A method for enhancing electrochemiluminescence reaction by in-situ induction of micro-nano bubbles on the surface of boron-doped diamond
By inducing micro-nano bubbles in situ on the surface of boron-doped diamond electrodes and constructing a three-phase interface microenvironment, the problems of low detection efficiency and insufficient sensitivity of existing ECL technology are solved, and efficient electrochemiluminescence reaction enhancement is achieved.
Patent Information
- Application Number
- CN202210751122.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2022-06-28
- Publication Date
- 2025-02-14
- Estimated Expiration
- 2042-06-28
AI Technical Summary
The existing electrochemiluminescence (ECL) technology has low detection efficiency and insufficient sensitivity in practical applications, and it is difficult to enhance the luminescence intensity in situ on the surface of boron-doped diamond electrodes.
Micro-nano bubbles are induced in situ on the surface of boron-doped diamond electrodes by electrochemical methods, constructing a three-phase interface microenvironment, and promoting electrochemiluminescence reactions.
The efficiency of in-situ enhanced electrochemiluminescence reaction is achieved, the operation process is simplified, the surface state of the electrode can be flexibly controlled, the detection sensitivity is improved, and the amount of co-reactants is reduced.
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Abstract
Description
Technical Field
[0001] The invention relates to a method for enhancing electrochemiluminescence reaction by in-situ inducing micro-nano bubbles on the surface of boron-doped diamond, and belongs to the technical field of electrochemiluminescence. Background Art
[0002] Electrochemiluminescence (ECL) is an important biochemical analysis technique. 2+ ECL technology using Ru(bpy)3 and its derivatives as substrate labels has paved the way for biosensing, commercial immunoassays, and DNA probe assays. 2+ When used as an ECL luminophore, it can be recycled in the reaction, and the signal can be amplified, thereby achieving the purpose of improving the detection sensitivity. However, the ECL reaction usually occurs at a higher potential, and the measured analytical signal (i.e., light) is affected by both the electrode material and its surface properties. Previous studies on ECL were usually based on metal electrodes, which face the problem of easy formation of oxide film and impurity adsorption on their surfaces, which interfere with the analytical signal. Compared with ordinary electrode materials (such as metal electrodes, glassy carbon electrodes, and graphite electrodes), boron-doped diamond electrodes (BDD) have a wider potential window in water, low background current, and are not easy to form an oxide layer on the surface. They are not easily contaminated and poisoned, are corrosion-resistant, can work at high oxidation potentials or reduction potentials, and have good chemical inertness. Therefore, they are very suitable for the study of electrochemiluminescence reactions in aqueous solutions.
[0003] In order to improve the detection efficiency of ECL in practical applications and achieve higher sensitivity and lower detection limit, methods for enhancing ECL have been developed, including surfactant modification, solvent method, co-reactant method and surface plasmon-based method. However, these methods usually require long surface modification processes or complex electrolyte systems, and cannot flexibly control the electrode surface state; and methods that can in situ enhance the ECL luminescence intensity of the BDD surface have not been reported. Summary of the invention
[0004] In view of the shortcomings of the prior art, the present invention provides a method for enhancing the electrochemiluminescence reaction by in-situ induction of micro-nano bubbles on the surface of boron-doped diamond. The present invention uses an electrochemical method to in-situ induce micro-nano bubbles on the surface of boron-doped diamond to construct a special three-phase (gas, liquid, solid) interface microenvironment, thereby promoting the interface electrochemiluminescence reaction. The method of the present invention has the advantages of in-situ enhancement, simple operation and controllable at any time.
[0005] The technical solution of the present invention is as follows:
[0006] A method for enhancing electrochemiluminescence reaction by in-situ induction of micro-nano bubbles on the surface of boron-doped diamond, comprising the steps of:
[0007] (1) Using boron-doped diamond electrode as working electrode, platinum mesh as counter electrode, and Ag / AgCl as reference electrode, an electrochemical reaction system was constructed:
[0008] (2) Using electrochemical cyclic voltammetry (CV) or chronoamperometry (IT) to drive the generation of micro-nano bubbles on the surface of the working electrode to construct a three-phase interface microenvironment;
[0009] (3) Using electrochemical cyclic voltammetry (CV), linear sweep voltammetry (LSV) or chronoamperometry (IT) to drive the electrochemiluminescence reaction.
[0010] Preferably, in step (1), the boron-doped diamond electrode further comprises the steps of washing and surface insulation treatment in sequence before being used as a working electrode; the washing step comprises: ultrasonically cleaning the boron-doped diamond electrode in acetone, anhydrous ethanol and deionized water in sequence to remove surface contaminants; the surface insulation treatment step comprises: insulating one side of the boron-doped diamond electrode with an insulating tape.
