Preparation method of PB / Cu-TCPP / PANI nano-composite and configuration method of electrochemical sensor for H2O2 detection
By preparing PB/Cu-TCPP/PANI nanocomposites, the problems of enzyme sensor instability and poor conductivity of 2D MOFs were solved, and a highly sensitive and stable H2O2 electrochemical sensor was constructed, which is suitable for H2O2 detection in food, pharmaceuticals, industry and environment.
Patent Information
- Application Number
- CN202410936740.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-07-12
- Publication Date
- 2025-12-16
AI Technical Summary
Existing enzyme-based H2O2 electrochemical sensors suffer from environmental instability, high cost, and poor repeatability. Furthermore, the poor conductivity of 2D MOFs limits their application.
Using Cu-TCPP as the substrate material, a PB/Cu-TCPP/PANI nanocomposite was prepared. A two-dimensional Cu-TCPP nanofilm was prepared by a surfactant-assisted method. Under acidic conditions, the oxidizing property of FeCl3-K3[Fe(CN)6] was used to polymerize C6H7N monomers on the Cu-TCPP surface to generate PANI, thereby controlling the aggregation of PB nanoparticles and constructing an electrochemical sensor.
It achieves high sensitivity and good stability in H2O2 detection, with a detection limit lower than existing methods. It has good anti-interference ability and practical application potential, and is suitable for H2O2 detection in food, pharmaceuticals, industry and environment.
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Figure CN121136433A_ABST
Abstract
Description
Technical Field
[0001] This disclosure relates to the field of chemical material preparation methods, and in particular to a method for preparing PB / Cu-TCPP / PANI nanocomposites and a method for constructing an electrochemical sensor for H2O2 detection. Background Technology
[0002] H2O2 is an important antioxidant medium in food, pharmaceuticals, clinical applications, industry, and the environment. The detection of low-content H2O2 is of great significance in modern medicine, environmental control, and industry. While enzyme-based electrochemical sensors exhibit high sensitivity and selectivity for H2O2, they generally suffer from environmental instability, high cost, and poor repeatability. Compared to enzyme sensors, non-enzyme sensors utilize functional nanocomposites, which offer advantages such as high stability, ease of handling, and a wide response range. In recent years, 2D MOFs have attracted considerable research interest due to their ease of preparation and tunable size and morphology, demonstrating excellent application prospects in catalysis and sensors. Furthermore, 2D MOFs possess peroxidase-like activity and are widely used in sensors to detect H2O2 in various environments. However, 2D MOFs also have certain limitations, such as poor conductivity. PANI, as a conductive polymer, offers advantages such as simple preparation and excellent conductivity. Therefore, PANI can be used to address the poor conductivity issue of 2D MOFs. In 1998, Karyakin et al. proposed PB as an "artificial peroxidase," as PB exhibits excellent peroxidase activity.
[0003] This disclosure proposes a method for constructing an electrochemical sensor for detecting H2O2 based on Cu-TCPP as the substrate material, by preparing PB / Cu-TCPP / PANI nanocomposites. Summary of the Invention
[0004] The purpose of this disclosure is to overcome the shortcomings of the prior art and provide a method for preparing PB / Cu-TCPP / PANI nanocomposites and a method for constructing an electrochemical sensor for H2O2 detection.
[0005] According to a first aspect of the present disclosure, a method for preparing a PB / Cu-TCPP / PANI nanocomposite is provided, comprising the following steps:
[0006] Step S1: Prepare a two-dimensional Cu-TCPP nanofilm;
[0007] Step S2: Prepare PB / Cu-TCPP / PANI nanocomposite.
[0008] In one embodiment, step S1, the preparation of the two-dimensional Cu-TCPP nanofilm includes:
[0009] Two-dimensional Cu-TCPP nanofilms were prepared using a surfactant-assisted method.
