Method for preparing homogeneous mesoporous copper oxide material and applications thereof

Abstract

The application discloses a preparation method of mesoporous copper oxide and application thereof. The preparation method comprises the following steps: S1, preparing a hydroxyl copper nitrate microplate by taking calcium carbonate paper as a substrate and copper nitrate as a solvent; S2, synthesizing an ordered copper hydroxide nanowire assembly through an alkali solution reaction; and S3, performing annealing treatment in a muffle furnace to obtain the mesoporous copper oxide microplate. Under the conditions of no hard template, no soft template and no strong acid treatment, the application provides a method for synthesizing the mesoporous copper oxide microplate material with uniform pore structure on the carbonic paper by adopting copper nitrate hydrolysis, alkali etching and annealing, and the synthesis method of the mesoporous structure has the advantages of simple operation, good controllability and low cost. The application also relates to application of the mesoporous copper oxide as an electrocatalyst material in the field of glucose electrochemical sensing.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of nanomaterials and electrochemistry, and particularly relates to a preparation method of mesoporous transition metal oxide and application thereof. BACKGROUND

[0002] Excessive glucose content in the human body can cause diabetes and its complications, and vice versa can cause symptoms such as brain hypoxia and myocardial ischemia, so that the detection of glucose content is crucial for monitoring the health level of the human body. So far, a series of methods for detecting glucose have been developed, including fluorescence method, colorimetric method, chromatography, surface plasmon resonance and electrochemical technology. Among them, the electrochemical method has attracted widespread attention due to its simple operation and fast response. Compared with enzyme-based sensors, non-enzyme electrochemical glucose sensors no longer use enzymes sensitive to environmental conditions, but use noble metals, transition metal compounds, carbon materials and conductive polymers as sensing materials. This greatly improves the stability of the sensor and reduces the overall cost.

[0003] A large number of studies have shown that the sensing performance and mass transfer capacity can be improved by constructing favorable adsorption sites in electrocatalysts. Among them, porosity engineering has been proven to be particularly effective. Micropores have a large specific surface area, but the small pore size hinders the passage of some large molecules, which limits the application of micropores. According to the Fick-diffusion empirical formula, macropores significantly improve the mass transfer efficiency, but it is difficult to maintain structural stability during the synthesis of macroporous materials, which may affect their overall performance. In contrast, mesoporous materials have been widely used due to their superior molecular diffusion, adjustable pore size and enhanced structural stability. Common mesoporous structural materials need to be prepared by hard template method or soft template method. Unfortunately, their synthesis involves complex steps of creating templates, which often need to be removed using acidic, alkaline solutions and high temperatures later, which not only increases the cost, but also may damage the pore structure and surface chemical properties of the material. Therefore, there is an urgent need to develop an economical and simple method to prepare mesoporous metal oxide materials. SUMMARY

[0004] In view of the deficiencies of the prior art, the present application provides a method for preparing mesoporous copper oxide material, aiming to provide an effective method with simple process, low cost and no template agent. The prepared copper oxide has interpenetrating mesoporous channels, connects to form a stable structure of microporous plates, and has excellent electrochemical glucose sensing performance.

[0005] To achieve the above-mentioned purpose, the technical solutions of the present application are as follows:

[0006] In a first aspect, the present application provides a method for preparing mesoporous copper oxide material, comprising the following steps:

[0007] S1: soaking calcium carbonate paper in copper nitrate solution to prepare hydroxyl copper nitrate micropanel / calcium carbonate paper;

[0008] S2: soaking the hydroxyl copper nitrate micropanel-calcium carbonate paper in an alkaline solution to obtain copper hydroxide nanowire assembly / calcium carbonate paper; before soaking the hydroxyl copper nitrate micropanel-calcium carbonate paper in the alkaline solution, removing residual copper nitrate solution on the surface of the hydroxyl copper nitrate micropanel-calcium carbonate paper;

[0009] S3: annealing treatment to obtain mesoporous copper oxide micropanel material. As a preferred solution, wherein,

