An electrode material for portable glucose sensing, and a preparation method and application thereof

Abstract

This invention discloses an electrode material for portable glucose sensing, its preparation method, and its application. A surfactant solution is prepared, and the pH of the solution is adjusted with acid. Cobalt cyanide and nickel salt are added, followed by a reducing agent. Hydrothermal treatment yields a faceted Prussian blue analogue, Ni. 1.67 Co 1.33 [Co(CN)6]2, Ni 1.67 Co 1.33 [Co(CN)6]2 is dispersed in anhydrous ethanol, a film-forming substance is added, and the mixture is ultrasonically treated for later use. A glassy carbon electrode is then pretreated, and the catalyst solution is dropwise added to the surface of the glassy carbon electrode. After drying, the electrode material is obtained and used as the working electrode in a portable glucose sensor. This invention utilizes a Prussian blue analogue, Ni... 1.67 Co 1.33 The [Co(CN)6]2 modified electrode and portable sensing device are assembled into a detection device, which has good portability and detection effect, high sensitivity, low detection limit and good anti-interference ability, and also shows good detection effect on actual serum samples.

Description

Technical Field

[0001] This invention belongs to the field of preparation and application technology of electrochemical glucose sensing electrode materials, specifically relating to an electrode material that can be used for portable glucose sensing, its preparation method and application. Background Technology

[0002] Portable sensors are gaining increasing attention in the field of medical management, particularly for monitoring chronic diseases such as diabetes and chronic wounds. Diabetes-related diseases are a leading cause of death, and the number of people with diabetes is expected to increase significantly in the coming years. Current enzyme-based point-of-care testing devices suffer from drawbacks such as poor electrode stability, high cost, and complex operation. Therefore, constructing an enzyme-free electrochemical glucose sensor and integrating it as the detection front end of a portable electrochemical detection system can create a portable, accurate, easy-to-operate, and low-cost glucose detection device, which is beneficial for diabetic patients to manage their own health. The glucose sensing electrode is a crucial component of portable sensors, and its performance directly affects key indicators such as sensitivity, stability, response time, and detection limit. Therefore, designing and optimizing suitable electrode materials is essential for improving the stability, selectivity, and response speed of portable glucose sensors.

[0003] Prussian blue (PB) and its analogues (PBA) are typical cyano coordination polymers. Due to their excellent electrochemical activity and unique structural features (including open framework structure, high specific surface area, and tunable metal active sites), they have attracted widespread attention in the field of electrochemical sensing and show promising application prospects. Compared with PB, PBA exhibits higher stability in neutral and alkaline solutions, allowing it to work with biorecognition elements in physiologically compatible media. Furthermore, some PBAs have been reported to show good selectivity for easily oxidized interfering substances, such as uric acid, oxalic acid, and ascorbic acid. Although PBA has proven to be a good active material for electrochemical sensor electrodes, its physicochemical properties (such as electrochemical activity, biocompatibility, and structural stability) still need continuous improvement through ongoing research to meet the requirements for constructing portable electrochemical sensors and wearable devices. Bimetallic PBA exhibits excellent electrochemical behavior due to its enhanced stability in alkaline solutions and unique cation permeability. The stoichiometry of the outer metal in bimetallic PBA plays a crucial role in its electrochemical behavior. Ni-Co Prussian blue analogue Ni x Co y [Co(CN)6]2 has two transition metals with tunable stoichiometric ratios in its outer coordination layer. If their morphology and stoichiometric coefficients can be precisely controlled, it holds promise for obtaining highly active electrode materials suitable for portable glucose sensing. Currently, there are no methods for controlling the synthesis of Ni with polyhedral morphology.1.67 Co 1.33 Reports on the use of [Co(CN)6]2 Prussian blue analogues in portable glucose sensors. Summary of the Invention

[0004] The purpose of this invention is to address the shortcomings of existing technologies by providing an electrode material for portable glucose sensing, its preparation method, and its application.