[0010] In one embodiment, the preparation of a two-dimensional Cu-TCPP nanofilm using a surfactant-assisted method includes:
[0011] S11. Dissolve 4.5-5.0 mg Cu(NO3)2·3H2O and 18.0-22.0 mg PVP in a mixture of 10.00-14.00 mL DMF and anhydrous ethanol, and then sonicate to dissolve the mixture. The volume ratio of DMF to anhydrous ethanol is 3:1.
[0012] S12. Dissolve 10.0-14.0 mg of TCPP in the solution obtained in step S11 and stir for 8-12 min.
[0013] S13. Transfer the solution obtained in step S12 to a 45.00-55.00 mL reaction vessel and place it in an oven at 75-85℃ for 3.5-4.5 h to obtain Cu-TCPP solution;
[0014] S14. After cooling the Cu-TCPP solution obtained in step S13 to room temperature, centrifuge to collect the product, wash it several times with anhydrous ethanol, and then dry the product in an oven at 45-55℃ for 3.5-4.5h to obtain a two-dimensional Cu-TCPP nanofilm.
[0015] In one embodiment, step S2, the preparation of the PB / Cu-TCPP / PANI nanocomposite includes:
[0016] S21. Weigh 60.0-63.0 mg of FeCl3·6H2O and 68.0-72.0 mg of K3[Fe(CN)6], and add them to 4.50-5.50 mL of 10.00-14.00 mol·L⁻¹ solution. -1 Dissolved in HCl solution;
[0017] S22. Weigh 8.0-13.0 mg of Cu-TCPP nanofilm powder prepared in step S1, add it to 18.00-20.00 mL of anhydrous ethanol, ultrasonically disperse for 18-22 min, add 38.0-42.0 μL of C6H7N solution, and stir in an ice bath for 18-22 min.
[0018] S23. Add 390.0-410.0 μL of the solution prepared in step S21 to the solution prepared in step S22, stir in an ice bath for 10-14 h, collect the product by centrifugation, wash several times with ultrapure water, and dry the product in an oven at 45-55℃ for 3.5-4.5 h to obtain PB / Cu-TCPP / PANI nanocomposite.
[0019] According to a second aspect of the present disclosure, a method for constructing an electrochemical sensor for H2O2 detection is provided, the method comprising the following steps:
[0020] Step S101: Pre-treat the glassy carbon electrode;
[0021] Step S102: Add 0.5-1.5 mg of PB / Cu-TCPP / PANI powder to 0.50-1.50 mL of aqueous solution and disperse by ultrasonication; wherein the PB / Cu-TCPP / PANI powder is prepared by the above-described method for preparing PB / Cu-TCPP / PANI nanocomposite.
[0022] S103. The solution obtained in step S102 is drop-coated onto the surface of the glassy carbon electrode treated in step S101 and dried at room temperature to obtain an electrochemical sensor for detecting H2O2.
[0023] In one embodiment, step S101, the pretreatment of the glassy carbon electrode includes:
[0024] S1011. Polish the glassy carbon electrode to a mirror finish;
[0025] S1012. The polished glassy carbon electrode is then ultrasonically cleaned sequentially with dilute HNO3, anhydrous ethanol, and distilled water at a concentration of 0.2-0.7 mol / L, and then air-dried.
[0026] The implementation of this disclosure includes the following technical effects:
[0027] In the method for preparing PB / Cu-TCPP / PANI nanocomposite disclosed in this invention, C6H7N plays two main roles: firstly, as a precursor of PANI; and secondly, as a reducing agent for FeCl3-K3[Fe(CN)6]. After adding C6H7N dropwise to the Cu-TCPP dispersion, C6H7N adsorbs onto the Cu-TCPP surface, which is beneficial for the polymerization reaction of C6H7N monomers on the Cu-TCPP surface. Under acidic conditions, FeCl3 and K3[Fe(CN)6] have strong oxidizing properties. Therefore, after adding a hydrochloric acid mixture of FeCl3·6H2O and K3[Fe(CN)6] dropwise to the above solution, the C6H7N monomers undergo a polymerization reaction on the Cu-TCPP surface to generate PANI; simultaneously, the FeCl3-K3[Fe(CN)6] in the solution...3+ Gradually reduced to Fe 2+ The generated Fe 2+ Will be combined with [Fe(CN)6] 3- Further reaction occurs to produce PB. Due to Fe 2+ The formation of Fe 3+ The slow reduction process allows for some control over the PB reaction rate, which is beneficial for reducing the aggregation of PB nanoparticles. Attached Figure Description
[0028] Figure 1 A flowchart illustrating a method for preparing PB / Cu-TCPP / PANI nanocomposites provided in this disclosure.