[0010] before the annealing treatment, removing residual potassium hydroxide solution on the surface of the ordered copper hydroxide nanowire assembly-calcium carbonate paper; treating the copper hydroxide nanowire assembly-calcium carbonate paper by ultrasonic method to obtain copper hydroxide nanowire assembly;

[0011] Further, in the optimized technical solution:

[0012] In step S1, the concentration of the copper nitrate solution is 0.09-0.26 g / mL, and in some specific embodiments, the solution concentration is 0.09, 0.13, 0.17, 0.21, 0.26 g / mL, or any value between them; the soaking time of the calcium carbonate paper in the copper nitrate solution is 4-20 hours, and in some specific embodiments, the soaking time is 4, 8, 12, 16, 20 hours, or any value between them.

[0013] In step S2, the alkaline solution is selected from potassium hydroxide or sodium hydroxide, and the concentration of the solution is 0.03-0.08 g / mL, and in some specific embodiments, the solution concentration is 0.03, 0.05, 0.07, 0.08 g / mL, or any value between them; the soaking time of the hydroxyl copper nitrate micropanel-calcium carbonate paper in the potassium hydroxide solution is 1-24 hours, and in some specific embodiments, the soaking time is 1, 4, 8, 12, 18, 24 hours, or any value between them.

[0014] In step S3, the ordered copper hydroxide nanowire assembly is separated from the calcium carbonate paper by ultrasonic method, the ultrasonic time is 30 minutes-3 hours, then collected by centrifugation method, the speed is 3000-6000 r / min, the centrifugation time is 3-15 minutes, the drying temperature is 40-60℃, and the drying time is 12-24 hours.

[0015] In the step S3, the annealing temperature is 250-500℃, and in some specific embodiments, the annealing temperature is 250, 300, 350, 400, 450, 500℃; the annealing time is 1-4 hours, and in some specific embodiments, the annealing time is 1, 2, 3, 4 hours or any value between them.

[0016] The core of the present application is to propose a novel synthesis path of mesoporous copper oxide material, which does not depend on traditional hard template, soft template or strong acid treatment method, but skillfully utilizes the uniform shrinkage of ordered copper hydroxide nanowires in the annealing process, so as to form a uniform distribution and uniform size mesoporous structure in the assembly (micron plate) composed of nanowires, and the ordered copper hydroxide nanowires can be prepared by using calcium carbonate paper as a substrate and then through a mild chemical synthesis method.

[0017] The present application mainly relates to a preparation method of mesoporous copper oxide material and its application in the field of electrochemical sensing. Specifically, the method is realized through the following steps:

[0018] S1, preparation of hydroxyl copper nitrate micron plate: taking calcium carbonate paper as a substrate, soaking in copper nitrate solution to form hydroxyl copper nitrate micron plate. This process utilizes the chemical reaction between hydrogen ions generated by copper nitrate hydrolysis and calcium carbonate, and promotes the hydrolysis of copper nitrate to synthesize hydroxyl copper nitrate micron plate, which lays a foundation for subsequent reactions.

[0019] S2, synthesis of ordered copper hydroxide nanowire assembly: soaking the hydroxyl copper nitrate micron plate in an alkaline solution to promote the ordered assembly of copper hydroxide nanowires. The key of this step is the concentration of alkaline solution and the soaking time, which controls the order of nanowire assembly and realizes the structure transformation.

[0020] S3, annealing treatment: annealing the ordered copper hydroxide nanowire assembly to obtain mesoporous copper oxide material. The annealing process is the key to realize the uniform shrinkage of nanowires and the formation of uniformly distributed and uniform size mesoporous structure, which is beneficial to exhibit good electrochemical performance.

[0021] In a second aspect, the present application provides a mesoporous copper oxide micron plate material obtained by the preparation method as described above. In a preferred embodiment, the obtained mesoporous copper oxide micron plate material has a thickness of 300-800 nm and an internal pore size of 10-20 nm. The structure is controllable: the mesoporous size is uniform, which is beneficial to improve the electrochemical reaction rate.

