 B 4 The alloy melt is spray-casted into an amorphous alloy strip and collected;

[0082] Step 6: Ni 64 Mo 16 P 16 B 4 The strip is cut into 2*2mm thin sheets for backup;

[0083] Step 7, apply conductive silver paste to the central circular area of ​​the commercial Poten-TC201 type screen-printed electrode, and after drying, place the thin sheet obtained in step 6 on it to fully contact and press it, and perform insulation treatment on the area except the thin sheet;

[0084] Step 8, connect the three-electrode working system (the amorphous alloy electrode prepared in the present invention is the working electrode, the carbon electrode is the counter electrode, and Ag / AgCl is the reference electrode) to the electrochemical workstation, and perform electrochemical testing in a 0.1M NaOH solution as the electrolyte solution. Place the electrolytic cell on a magnetic stirring table with a rotation speed of 200 r / min and a temperature of 25°C.

[0085] Step 9, perform cyclic voltammetry test to activate the surface of the working electrode, set the voltage window to 0.1V-0.4V, the scan rate to 50mV / s, and the number of scan segments to 20.

[0086] Step 10, setting the chronoamperometric detection, and setting the potential to 0.3 V. Glucose solutions of different concentrations were added dropwise to the electrolytic cell so that the glucose concentration in the electrolyte solution changed continuously from 80 μM to 248 μM.

[0087] Figure 5 For you 64 Mo 16 P 16 B 4 Actual test photo of the amorphous alloy strip micro-sensing system.

[0088] Electrochemical tests were also performed. Figure 6 As shown in a, as the glucose concentration in the electrolytic cell continues to change, the IT curve also shows a consistent current response. By statistically analyzing the current response in the IT curve at different glucose concentrations and performing linear fitting, the electrochemical sensitivity of the electrode to glucose can be obtained. 64 Mo 16 P 16 B 4 The sensitivity of the amorphous alloy strip microsensor system to glucose is 4.3678 mA cm -2 mM, such as Figure 6 This shows that the Ni constructed in the present invention 64 Mo 16 P 16 B 4The amorphous alloy strip microsensor system has the capability of continuous glucose detection.

[0089] Comparative Example 1

[0090] Step 1: Take high-purity Ni, Mo, P, and B (purity above 99.95%) and accurately weigh them according to the ingot composition ratio, and use induction melting and arc melting methods in turn to obtain Ni 64 Mo 16 P 16 B 4 Alloy ingots;

[0091] Step 2: Ni obtained in step 1 64 Mo 16 P 16 B 4 The alloy ingot was placed in a quartz tube with a casting port diameter of 0.8 mm and evacuated;

[0092] Step 3, after the vacuum environment is formed, high-purity argon gas is filled in as a protective gas, and the speed of the copper roller is set to 4500 rpm;

[0093] Step 4: Turn on the induction heating power supply and slowly increase it to 20A. 64 Mo 16 P 16 B 4 The alloy ingot is heated to boiling state and maintained for 10 seconds;

[0094] Step 5: Ni 64 Mo 16 P 16 B 4 The alloy melt is spray-cast into a crystalline alloy strip and collected;

[0095] Step 6, coating the first surface of the clean copper sheet with conductive silver paste, placing the thin sheet obtained in step 5 on the first surface after drying to fully contact and press, and performing insulation treatment on the area other than the thin sheet;

[0096] Step 7, connect the three-electrode working system (the amorphous alloy electrode prepared in the present invention is the working electrode, the platinum sheet electrode is the counter electrode, and the Ag / AgCl is the reference electrode) to the electrochemical workstation, and perform electrochemical testing in a 0.1M NaOH solution as the electrolyte solution. Place the electrolytic cell on a magnetic stirring table with a rotation speed of 300 r / min and a temperature of 25°C.

[0097] Step 8, perform cyclic voltammetry test to activate the surface of the working electrode, set the voltage window to 0.15V to 0.65V, the scan rate to 50mV / s, and the number of scan segments to 20.

[0098] Step 9, setting the chronoamperometric detection and setting the potential to 0.5 V. Glucose solutions of different concentrations were added dropwise to the electrolytic cell so that the glucose concentration in the electrolyte solution varied continuously from 100 μM to 1000 μM.

[0099] The alloy strip was tested by XRD, with a scanning angle range (2θ) of 20° to 60° and a scanning step of 0.02°. The results showed that in addition to the diffuse peak representing the amorphous structure at about 38° 2θ, there was also a strong diffraction peak representing the crystal, which indicated that the strip prepared by reducing the copper roller speed had crystallized. Figure 7 As shown in a in .

[0100] Electrochemical tests were also performed. Figure 7 As shown in Figure b, as the glucose concentration in the electrolytic cell continues to change, the IT curve also shows a consistent current response. By statistically analyzing the current response in the IT curve at different glucose concentrations and performing linear fitting, the electrochemical sensitivity of the electrode to glucose can be obtained. 64 Mo 16 P 16 B 4 The sensitivity of the crystalline alloy strip microsensor system to glucose is 0.905 mA cm -2 mM. Figure 7 This shows that the Ni 64 Mo 16 P 16 B 4 Amorphous alloy strips have higher glucose detection sensitivity due to the larger number of highly active unsaturated sites on the surface of amorphous materials.

[0101] In summary, Ni 64 Mo 16 P 16 B 4 The amorphous alloy strip electrode has ultra-high sensitivity to glucose detection. 64 Mo 16 P 16 B 4 The amorphous alloy strip microsensor system has the capability of continuous glucose detection.

Claims

1. An amorphous alloy electrode material for electrochemical glucose detection sensing, It is characterized in that The electrode material is an amorphous alloy, and its chemical composition expression is Ni 60+x Mo 20-x P 16 B 4, x=0~8, preferably x=4~6, and x is more preferably 4.

2. The method for preparing the electrode material according to claim 1, It is characterized in that The following steps are involved: Step 1, according to the chemical composition of the electrode material, using induction melting and arc melting methods to prepare alloy ingots; Step 2, preparing an amorphous alloy strip by a vacuum single-roll spinning method using the obtained alloy ingot; Step 3, cutting the obtained strip into sheets of required size as electrode material.

3. The method according to claim 2, It is characterized in that In step 1, the induction melting current is 20 A and the arc melting current is 160 A.

4. The method according to claim 2, It is characterized in that In step 2, when the amorphous alloy strip is prepared by vacuum single-roll spinning method, the diameter of the quartz tube injection nozzle is 0.7-0.9 mm, and the optimal diameter is 0.8 mm.

5. The method according to claim 2, It is characterized in that In step 2, when the amorphous alloy strip is prepared by vacuum single-roll spinning method, the rotation speed of the copper roller is above 5000 rpm.

6. An amorphous alloy electrode for electrochemical glucose detection sensing, It is characterized in that Prepared from the electrode material according to claim 1.

7. The amorphous alloy electrode according to claim 6, It is characterized in that The preparation steps of the amorphous alloy electrode are as follows: coating a conductive silver paste on one surface of a clean copper sheet or a central circular area of ​​a commercial Poten-TC201 type screen-printed electrode, placing the electrode material on the conductive silver paste after drying to fully contact and press it, and performing insulation treatment on the area other than the electrode material.

8. Use of the amorphous alloy electrode as claimed in claim 6 in detecting glucose.

9. The use according to claim 8, It is characterized in that The glucose includes glucose in blood sugar.

Citation Information

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