[0029] Figure 2 This is a flowchart illustrating the preparation of two-dimensional Cu-TCPP nanofilms using a surfactant-assisted method in an embodiment of this disclosure.
[0030] Figure 3 This is a flowchart illustrating the preparation of PB / Cu-TCPP / PANI nanocomposites according to embodiments of this disclosure.
[0031] Figure 4 This is a flowchart illustrating a method for constructing an electrochemical sensor for H2O2 detection, as provided in an embodiment of this disclosure.
[0032] Figure 5 This is a schematic diagram illustrating the construction process and detection principle of an electrochemical sensor based on PB / Cu-TCPP / PANI.
[0033] Figure 6 The It curves of H2O2 obtained using PB / Cu-TCPP / PANI / GCE at different operating potentials are shown.
[0034] Figure 7 The It response curves of different concentrations of H2O2 obtained using PB / Cu-TCPP / PANI / GCE at an operating potential of -0.75V are shown.
[0035] Figure 8 for Figure 7 Zoom in at 1250-1350s.
[0036] Figure 9 The graph shows the linear relationship between the response current and the H2O2 concentration.
[0037] Figure 10 The It curves of H2O2 and interfering substances were obtained in PBS (pH=7.2) solution using PB / Cu-TCPP / PANI / GCE when the applied potential was -0.75V. Detailed Implementation
[0038] Exemplary embodiments will now be described in detail, examples of which are illustrated in the accompanying drawings. When the following description relates to the drawings, unless otherwise indicated, the same numerals in different drawings denote the same or similar elements. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with this disclosure. Rather, they are merely examples of apparatuses and methods consistent with some aspects of this disclosure as detailed in the appended claims.
[0039] Figure 1 A flowchart illustrating a method for preparing a PB / Cu-TCPP / PANI nanocomposite according to an embodiment of this disclosure. Figure 1 As shown, the method includes the following steps:
[0040] Step S1: Prepare a two-dimensional Cu-TCPP nanofilm;
[0041] In one embodiment, step S1, the preparation of the two-dimensional Cu-TCPP nanofilm includes:
[0042] Two-dimensional Cu-TCPP nanofilms were prepared using a surfactant-assisted method.
[0043] In one embodiment, such as Figure 2 As shown, the preparation of two-dimensional Cu-TCPP nanofilms using the surfactant-assisted method includes:
[0044] S11. Dissolve 4.5-5.0 mg Cu(NO3)2·3H2O and 18.0-22.0 mg PVP in a mixture of 10.00-14.00 mL DMF and anhydrous ethanol, and then sonicate to dissolve the mixture. The volume ratio of DMF to anhydrous ethanol is 3:1.
[0045] S12. Dissolve 10.0-14.0 mg of TCPP in the solution obtained in step S11 and stir for 8-12 min.
[0046] S13. Transfer the solution obtained in step S12 to a 45.00-55.00 mL reactor and place it in an oven at 75-85℃ for 3.5-4.5 h to obtain a Cu-TCPP solution.
[0047] S14. After cooling the Cu-TCPP solution obtained in step S13 to room temperature, centrifuge to collect the product, wash it several times with anhydrous ethanol, and then dry the product in an oven at 45-55℃ for 3.5-4.5h to obtain a two-dimensional Cu-TCPP nanofilm.
[0048] Step S2: Prepare PB / Cu-TCPP / PANI nanocomposite.