[0022] In a third aspect, the present application provides a use of the mesoporous copper oxide material as described above in electrochemical sensing, for constructing an enzyme-free electrochemical sensor for detecting glucose content.

[0023] The mesoporous copper oxide material obtained by the preparation method of the present application has promising application value in the field of electrochemical glucose sensing, mainly in its performance as an electrocatalyst material. The mesoporous copper oxide can be used to prepare a high-performance enzyme-free glucose sensor. The preparation method of such a sensor includes using the mesoporous copper oxide microplate as an electrode material, and analyzing the morphology and structure of the sample by scanning electron microscopy, X-ray diffraction, and nitrogen adsorption-desorption instrument, etc. In practical applications, the mesoporous copper oxide material exhibits good catalytic activity and sensitivity. Studies have shown that the mesoporous copper oxide microplate exhibits a linear response to glucose detection in the concentration range of 0.003 to 1.8501 mM, and exhibits a reasonable detection limit of 0.054 μM and a high sensitivity of 1499.2 μA mM^-1cm^-2 in the alkaline pH range. The mesoporous copper oxide material of the present application has potential application value in the field of electrochemical glucose sensing, and its performance is mainly improved by optimizing the pore structure and other factors, and these performance improvements are achieved by the preparation method of the present application.

[0024] In summary, the present application not only opens up a new way to construct mesoporous structures in copper oxide materials, but also demonstrates its great potential in the field of electrochemical sensing, especially in glucose detection, and is expected to become an important part of future diabetes management tools.

[0025] The advantages and beneficial effects of the present application are as follows:

[0026] 1. Simple process and low cost: The preparation method used in the present application does not require the use of complex hard or soft templates, avoiding the high temperature and acid-base treatment steps in traditional methods, reducing production cost and operation difficulty.

[0027] 2. Uniform pore structure: The prepared mesoporous copper oxide material has good porosity and uniform pore size (10-20 nm), which makes it have superior molecular diffusion and mass transfer ability in electrochemical reaction, which is beneficial to the rapid adsorption of glucose on the active sites on the material surface, and improves the catalytic performance.

[0028] 3. Excellent electrochemical performance: The application of mesoporous copper oxide materials in glucose electrochemical sensors shows good catalytic activity and sensitivity, which can effectively detect glucose in a wide concentration range (0.003 to 1.8501 mM) with a sensitivity of 1499.2 μA mM^-1cm^-2.

[0029] 4. Environmental friendliness: The preparation process of the present application avoids the use of harmful chemicals to the environment, conforms to the concept of sustainable development, and has good environmental friendliness.

[0030] 5. Wide application prospect: In addition to the application in glucose detection, mesoporous copper oxide materials can also be extended to other electrochemical sensing fields, which has great market potential and application value.

[0031] In summary, the present application not only has innovation in technology, but also shows significant advantages in economy and environmental protection, providing a new idea and method for the development of electrochemical sensors. BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1 SEM image of the mesoporous copper oxide microplate material of Example 1 of the present application;

[0033] Figure 2 TEM image of the mesoporous copper oxide microplate material of Example 1 of the present application;

[0034] Figure 3 BET image of the mesoporous copper oxide microplate material of Example 1 of the present application;

[0035] Figure 4 XRD image of the mesoporous copper oxide microplate material of Example 1 of the present application;

[0036] Figure 5 Cyclic voltammogram of the mesoporous copper oxide microplate material obtained in Example 1 after modification on the surface of indium tin oxide glass to construct a sensing electrode, in response to the oxidation reaction of different concentrations of glucose;

[0037] Figure 6 Cyclic voltammogram of the mesoporous copper oxide microplate material obtained in Example 1 after modification on the surface of indium tin oxide glass to construct a sensing electrode, in response to the oxidation reaction of different concentrations of glucose;

[0038] Figure 7 Current response curve of the mesoporous copper oxide microplate material obtained in Example 1 after modification on the surface of indium tin oxide glass to construct a sensing electrode, in response to glucose at different detection voltages;

[0039] Figure 8The current response curve of dropping glucose and the linear relationship curve of current density-glucose concentration are compared after the mesoporous copper oxide micro-plate obtained in Example 1 is modified on the surface of an indium tin oxide glass to construct a sensing electrode;

[0040] Figure 9 The influence of various test agents on the glucose oxidation current signal is observed after the mesoporous copper oxide micro-plate obtained in Example 1 is modified on the surface of an indium tin oxide glass to construct a sensing electrode.