[0005] The specific technical solution is as follows: 1) Prussian blue analogue Ni 1.67 Co 1.33 Preparation of [Co(CN)6]2 A certain amount of surfactant was weighed and dissolved in deionized water under stirring. After complete dissolution, the pH of the solution was adjusted with acid. Then, a certain amount of cobalt cyanide was added to the solution under stirring. After complete dissolution, a certain amount of nickel salt was added in proportion and stirred for 10 minutes. Finally, a small amount of reducing agent was added to the solution and sonicated for 10 minutes. The treated solution was transferred to a hydrothermal reactor and hydrothermally treated for a certain time under the set temperature conditions. Finally, the precipitate was separated, washed, and dried to obtain a polyhedral Prussian blue analogue, Ni. 1.67 Co 1.33 [Co(CN)6]2.

[0006] Preferably, the surfactant is one of polyvinylpyrrolidone or sodium dodecylbenzenesulfonate.

[0007] Preferably, the acid is one of hydrochloric acid, acetic acid, and nitric acid.

[0008] Preferably, the pH value of the solution is 1-4.

[0009] Preferably, the cobalt cyanide is one of K3[Co(CN)6] or Na3[Co(CN)6].

[0010] Preferably, the nickel salt is one of nickel acetate, nickel chloride, nickel nitrate, and nickel sulfate.

[0011] Preferably, the reducing agent is ascorbic acid.

[0012] Preferably, the ratio of nickel salt to cobalt cyanide is 1:2 in molar ratio.

[0013] Preferably, the hydrothermal treatment temperature is 100-170ºC.

[0014] Preferably, the hydrothermal treatment time is 3-10 hours.

[0015] 2) Prussian blue analogue Ni1.67 Co 1.33 Modification of glassy carbon electrodes with [Co(CN)6]2 Prussian blue analogue Ni 1.67 Co 1.33 The modification process of the glassy carbon electrode by [Co(CN)6]2 is as follows: a certain amount of Prussian blue analog Ni is weighed out. 1.67 Co 1.33 [Co(CN)6]2 was dispersed in anhydrous ethanol, and a certain amount of film-forming material was added. The mixture was then sonicated for 10 minutes to form a uniform suspension for later use. Separately, the glassy carbon electrode was polished with 1.0 and 0.3 μm Al2O3 to remove surface contaminants, and then ultrasonically cleaned with ethanol solution, nitric acid solution, and deionized water, respectively. After cleaning, the electrode was activated in sulfuric acid solution. Finally, a certain amount of catalyst solution was dropped onto the polished glassy carbon electrode surface. After natural drying, the electrode was further dried in a 60°C oven for 10 minutes. After cooling, it was ready for experimental use.

[0016] Preferably, the film-forming substance is Nafion reagent.

[0017] Preferably, the ethanol solution and nitric acid solution are respectively a 1:1 volume ratio of ethanol aqueous solution and a 1:1 volume ratio of nitric acid aqueous solution.

[0018] Preferably, the activation conditions are as follows: the electrode is activated in 0.5-1 mol / L H2SO4 solution using cyclic voltammetry, with a scan range of 1.0 to -1.0 V.

[0019] 3) Portable glucose sensing applications The Prussian blue analogue Ni prepared in step 2 1.67 Co 1.33 A [Co(CN)6]2 modified glassy carbon electrode was used as the working electrode, and its portable glucose sensing performance was determined using a three-electrode system in an alkaline electrolyte solution. Specifically, the three-electrode system was connected to a micro-electrochemical workstation via electrode wires, and the micro-workstation was connected to a smartphone via a data cable. The smartphone provided power to the micro-workstation via the data cable and used an app to set and control the testing methods. Electrochemical sensing performance was primarily tested using cyclic voltammetry and chronoamperometry.

[0020] Preferably, the alkaline electrolyte solution is either NaOH or KOH solution.

[0021] Preferably, the reference electrode of the three-electrode system is either a silver-silver chloride electrode or a saturated calomel electrode.

[0022] Preferably, the counter electrode of the three-electrode system is a Pt wire electrode or a Pt sheet electrode.