[0049] In one embodiment, such as Figure 3 As shown, in step S2, the preparation of the PB / Cu-TCPP / PANI nanocomposite includes:
[0050] S21. Weigh 60.0-63.0 mg of FeCl3·6H2O and 68.0-72.0 mg of K3[Fe(CN)6], and add them to 4.50-5.50 mL of 10.00-14.00 mol·L⁻¹ solution. -1 Dissolved in HCl solution;
[0051] S22. Weigh 8.0-13.0 mg of Cu-TCPP nanofilm powder prepared in step S1, add it to 18.00-20.00 mL of anhydrous ethanol, ultrasonically disperse for 18-22 min, add 38.0-42.0 μL of C6H7N solution, and stir in an ice bath for 18-22 min.
[0052] S23. Add 390.0-410.0 μL of the solution prepared in step S21 to the solution prepared in step S22, stir in an ice bath for 10-14 h, collect the product by centrifugation, wash several times with ultrapure water, and dry the product in an oven at 45-55℃ for 3.5-4.5 h to obtain PB / Cu-TCPP / PANI nanocomposite.
[0053] In the method for preparing PB / Cu-TCPP / PANI nanocomposite disclosed in this invention, C6H7N plays two main roles: firstly, as a precursor of PANI; and secondly, as a reducing agent for FeCl3-K3[Fe(CN)6]. After adding C6H7N dropwise to the Cu-TCPP dispersion, C6H7N adsorbs onto the Cu-TCPP surface, which is beneficial for the polymerization reaction of C6H7N monomers on the Cu-TCPP surface. Under acidic conditions, FeCl3 and K3[Fe(CN)6] have strong oxidizing properties. Therefore, after adding a hydrochloric acid mixture of FeCl3·6H2O and K3[Fe(CN)6] dropwise to the above solution, the C6H7N monomers undergo a polymerization reaction on the Cu-TCPP surface to generate PANI; simultaneously, the FeCl3-K3[Fe(CN)6] in the solution... 3+ Gradually reduced to Fe 2+ The generated Fe 2+ Will be combined with [Fe(CN)6] 3- Further reaction occurs to produce PB. Due to Fe 2+ The formation of Fe 3+ The slow reduction process allows for some control over the PB reaction rate, which is beneficial for reducing the aggregation of PB nanoparticles.
[0054] Figure 4This is a flowchart illustrating a method for constructing an electrochemical sensor for H2O2 detection, provided in an embodiment of this disclosure. Figure 4 As shown, the method includes the following steps:
[0055] Step S101: Pre-treat the glassy carbon electrode;
[0056] Step S102: Add 0.5-1.5 mg of PB / Cu-TCPP / PANI powder to 0.50-1.50 mL of aqueous solution and disperse by ultrasonication; wherein the PB / Cu-TCPP / PANI powder is prepared according to the above-described method for preparing PB / Cu-TCPP / PANI nanocomposite.
[0057] S103. The solution obtained in step S102 is drop-coated onto the surface of the glassy carbon electrode treated in step S101 and dried at room temperature to obtain an electrochemical sensor for detecting H2O2.
[0058] In one embodiment, the pretreatment of the glassy carbon electrode includes:
[0059] S1011. Polish the glassy carbon electrode to a mirror finish;
[0060] S1012. The polished glassy carbon electrode is then ultrasonically cleaned sequentially with dilute HNO3, anhydrous ethanol, and distilled water at a concentration of 0.2-0.7 mol / L, and then air-dried.
[0061] Example 1
[0062] This embodiment will provide a specific example to illustrate the preparation method of the PB / Cu-TCPP / PANI nanocomposite disclosed herein.
[0063] 1. Preparation of two-dimensional Cu-TCPP nanofilms
[0064] Preparation of two-dimensional Cu-TCPP nanofilms: Two-dimensional Cu-TCPP nanofilms were prepared using a surfactant-assisted method. 5.0 mg Cu(NO3)2·3H2O and 20.0 mg PVP were dissolved in a mixture of 12.00 mL DMF and anhydrous ethanol (DMF:ethanol volume ratio 3:1) and dissolved by sonication. Then, 12.0 mg TCPP was dissolved in the same solution and stirred for 10 min. The solution was then transferred to a 50.00 mL reactor and reacted at 80 °C for 4 h. Finally, the prepared Cu-TCPP was cooled to room temperature. The product was collected by centrifugation, washed three times with anhydrous ethanol, and dried in a 50 °C oven for 4 h to obtain the two-dimensional Cu-TCPP nanofilm.