[0041] Figure 10 The SEM image of the porous copper oxide material of the present application;

[0042] Figure 11 The TEM image of the porous copper oxide material of the present application;

[0043] Figure 12 The BET image of the porous copper oxide material of the present application;

[0044] Figure 13 The XRD image of the porous copper oxide material of the present application;

[0045] Figure 14 The current response curve of dropping glucose and the linear relationship curve of current density-glucose concentration are compared after the porous copper oxide obtained in the comparative example is modified on the surface of an indium tin oxide glass to construct a sensing electrode. DETAILED DESCRIPTION

[0046] In order to make the purpose, technical scheme and points of the present application more clear and understandable, the present application is further described in detail below in combination with examples. The specific examples described herein are only used to explain the present application and do not constitute any limitation on the present application.

[0047] Example 1

[0048] 1) 2.416 g of copper nitrate solid is weighed and dissolved in 20 mL of ultrapure water to prepare a copper nitrate solution. A 2.5 cm x 2.5 cm calcium carbonate paper is soaked for 6 hours, and then washed with deionized water to remove residual liquid to obtain a hydroxyl copper nitrate micro-plate / calcium carbonate paper;

[0049] 2) 1.12 g of potassium hydroxide solid is weighed and dissolved in 20 mL of ultrapure water to prepare a copper nitrate solution. The hydroxyl copper nitrate micro-plate / calcium carbonate paper prepared in step 1) is soaked therein for 4 hours, and then washed with deionized water to remove residual liquid to obtain an ordered copper hydroxide nanowire assembly / calcium carbonate paper;

[0050] 3) The ordered copper hydroxide nanowire assembly / calcium carbonate paper obtained in step 2) is placed in deionized water and ultrasonicated for 30 minutes, and then centrifuged at 5000 r / min for 5 minutes, and the supernatant is removed and dried in an oven at 50°C for 12 hours to obtain the ordered copper hydroxide nanowire assembly;

[0051] 4) The ordered copper hydroxide nanowire assembly obtained in step 3) is placed in a porcelain boat, and annealed at 350°C for 2h in a muffle furnace, and after natural cooling, mesoporous copper oxide micropanel powder is obtained. The scanning electron microscope (SEM) image is shown in Figure 1 , which shows that the prepared sample has mesoporous pores, and the micropanel does not collapse and the structure is stable; the transmission electron microscope (TEM) image is shown in Figure 2 , which further shows that the prepared sample has mesoporous pores; the specific surface area detection (BET) image is shown in Figure 3 , which shows that the average size of the prepared mesoporous pore sample is 13.48 nm, the BET specific surface area is 30.13 m^2g^-1, and the pore volume is 0.14 m^3g^-1; the X-ray diffraction (XRD) image is shown in Figure 4 , which shows that the prepared sample is a pure phase copper oxide crystal.

[0052] Example 2

[0053] 1) 2.416g of copper nitrate solid is weighed and dissolved in 20mL of ultrapure water to prepare a copper nitrate solution. A 2.5cm x 2.5cm calcium carbonate paper is soaked for 4 hours, and then washed with deionized water to remove residual liquid to obtain a hydroxyl copper nitrate micropanel / calcium carbonate paper;

[0054] 2) 1.12g of potassium hydroxide solid is weighed and dissolved in 20mL of ultrapure water to prepare a copper nitrate solution. The hydroxyl copper nitrate micropanel / calcium carbonate paper prepared in step 1) is soaked therein for 2 hours, and then washed with deionized water to remove residual liquid to obtain an ordered copper hydroxide nanowire assembly / calcium carbonate paper;

[0055] 3) The ordered copper hydroxide nanowire assembly / calcium carbonate paper obtained in step 2) is placed in deionized water and ultrasonicated for 60 minutes, and then centrifuged at 6000 r / min for 3 minutes, and the supernatant is removed and dried in an oven at 50°C for 12 hours to obtain the ordered copper hydroxide nanowire assembly;

[0056] 4) The ordered copper hydroxide nanowire assembly obtained in step 3) is placed in a porcelain boat, and annealed at 350°C for 1h in a muffle furnace, and after natural cooling, mesoporous copper oxide micropanel powder is obtained.