[0023] By employing the above-described technology, the beneficial effects of the present invention compared to the prior art are as follows: 1) The Prussian blue analogue Ni obtained by the present invention using a specific technique 1.67 Co 1.33 [Co(CN)6]2 has a polyhedral structure with a size of approximately 1 μm. The two transition metals in its outer coordination layer are Ni and Co. By adjusting the Ni / Co ratio in the raw materials and using a suitable reducing agent, the Ni / Co stoichiometric ratio of the outer coordination layer of the product is 1.67:1.33, and the crystal form is a cubic phase structure.

[0024] 2) The preparation method is simple, the active sites are easy to adjust, it has excellent electrochemical activity, and the process is suitable for industrial production.

[0025] 3) Ni, a Prussian blue analogue 1.67 Co 1.33 The [Co(CN)6]2 modified electrode and portable sensing device are assembled into a detection device, which has good portability and detection effect, high sensitivity, low detection limit and good anti-interference ability, and also shows good detection effect on actual serum sample detection. The portable glucose sensor based on smartphone proposed in this work is used for rapid, simple and mobile glucose measurement, and has good application value in diabetes care as well as the food and pharmaceutical industries. Attached Figure Description

[0026] Figure 1 This invention is based on the Prussian blue analog Ni prepared in Example 1. 1.67 Co 1.33 SEM image of [Co(CN)6]2.

[0027] Figure 2 This is a schematic diagram of a portable glucose sensing device based on a smartphone, assembled according to Embodiment 1 of the present invention.

[0028] Figure 3 This invention is based on the Prussian blue analogue Ni prepared in Example 2. 1.67 Co 1.33 XRD comparison of [Co(CN)6]2 and other Prussian blue analogues.

[0029] Figure 4 These are cyclic voltammetry curves measured using the portable glucose sensor assembled in Example 3 of this invention, as well as comparison curves with other Prussian blue analogues.

[0030] Figure 5This is a chronoamperometry curve measured by the portable glucose sensor assembled based on Example 4 of the present invention.

[0031] Figure 6 This is a linear fit of the chronoampere curve measured by the portable glucose sensor assembled in Example 4 according to the present invention.

[0032] Figure 7 This is a chronoamperotropic curve of a serum sample measured by the portable glucose sensor assembled in Example 5 of this invention. Detailed Implementation

[0033] The present invention will be further described below with reference to the accompanying drawings and embodiments, but the scope of protection of the present invention is not limited thereto.

[0034] Example 1

[0035] 1) Weigh 2g of polyvinylpyrrolidone and dissolve it in 44ml of deionized water under stirring. After complete dissolution, adjust the pH of the solution to 1 with hydrochloric acid. Then, under stirring, add 2mmol of K3[Co(CN)6] to the solution and dissolve it completely. Then, add 1mmol of nickel acetate and stir for 10min. Finally, add 0.6mmol of ascorbic acid to the solution and sonicate for 10min. Transfer the treated solution to a hydrothermal reactor and hydrothermally treat it at 100ºC for 10h. Finally, separate, wash, and dry the precipitate to obtain the polyhedral Prussian blue analog Ni. 1.67 Co 1.33 [Co(CN)6]2.

[0036] Figure 1 Ni, a Prussian blue analog prepared based on this embodiment 1.67 Co 1.33 The SEM image of [Co(CN)6]2 shows that the product has a polyhedral structure with an average size of about 1 μm.

[0037] 2) Weigh 10 mg of Prussian blue analogue Ni 1.67 Co 1.33[Co(CN)6]2 was dispersed in 10 ml of anhydrous ethanol, and 10 μL of Nafion reagent was added. The mixture was then sonicated for 10 minutes to form a homogeneous suspension for later use. Separately, the glassy carbon electrode was polished with 1.0 μm and 0.3 μm Al2O3 to remove surface contaminants. Finally, it was ultrasonically cleaned with a 1:1 volume ratio of ethanol-water solution, a 1:1 volume ratio of nitric acid-water solution, and deionized water, respectively. After cleaning, the electrode was activated in 0.5 mol / L sulfuric acid solution (using cyclic voltammetry to scan 50 cycles from -0.1 V to 0.1 V). Finally, 10 μL of catalyst solution was dropped onto the polished glassy carbon electrode surface. After natural drying, the electrode was further dried in a 60°C oven for 10 minutes. After cooling, it was ready for experimental use.