[0065] 2. Preparation of PB / Cu-TCPP / PANI nanocomposites
[0066] Preparation of PB / Cu-TCPP / PANI: ① Weigh 61.8 mg FeCl3·6H2O and 70.4 mg K3[Fe(CN)6] into 5.00 mL of 12.00 mol·L⁻¹ -1 Dissolve in HCl solution. ② Weigh 10.5 mg Cu-TCPP, add 20.00 mL of anhydrous ethanol, sonicate for 20 min, add 40.0 μL of C6H7N solution, and stir in an ice bath for 20 min. Add 400.0 μL of solution ① to the solution in ② above, and stir in an ice bath for 12 h. After centrifugation, washing three times with ultrapure water, and drying at 50 °C, the PB / Cu-TCPP / PANI nanocomposite can be obtained.
[0067] Example 2
[0068] This embodiment will provide a specific description of the electrochemical sensor construction method for H2O2 detection disclosed herein.
[0069] GCE was polished, cleaned, and dried. 1.0 mg PB / Cu-TCPP / PANI powder was ultrasonically dispersed in 1.00 mL of ultrapure water, and then 7.0 μL of 1.0 mg / mL solution was added. -1 The PB / Cu-TCPP / PANI dispersion was drop-coated onto the treated GCE surface and air-dried at room temperature. The resulting modified electrode was labeled PB / Cu-TCPP / PANI / GCE.
[0070] Figure 5 This is a schematic diagram illustrating the construction process and detection principle of the electrochemical sensor based on PB / Cu-TCPP / PANI disclosed in this publication.
[0071] It should be noted that in this disclosure, PB is the abbreviation for Prussian blue, TCPP is meso-tetra(4-carboxyphenyl)porphyrin, PANI is polyaniline, PVP is polyvinylpyrrolidone, and DMF is N,N-dimethylformamide.
[0072] The specific implementation process of using the electrochemical sensor in this disclosure to detect H2O2 is as follows:
[0073] A three-electrode system was constructed using GCE (glassy carbon electrode, diameter: 3 mm) or PB / Cu-TCPP / PANI / GCE sensors as working electrodes, a saturated calomel electrode (Hg(l)|Hg2Cl2(s)|KCl) as the reference electrode, and a platinum wire as the counter electrode. The It method was employed, with a working potential of -0.85 V and a 0.10 mol·L⁻¹ N₂ saturated atmosphere. -1Electrochemical measurements were performed in PBS (pH 7.2) electrolyte with different concentrations of H2O2 added.
[0074] The It curve method was used, with PB / Cu-TCPP / PANI / GCE, to study the effect of different working potentials on the continuous addition of 1.00 mmol·L⁻¹. -1 The effect of H2O2 on the chronocurrent response.
[0075] Figure 6 The It curves of H2O2 obtained using PB / Cu-TCPP / PANI / GCE at different operating potentials are shown. Figure 6 It can be clearly observed that within the range of -0.70V to 0.90V, the current response increases with the gradual increase of the applied potential, while the baseline becomes increasingly unstable and the noise increases. Among these, the operating potential of -0.85V yields a larger chronocurrent response, lower noise, and a more stable baseline. Therefore, -0.85V was chosen as the operating potential in the experiment. A new method for detecting H2O2 based on a PB / Cu-TCPP / PANI electrochemical sensor was constructed.
[0076] Figure 7 The It response curves of different concentrations of H2O2 obtained using PB / Cu-TCPP / PANI / GCE at an operating potential of -0.75V are shown.
[0077] Figure 8 for Figure 7 Zoom in at 1250-1350s. (From...) Figure 8 As can be seen, the response time is less than 3 seconds.