[0057] Example 3

[0058] 1) Take copper nitrate solid 3.866 g, dissolve with 20 mL ultrapure water to configure copper nitrate solution, immerse 2.5 cm x 2.5 cm calcium carbonate paper for 6 hours, after taking out, rinse the surface with deionized water to remove residual liquid, obtain hydroxyl copper nitrate micron plate / calcium carbonate paper;

[0059] 2) Take potassium hydroxide solid 1.12 g, dissolve with 20 mL ultrapure water to configure copper nitrate solution, immerse the hydroxyl copper nitrate micron plate / calcium carbonate paper prepared in step 1) therein, react for 4 hours, after taking out, rinse the surface with deionized water to remove residual liquid, obtain ordered copper hydroxide nanowire assembly / calcium carbonate paper;

[0060] 3) Place the ordered copper hydroxide nanowire assembly / calcium carbonate paper obtained in step 2) in deionized water, ultrasonic for 30 minutes, then centrifuge for 5 minutes at a speed of 5000 r / min, remove the supernatant, set 50℃ in the oven and dry for 18 hours to obtain ordered copper hydroxide nanowire assembly;

[0061] 4) Place the ordered copper hydroxide nanowire assembly obtained in step 3) in a porcelain boat, set the muffle furnace at 400℃, anneal for 2h, and after natural cooling, mesoporous copper oxide micron plate powder can be obtained.

[0062] Example 4

[0063] 1) Take copper nitrate solid 3.866 g, dissolve with 20 mL ultrapure water to configure copper nitrate solution, immerse 2.5 cm x 2.5 cm calcium carbonate paper for 6 hours, after taking out, rinse the surface with deionized water to remove residual liquid, obtain hydroxyl copper nitrate micron plate / calcium carbonate paper;

[0064] 2) Take potassium hydroxide solid 1.12 g, dissolve with 20 mL ultrapure water to configure copper nitrate solution, immerse the hydroxyl copper nitrate micron plate / calcium carbonate paper prepared in step 1) therein, react for 4 hours, after taking out, rinse the surface with deionized water to remove residual liquid, obtain ordered copper hydroxide nanowire assembly / calcium carbonate paper;

[0065] 3) Place the ordered copper hydroxide nanowire assembly / calcium carbonate paper obtained in step 2) in deionized water, ultrasonic for 30 minutes, then centrifuge for 5 minutes at a speed of 5000 r / min, remove the supernatant, set 50℃ in the oven and dry for 18 hours to obtain ordered copper hydroxide nanowire assembly;

[0066] 4) Place the ordered copper hydroxide nanowire assembly obtained in step 3) in a porcelain boat, set the muffle furnace at 400℃, anneal for 2h, and after natural cooling, mesoporous copper oxide micron plate powder can be obtained.

[0067] Test example

[0068] The mesoporous copper oxide material obtained in Example 1 was used as an electrocatalyst for the electrochemical oxidation of glucose. 3 mg of the copper oxide material was weighed on an analytical balance, and 500 μL of ultrapure water, 400 μL of an ethanol solution, and 100 μL of a 0.5 wt% nafion solution were added. The mixture was ultrasonicated for 1 h in an ultrasonic machine to uniformly disperse the electrocatalyst in the solution without agglomeration. Before the sensing electrode was prepared using a drop casting method, the indium tin oxide conductive glass was ultrasonicated in acetone, ethanol, and deionized water for 5 min each, and then dried with nitrogen. 10 μL of the sample solution was dropped onto the treated indium tin oxide glass conductive surface to obtain an electrode film with a uniform thickness. During the entire electrochemical test, the mesoporous copper oxide / indium tin oxide glass was used as the working electrode, silver / silver chloride was used as the reference electrode, platinum wire was used as the auxiliary electrode, and 0.1 M sodium hydroxide solution was used as the electrolyte.