[0038] 3) The Prussian blue analogue Ni prepared in step 2 1.67 Co 1.33 The portable glucose sensing performance was determined using a three-electrode system with a [Co(CN)6]2 modified glassy carbon electrode as the working electrode, a Pt sheet as the counter electrode, and a silver / silver chloride electrode as the reference electrode in a 0.1M NaOH electrolyte solution.

[0039] Figure 2 In this embodiment, Ni is based on the Prussian blue analogue. 1.67 Co 1.33 A schematic diagram of a portable glucose sensing device based on a smartphone, assembled using a [Co(CN)6]2 modified glassy carbon electrode as the working electrode. Specifically, the three-electrode system is connected to a micro-electrochemical workstation via electrode wires, and the micro-workstation is connected to the smartphone via a data cable. The smartphone provides power to the micro-workstation via the data cable and sets and controls the testing methods via an app. The electrochemical sensing performance is mainly tested using cyclic voltammetry and chronoamperometry.

[0040] Example 2

[0041] 1) Weigh 1.5g of sodium dodecylbenzenesulfonate and dissolve it in 30ml of deionized water under stirring. After complete dissolution, adjust the pH of the solution to 4 with hydrochloric acid. Then, under stirring, add 1.6mmol of Na3[Co(CN)6] to the solution. After complete dissolution, add 0.8mmol of nickel chloride and stir for 10min. Finally, add 0.5mmol of ascorbic acid to the solution and sonicate for 10min. Transfer the treated solution to a hydrothermal reactor and hydrothermally treat it at 170ºC for 3h. Finally, separate, wash, and dry the precipitate to obtain the polyhedral Prussian blue analog Ni. 1.67 Co 1.33 [Co(CN)6]2.

[0042] Figure 3Ni, a Prussian blue analogue prepared based on this embodiment 1.67 Co 1.33 XRD comparison of [Co(CN)6]2 and other Prussian blue analogues. The figures show that as the proportion of Ni in the outer coordination layer increases, the position of the (200) plane diffraction peak near 17.3º gradually shifts to the right. 1.67 Co 1.33 The diffraction peaks of [Co(CN)6]2 lie between those of pure Co3[Co(CN)6]2 and Ni3[Co(CN)6]2. Furthermore, from CoNi... 1.67 Co 1.33 The diffraction peak intensity of [Co(CN)6]2 indicates that the product has good crystallinity and a cubic phase structure.

[0043] 2) Weigh out 8 mg of Prussian blue analogue Ni 1.67 Co 1.33 [Co(CN)6]2 was dispersed in 8 ml of anhydrous ethanol, and 10 μL of Nafion reagent was added. The mixture was then sonicated for 10 minutes to form a homogeneous suspension for later use. Separately, the glassy carbon electrode was polished with 1.0 μm and 0.3 μm Al2O3 to remove surface contaminants. Finally, it was ultrasonically cleaned with a 1:1 volume ratio of ethanol-water solution, a 1:1 volume ratio of nitric acid-water solution, and deionized water, respectively. After cleaning, the electrode was activated in a 1 mol / L sulfuric acid solution (using cyclic voltammetry to scan from -0.1 V to 0.1 V for 30 cycles). Finally, 10 μL of catalyst solution was dropped onto the polished glassy carbon electrode surface. After natural drying, the electrode was further dried in a 60°C oven for 10 minutes. After cooling, it was ready for experimental use.

[0044] 3) The Prussian blue analogue Ni prepared in step 2 1.67 Co 1.33 A portable glucose sensing device was determined using a three-electrode system with a [Co(CN)6]2 modified glassy carbon electrode as the working electrode, a Pt wire electrode as the counter electrode, and a saturated calomel electrode as the reference electrode, in a 0.1 M KOH electrolyte solution. The portable glucose sensing device was connected via an electrode wire to a micro-electrochemical workstation, which in turn was connected to a smartphone via a data cable. The smartphone provided power to the micro-electrochemical workstation via the data cable and used an app to set and control the testing methods. Electrochemical sensing performance was primarily tested using cyclic voltammetry and chronoamperometry.