[0078] Figure 9 The graph shows the linear relationship between the response current and the H2O2 concentration. Figure 9 As can be seen, the obtained chronoampere current exhibits a good linear relationship with the H2O2 concentration, with a linear range of 0.050-7.85 mmol·L. -1 The linear regression equation is: I p (μA)=17.62·C(mmol·L -1 The value was +18.17 (r = 0.9998), and the limit of detection was 0.02 mmol / L. -1 The sensitivity is 251.7 μA (mmol·L⁻¹). -1 ) -1 cm -2 .
[0079] The performance of the H2O2 electrochemical sensor constructed according to the electrochemical sensor construction method for detecting H2O2 in this disclosure and the H2O2 electrochemical sensing method reported in the literature are listed in Table 1.
[0080] Table 1. Comparison of analytical performance of the H2O2 electrochemical sensing methods constructed in the literature and in this disclosure.
[0081]
[0082]
[0083] As shown in Table 1, the PB / Cu-TCPP / PANI nanocomposite prepared by this disclosure using two-dimensional Cu-TCPP as the substrate material, and the H2O2 electrochemical sensing method based on PB / Cu-TCPP / PANI constructed by this disclosure, have a detection limit 1.5 times lower than that of Ag NW / GCE, which has the lowest detection limit in the table, compared with the previously reported related sensing methods for detecting H2O2.
[0084] The selectivity of the electrochemical sensor for detecting H2O2 prepared based on PB / Cu-TCPP / PANI in this disclosure will be discussed below using the It curve method.
[0085] Figure 10 It curves of H2O2 and interfering substances were obtained in PBS (pH = 7.2) solution using PB / Cu-TCPP / PANI / GCE at an applied potential of -0.75V, where the concentrations of both H2O2 and interfering substances were 0.50 mmol·L⁻¹. -1 .Depend on Figure 10 It can be seen that when 0.50 mmol·L⁻¹ is added... -1 A noticeable current response was observed when H₂O₂ was added. However, when 0.50 mmol·L⁻¹ was added... -1 When interfering substances (Glu, CH3CH2OH, NaNO2, AP, UA, and AA) are present, the current response is negligible, indicating that the sensing method has good anti-interference ability for H2O2 detection. UA is uric acid, AP is acetaminophen, and AA is ascorbic acid.
[0086] To evaluate the practical application potential of the PB / Cu-TCPP / PANI / GCE method disclosed herein, it was used to detect H2O2 in disinfectant water samples. Disinfectant sample 1 (H2O2 content: 2.7%-3.3%, wt%) was produced by AA; disinfectant sample 2 (H2O2 content: 2.5%-3.5%, wt%) was produced by BB. The disinfectant samples were used directly for electrochemical testing without any treatment. The results of determining H2O2 in disinfectant water samples using the electrochemical sensor construction method of this disclosure and the potassium permanganate titration method according to national standard GB / T 1616-2014 "Industrial Hydrogen Peroxide" are listed in Table 2.
[0087] Table 2. Results of the electrochemical sensing method and titration method for determining H2O2 in disinfectant water disclosed herein.
[0088]
[0089]
[0090] a) The average of the three determinations; b) Recovery rate (%) = [(c spiked sample - c sample) / c spiked] * 100%.
[0091] As shown in Table 2, the electrochemical sensor for H2O2 detection constructed in this disclosure achieved recoveries of 99.20%-99.80% and 100.4%-100.6% for disinfectant sample 1 and disinfectant sample 2, respectively, with RSDs less than 5.0%. The results indicate that this method is not significantly different from the standard potassium permanganate titration method and can be used for the detection of H2O2 in real samples.
[0092] Other embodiments of this disclosure will readily occur to those skilled in the art upon consideration of the specification and practice of the disclosure herein. This disclosure is intended to cover any variations, uses, or adaptations of this disclosure that follow the general principles of this disclosure and include common knowledge or customary techniques in the art not disclosed herein. The specification and examples are to be considered exemplary only, and the true scope and spirit of this disclosure are indicated by the following claims.