[0069] The cyclic voltammetry (CV) test selected a voltage test range of 0-0.8 V, and was performed in a sodium hydroxide solution containing 0-2 M glucose at a scan rate of 50 mV / s. The data are summarized in Table 1, Figure 5 The results show that the mesoporous copper oxide can be used for the electrocatalytic oxidation of glucose, and the glucose oxidation peak current increases with increasing glucose concentration, indicating good catalytic activity.

[0070] The cyclic voltammetry (CV) test selected a voltage test range of 0-0.8 V, and was performed in a 0.1 M potassium chloride solution containing 5 mM potassium ferricyanide / potassium ferrocyanide at a scan rate of 10-140 mV / s. The results are summarized in Table 2, Figure 6 By fitting the linear relationship between the scan rate and the redox peak current, the electrochemical area of the sensing electrode was calculated to be 0.4313 cm 2 , which is much higher than the drop-cast area of 0.1256 cm 2 on the surface of the indium tin oxide glass;

[0071] The time-current test technique was used to perform the electrocatalytic oxidation of glucose at a voltage of 0.40 V-0.60 V vs. Ag|AgCl. The data are summarized in Table 3, Figure 7 The results show that the glucose oxidation current response increases with increasing detection voltage, but there is little difference in the current response when the detection voltage reaches 0.5 V and 0.55 V. Therefore, 0.55 V was selected for performance testing.

[0072] The time-current test technique was used to perform the electrocatalytic oxidation of glucose at 0.55 V vs. Ag|AgCl by adding different concentrations of glucose solution. The time-current step curve and the concentration-current density linear relationship straight line were obtained. Figure 8), the results show that the sensitivity of the glucose electrochemical sensor constructed by the mesoporous copper oxide reaches 1499.2 muA mM^-1cm^-2, and the linear range is 0.003 to 1.8501 mM.

[0073] Using time-current test technology, 0.5 mM glucose, 0.05 mM potassium chloride, 0.05 mM lactic acid, 0.05 mM uric acid, 0.05 mM ascorbic acid, 0.05 mM fructose, 0.05 mM acetaminophen, 0.05 mM cysteine, 0.05 mM dopamine, 0.5 mM glucose, Figure 9 The detection results show that the sensor has excellent selectivity.

[0074] The technical scheme of the present application is not limited to the above specific embodiments, and any technical modification made according to the technical scheme of the present application falls within the protection scope of the present application.

[0075] Comparative example

[0076] 1) 2.416 g of copper nitrate solid was weighed and dissolved in 20 mL of ultrapure water to prepare a copper nitrate solution. A 2.5 cm x 2.5 cm calcium carbonate paper was soaked for 6 hours, and then washed with deionized water to remove residual liquid, to obtain a hydroxyl copper nitrate micron plate / calcium carbonate paper;

[0077] 2) The ordered copper hydroxide nanowire assembly / calcium carbonate paper obtained in step 1) was placed in deionized water and ultrasonicated for 60 minutes, and then centrifuged at 5000 r / min for 10 minutes. The supernatant was removed and dried in an oven at 50 DEG C for 15 hours to obtain a hydroxyl copper nitrate micron plate powder;

[0078] 3) The hydroxyl copper nitrate micron plate powder obtained in step 2) was placed in a porcelain boat, and annealed at 350 DEG C for 2 hours in a muffle furnace. After natural cooling, a porous copper oxide powder was obtained. The scanning electron microscope (SEM) picture is shown in Figure 10 , which shows that the surface of the prepared sample does not form a uniform mesoporous structure; the transmission electron microscope (TEM) picture is shown in Figure 11 , which further shows that the surface of the prepared sample has only a small amount of pore structure; the specific surface area detection (BET) picture is shown in Figure 12 , which shows that the pore size of the prepared copper oxide sample is mainly concentrated in 1.8 nm, 3.83 nm and 11.7 nm, and there are mesopores and micropores. The BET specific surface area is 2.98 m^2g^-1, and the pore volume is 0.01 m^3g^-1; the X-ray diffraction (XRD) image is shown in Figure 13 , which shows that the prepared sample is a pure phase copper oxide crystal;