[0045] Example 3

[0046] 1) Weigh 1.5g of polyvinylpyrrolidone and dissolve it in 40ml of deionized water under stirring. After complete dissolution, adjust the pH of the solution to 3 with nitric acid. Then, under stirring, add 1.8mmol of K3[Co(CN)6] to the solution. After complete dissolution, add 0.9mmol of nickel nitrate and stir for 10min. Finally, add 0.6mmol of ascorbic acid to the solution and sonicate for 10min. Transfer the treated solution to a hydrothermal reactor and hydrothermally treat it at 120ºC for 8h. Finally, separate, wash, and dry the precipitate to obtain the polyhedral Prussian blue analog Ni. 1.67 Co 1.33 [Co(CN)6]2.

[0047] 2) Weigh out 5 mg of Prussian blue analogue Ni 1.67 Co 1.33 [Co(CN)6]2 was dispersed in 5 ml of anhydrous ethanol, and 5 μL of Nafion reagent was added. The mixture was then sonicated for 10 minutes to form a homogeneous suspension for later use. Separately, the glassy carbon electrode was polished with 1.0 μm and 0.3 μm Al2O3 to remove surface contaminants. Finally, it was ultrasonically cleaned with a 1:1 volume ratio of ethanol-water solution, a 1:1 volume ratio of nitric acid-water solution, and deionized water, respectively. After cleaning, the electrode was activated in 0.8 mol / L sulfuric acid solution (using cyclic voltammetry to scan from -0.1 V to 0.1 V for 40 cycles). Finally, 10 μL of catalyst solution was dropped onto the polished glassy carbon electrode surface. After natural drying, the electrode was further dried in a 60°C oven for 10 minutes. After cooling, it was ready for experimental use.

[0048] 3) The Prussian blue analogue Ni prepared in step 2 1.67 Co 1.33 A portable glucose sensing device was determined using a three-electrode system with a [Co(CN)6]2 modified glassy carbon electrode as the working electrode, a Pt sheet electrode as the counter electrode, and a silver / silver chloride electrode as the reference electrode, in 0.1 M NaOH electrolyte solution. The portable glucose sensing device was connected via electrode wires to a micro-electrochemical workstation, which in turn was connected to a smartphone via a data cable. The smartphone provided power to the micro-electrochemical workstation via the data cable and used an app to set and control the testing methods. Electrochemical sensing performance was primarily tested using cyclic voltammetry and chronoamperometry.

[0049] Figure 4 Cyclic voltammetry curves and comparison curves with other Prussian blue analogues were obtained for the portable sensor assembled based on this embodiment. Specific test conditions were: glucose concentration 1 mmol / L, electrolyte solution 0.1 M NaOH, and voltage scan rate 50 mV / s. The figure clearly shows that Ni...1.67 Co 1.33 The [Co(CN)6]2 modified electrode exhibits a pair of redox peaks, indicating that the electrode has good electrochemical oxidation performance for glucose. Additionally, Ni... 1.67 Co 1.33 The oxidation current of the [Co(CN)6]2 modified electrode is greater than that of other comparative samples, indicating that the Ni prepared by this method... 1.67 Co 1.33 [Co(CN)6]2 outperformed the control sample in glucose sensing.

[0050] Example 4

[0051] 1) Weigh 3g of polyvinylpyrrolidone and dissolve it in 60ml of deionized water under stirring. After complete dissolution, adjust the pH of the solution to 2 with acetic acid. Then, under stirring, add 3mmol of K3[Co(CN)6] to the solution. After complete dissolution, add 1.5mmol of nickel sulfate and stir for 10min. Finally, add 1mmol of ascorbic acid to the solution and sonicate for 10min. Transfer the treated solution to a hydrothermal reactor and hydrothermally treat it at 150ºC for 5h. Finally, separate, wash, and dry the precipitate to obtain the polyhedral Prussian blue analog Ni. 1.67 Co 1.33 [Co(CN)6]2.