[0093] It should be understood that this disclosure is not limited to the precise structures described above and shown in the accompanying drawings, and various modifications and changes can be made without departing from its scope. The scope of this disclosure is limited only by the appended claims.
Claims
1. A method for preparing PB / Cu-TCPP / PANI nanocomposite, characterized in that, Includes the following steps: Step S1: Prepare a two-dimensional Cu-TCPP nanofilm; Step S2: Prepare PB / Cu-TCPP / PANI nanocomposite.
2. The method for preparing PB / Cu-TCPP / PANI nanocomposite according to claim 1, characterized in that, In step S1, the preparation of the two-dimensional Cu-TCPP nanofilm includes: Two-dimensional Cu-TCPP nanofilms were prepared using a surfactant-assisted method.
3. The method for preparing PB / Cu-TCPP / PANI nanocomposite according to claim 2, characterized in that, The preparation of two-dimensional Cu-TCPP nanofilms using a surfactant-assisted method includes: S11. Dissolve 4.5-5.0 mg Cu(NO3)2·3H2O and 18.0-22.0 mg PVP in a mixture of 10.00-14.00 mL DMF and anhydrous ethanol, and then sonicate to dissolve the mixture. The volume ratio of DMF to anhydrous ethanol is 3:
1. S12. Dissolve 10.0-14.0 mg of TCPP in the solution obtained in step S11 and stir for 8-12 min. S13. Transfer the solution obtained in step S12 to a 45.00-55.00 mL reaction vessel and place it in an oven at 75-85℃ for 3.5-4.5 h to obtain Cu-TCPP solution; S14. After cooling the Cu-TCPP solution obtained in step S13 to room temperature, centrifuge to collect the product, wash it several times with anhydrous ethanol, and then dry the product in an oven at 45-55℃ for 3.5-4.5h to obtain a two-dimensional Cu-TCPP nanofilm.
4. The method for preparing PB / Cu-TCPP / PANI nanocomposite according to claim 1, characterized in that, In step S2, the preparation of the PB / Cu-TCPP / PANI nanocomposite includes: S21. Weigh 60.0-63.0 mg of FeCl3·6H2O and 68.0-72.0 mg of K3[Fe(CN)6], and add them to 4.50-5.50 mL of 10.00-14.00 mol·L⁻¹ -1 Dissolved in HCl solution; S22. Weigh 8.0-13.0 mg of Cu-TCPP nanofilm powder prepared in step S1, add it to 18.00-20.00 mL of anhydrous ethanol, ultrasonically disperse for 18-22 min, add 38.0-42.0 μL of C6H7N solution, and stir in an ice bath for 18-22 min. S23. Add 390.0-410.0 μL of the solution prepared in step S21 to the solution prepared in step S22, stir in an ice bath for 10-14 h, collect the product by centrifugation, wash several times with ultrapure water, and dry the product in an oven at 45-55℃ for 3.5-4.5 h to obtain PB / Cu-TCPP / PANI nanocomposite.
5. A method for constructing an electrochemical sensor for H2O2 detection, characterized in that, The method includes the following steps: Step S101: Pre-treat the glassy carbon electrode; Step S102: Add 0.5-1.5 mg of PB / Cu-TCPP / PANI powder to 0.50-1.50 mL of aqueous solution and disperse by ultrasonication; wherein the PB / Cu-TCPP / PANI powder is prepared by the method for preparing PB / Cu-TCPP / PANI nanocomposite according to any one of claims 1 to 5; S103. The solution obtained in step S102 is drop-coated onto the surface of the glassy carbon electrode treated in step S101 and dried at room temperature to obtain an electrochemical sensor for detecting H2O2.
6. The method for constructing an electrochemical sensor for H2O2 detection according to claim 5, characterized in that, In step S101, the pretreatment of the glassy carbon electrode includes: S1011. Polish the glassy carbon electrode to a mirror finish; S1012. The polished glassy carbon electrode is then ultrasonically cleaned sequentially with dilute HNO3, anhydrous ethanol, and distilled water at a concentration of 0.2-0.7 mol / L, and then air-dried.