[0079] 4) The porous copper oxide material obtained in the above Example 1 was used as an electrocatalyst for the electrochemical oxidation of glucose. 3 mg of the copper oxide material was weighed on an analytical balance, and 500 μL of ultrapure water, 400 μL of an ethanol solution, and 100 μL of a 0.5 wt% nafion solution were added. The mixture was placed in an ultrasonic machine for 1 h to uniformly disperse the electrocatalyst in the solution without agglomeration. 10 μL of the sample was dropped onto a treated indium tin oxide glass conductive surface to obtain a uniform thickness of the electrode film as a comparative electrode. A time-current test technique was used to add a glucose solution of different concentrations at 0.55 V vs. Ag|AgCl to obtain a time-current step curve and a linear relationship between the concentration and the current density (Figure 19) Figure 14 ), and the results showed that the sensitivity of the comparative electrode was only 281.7 μA mM"1cm"2, and the linear range was 0.0030-0.5108 mM, fully demonstrating that the mesoporous structure with uniform pore distribution and pore size is crucial for improving the sensing performance in the process of glucose electrochemical sensing.

Claims

1. Use of a mesoporous copper oxide material in electrochemical sensing, characterized in that: The application relates to a method for preparing a mesoporous copper oxide material, and a method for constructing an enzyme-free electrochemical sensor for detecting the content of glucose. S1: soaking calcium carbonate paper in copper nitrate solution to prepare a hydroxyl copper nitrate micropanel-calcium carbonate paper; S2: soaking the hydroxyl copper nitrate micropanel-calcium carbonate paper in an alkaline solution to obtain an ordered copper hydroxide nanowire assembly / calcium carbonate paper; S3: performing annealing treatment to obtain a mesoporous copper oxide micropanel material; In step S2, before soaking the hydroxyl copper nitrate micropanel / calcium carbonate paper in the alkaline solution, the residual copper nitrate solution on the surface of the hydroxyl copper nitrate micropanel / calcium carbonate paper is removed; In step S3, before the annealing treatment, the residual potassium hydroxide solution on the surface of the ordered copper hydroxide nanowire assembly-calcium carbonate paper is removed; The ordered copper hydroxide nanowire assembly / calcium carbonate paper is treated by an ultrasonic method to obtain a copper hydroxide nanowire assembly; In step S1, the concentration of the copper nitrate solution is 0.09-0.26 g / mL; and the soaking time of the calcium carbonate paper in the copper nitrate solution is 4-20 hours; In step S2, the alkaline solution is a potassium hydroxide or sodium hydroxide solution, and the concentration of the solution is 0.03-0.08 g / mL; The soaking time of the hydroxyl copper nitrate micropanel / calcium carbonate paper in the alkaline solution is 1-24 hours; In step S3, the annealing temperature is 250-500 DEG C, and the annealing time is 1-4 hours.

2. Use of the mesoporous copper oxide material according to claim 1 in electrochemical sensing, characterized in that: In step S3, when the ordered copper hydroxide nanowire assembly / calcium carbonate paper is treated by the ultrasonic method, the solvent is deionized water, the ultrasonic time is 30 minutes-3 hours, then the centrifugal collection method is adopted, the rotating speed is 3000-6000 r / min, the centrifugal time is 3-15 minutes, and the drying is performed at 40-60 DEG C for 12-24 hours.

3. Use of the mesoporous copper oxide material according to claim 2 in electrochemical sensing, characterized in that: The thickness of the mesoporous copper oxide micropanel material is 300-800 nm, and the pore size is concentrated in 10-20 nm.

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