[0052] 2) Weigh out 6 mg of Prussian blue analogue Ni 1.67 Co 1.33 [Co(CN)6]2 was dispersed in 6 ml of anhydrous ethanol, and 6 μL of Nafion reagent was added. The mixture was then sonicated for 10 minutes to form a homogeneous suspension for later use. Separately, the glassy carbon electrode was polished with 1.0 μm and 0.3 μm Al2O3 to remove surface contaminants. Finally, it was ultrasonically cleaned with a 1:1 volume ratio of ethanol-water solution, a 1:1 volume ratio of nitric acid-water solution, and deionized water, respectively. After cleaning, the electrode was activated in 0.7 mol / L sulfuric acid solution (using cyclic voltammetry to scan from -0.1 V to 0.1 V for 45 cycles). Finally, 10 μL of catalyst solution was dropped onto the polished glassy carbon electrode surface. After natural drying, the electrode was further dried in a 60°C oven for 10 minutes. After cooling, it was ready for experimental use.

[0053] 3) The Prussian blue analogue Ni prepared in step 2 1.67 Co 1.33A portable glucose sensing device was determined using a three-electrode system with a [Co(CN)6]2-modified glassy carbon electrode as the working electrode, a Pt sheet electrode as the counter electrode, and a saturated calomel electrode as the reference electrode, in a 0.1 M KOH electrolyte solution. The portable glucose sensing device was connected via an electrode wire to a micro-electrochemical workstation, which in turn was connected to a smartphone via a data cable. The smartphone provided power to the micro-electrochemical workstation via the data cable and used an app to set and control the testing methods. Electrochemical sensing performance was primarily tested using cyclic voltammetry and chronoamperometry.

[0054] like Figure 5 As shown, the chronoamperometry curves were obtained by continuously adding a certain amount of glucose to the electrolyte solution under an applied voltage of 0.55V. It can be clearly seen from the figure that the electrochemical response signal of the electrode continuously increases with the increase of glucose concentration, indicating that the electrode has good sensing performance for glucose. Figure 6 The figure shows the linear fitting results of the chronoamperometry curve obtained by the portable sensor assembled in this embodiment. As can be seen from the figure, the corresponding signal of the electrode and the glucose concentration have a good linear relationship, and the sensitivity of the electrochemical sensor is 668.08 μA·mM. -1 ·cm -2 The linear range is 3-6000μM, and the detection limit is 1μM.

[0055] Example 5

[0056] 1) Weigh 2g of sodium dodecylbenzenesulfonate and dissolve it in 50ml of deionized water under stirring. After complete dissolution, adjust the pH of the solution to 2 with nitric acid. Then, under stirring, add 2mmol of K3[Co(CN)6] to the solution. After complete dissolution, add 1mmol of nickel nitrate and stir for 10min. Finally, add 0.7mmol of ascorbic acid to the solution and sonicate for 10min. Transfer the treated solution to a hydrothermal reactor and hydrothermally treat it at 140ºC for 6h. Finally, separate, wash, and dry the precipitate to obtain the polyhedral Prussian blue analog Ni. 1.67 Co 1.33 [Co(CN)6]2.

[0057] 2) Weigh out 5 mg of Prussian blue analogue Ni 1.67 Co 1.33[Co(CN)6]2 was dispersed in 5 ml of anhydrous ethanol, and 5 μL of Nafion reagent was added. The mixture was then sonicated for 10 minutes to form a homogeneous suspension for later use. Separately, the glassy carbon electrode was polished with 1.0 μm and 0.3 μm Al2O3 to remove surface contaminants. Finally, it was ultrasonically cleaned with a 1:1 volume ratio of ethanol-water solution, a 1:1 volume ratio of nitric acid-water solution, and deionized water, respectively. After cleaning, the electrode was activated in a 1 mol / L sulfuric acid solution (using cyclic voltammetry to scan from -0.1 V to 0.1 V for 30 cycles). Finally, 10 μL of catalyst solution was dropped onto the polished glassy carbon electrode surface. After natural drying, the electrode was further dried in a 60°C oven for 10 minutes. After cooling, it was ready for experimental use.

[0058] 3) The Prussian blue analogue Ni prepared in step 2 1.67 Co 1.33 A portable glucose sensing device was determined using a three-electrode system with a [Co(CN)6]2 modified glassy carbon electrode as the working electrode, a Pt sheet electrode as the counter electrode, and a silver / silver chloride electrode as the reference electrode, in 0.1 M NaOH electrolyte solution. The portable glucose sensing device was connected via electrode wires to a micro-electrochemical workstation, which in turn was connected to a smartphone via a data cable. The smartphone provided power to the micro-electrochemical workstation via the data cable and used an app to set and control the testing methods. Electrochemical sensing performance was primarily tested using cyclic voltammetry and chronoamperometry.

[0059] Figure 7 The figure shows the chronoamperometry curve of the portable sensor assembled in this embodiment, measured with an applied voltage of 0.55V in the presence of a serum sample. The graph demonstrates that the portable sensor exhibits excellent response to glucose in the serum sample. Based on multiple measurements, the recovery rate of the sensor for serum sample testing ranges from 101.50% to 102.28%, indicating that the assembled portable sensor has good practical application performance.

Claims

1. An application of an electrode material for portable glucose sensing, characterized in that, The steps include: Ni 1.67 Co 1.33 The electrode material modified with [Co(CN)6]2 glassy carbon was used as the working electrode. Its portable glucose sensing performance was determined in an alkaline electrolyte solution using a three-electrode system. Specifically, the three-electrode system was connected to a micro electrochemical workstation via an electrode wire. The micro workstation was connected to a smartphone via a data cable. The smartphone provided power to the micro workstation via the data cable and set and controlled the test method via an APP. The electrochemical sensing performance was mainly tested by cyclic voltammetry and chronoamperometry. A method for preparing electrode materials that can be used in portable glucose sensors includes the following steps: 1) Weigh out the surfactant and dissolve it in deionized water under stirring. After complete dissolution, adjust the pH of the solution to 1-4 with acid. 2) Under stirring conditions, add cobalt cyanide compound to the solution in step 1), add nickel salt after complete dissolution, stir, add reducing agent, and sonicate. 3) The treated solution is transferred to a hydrothermal reactor for hydrothermal treatment. Finally, the precipitate is separated, washed, and dried to obtain Ni with a multifaceted structure. 1.67 Co 1.33 [Co(CN)6]2; 4) The Ni obtained in step 3) 1.67 Co 1.33 [Co(CN)6]2 was dispersed in anhydrous ethanol, and a film-forming substance was added. The mixture was then sonicated to form a uniform suspension for later use. 5) Polish the glassy carbon electrode, wash away surface dirt, ultrasonically clean it, activate it, and finally drop the suspension from step 4) onto the surface of the treated glassy carbon electrode, dry and cool it to obtain the electrode material.

2. The application as described in claim 1, characterized in that, In step 1), the surfactant is polyvinylpyrrolidone or sodium dodecylbenzenesulfonate, and the acid is one of hydrochloric acid, acetic acid, or nitric acid.

3. The application as described in claim 1, characterized in that, In step 2), the cobalt cyanide compound is one of K3[Co(CN)6] or Na3[Co(CN)6], the nickel salt is one of nickel acetate, nickel chloride, nickel nitrate, or nickel sulfate, and the reducing agent is ascorbic acid.

4. The application as described in claim 1, characterized in that, In step 3), the hydrothermal treatment temperature is 100-170℃, and the treatment time is 3-10h.

5. The application as described in claim 1, characterized in that, The film-forming substance in step 4) is Nafion reagent, and the mixture is sonicated for 10 minutes.

6. The application as described in claim 1, characterized in that, The polishing process in step 5) involves polishing with 1.0 μm and 0.3 μm Al2O3 respectively; the ultrasonic cleaning process involves ultrasonic cleaning with ethanol solution, nitric acid solution and deionized water respectively; the activation process involves activating the electrode in 0.5-1 mol / L sulfuric acid solution using cyclic voltammetry, with a scan range of 1.0 to -1.0 V; the drying process involves first air drying, and then further drying the electrode in an oven at 60℃ for 10 min.

7. The application as described in claim 1, characterized in that, The alkaline electrolyte solution is either NaOH or KOH solution. The reference electrode of the three-electrode system is either a silver-silver chloride electrode or a saturated calomel electrode. The counter electrode of the three-electrode system is either a Pt wire electrode or a Pt sheet electrode.

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