[0011] Preferably, according to the present invention, in step (1), the electrolyte used in the electrochemical reaction system is a mixed solution of Ru(bpy)3Cl2, tri-n-propylamine (TPrA), and PBS buffer; in the electrolyte, the concentration of Ru(bpy)3Cl2 is 0.1-5 mmol / L, and the concentration of tri-n-propylamine (TPrA) is 10-200 mmol / L.
[0012] According to the present invention, in step (2), electrochemical cyclic voltammetry (CV) or chronoamperometry (iT) can be performed according to the prior art.
[0013] Preferably, according to the present invention, in step (2), the potential scanning range of the electrochemical cyclic voltammetry is -2.5V to 0V or 0V to 2.5V, and the number of scanning cycles is 2-8 times; the potential setting range of the chronoamperometry is -2.5V to 2.5V, and the reaction time is 20-100s.
[0014] Preferably, in step (2), the potential scanning range of the electrochemical cyclic voltammetry is -2.0 V to 0 V, and the number of scanning cycles is 3-5 times; the potential of the chronoamperometry is set to -2.0 V, and the reaction time is 50 s.
[0015] Preferably according to the present invention, in step (3), the potential scanning range of electrochemical cyclic voltammetry or linear sweep voltammetry is 0 to 1.4 V, and the potential setting range of chronoamperometry is 1.0 to 1.4 V.
[0016] Preferably, according to the present invention, in step (3), electrochemical cyclic voltammetry (CV), linear sweep voltammetry (LSV) or chronoamperometry (IT) is used to drive the electrochemiluminescence reaction, and the electrochemical reaction current and the luminescence spectrum are tested simultaneously.
[0017] The technical features and beneficial effects of the present invention are:
[0018] (1) The present invention utilizes an electrochemical method to in-situ induce micro-nano bubbles on the surface of boron-doped diamond, which has the advantages of in-situ generation, simple operation, flexible regulation, and reusable electrodes. In addition, the in-situ induction process is green, non-toxic, and low-cost.
[0019] (2) The working electrode of the reaction system of the present invention adopts a BDD electrode, which has the advantages of low surface adsorption characteristics and stable surface properties. It will not form an oxide film or adsorb other impurities when reacting at a high potential. Therefore, when conducting electrochemiluminescence research, there will be no interference from any other reactions, and a significant luminescence effect can be obtained, and the reasons for the enhancement or weakening of luminescence can be easily analyzed.
[0020] (3) The present invention can control the formation of an appropriate amount of micro-nano bubbles on the electrode surface by controlling the potential applied in electrochemical cyclic voltammetry (CV) or chronoamperometry (IT), the number of scanning cycles, the induced reaction time, etc., to form a three-phase interface microenvironment in the solution. The interface has the characteristics of strong electric field and low dielectric constant. The large electric field strength reduces the reaction activation energy, and the low dielectric constant of the interface promotes the metal-ligand charge transfer excited state. 3 MLCT state and metallic charge transfer excited state 3 The pre-equilibrium between the MC states (the main pathway for non-radiative decay) 3 The MLCT state moves, which helps to promote the radiative luminescence process of Ru(bpy)3Cl2 and achieve the purpose of enhancing the electrochemiluminescence reaction.
[0021] (4) Compared with the prior art, the method of in-situ induction of micro-nano bubbles on the surface of boron-doped diamond to enhance the electrochemiluminescence reaction proposed in the present invention solves the problem of low luminescence efficiency of the original electrochemiluminescence system. Considering that the co-reactant (TPrA) has certain toxicity, this enhancement method creates conditions for reducing the amount of TPrA used, and at the same time lays the foundation for obtaining higher sensitivity in practical ECL analysis and detection. BRIEF DESCRIPTION OF THE DRAWINGS
[0022] Figure 1 Cyclic voltammetry curves of hydrogen generation induced by the boron-doped diamond surface in Example 1 and Example 3;
[0023] Figure 2 This is a schematic diagram of the electrochemiluminescence reaction testing device described in Example 1 of the present invention;
[0024] Figure 3 (a) is the first cycle of the cyclic voltammetry curves of Sample I and Sample II measured when the electrochemiluminescence reaction was driven by cyclic voltammetry in Example 1; Figure 3 (b) is the second cycle of the cyclic voltammetry curves of Sample I and Sample II measured when the electrochemiluminescence reaction is driven by cyclic voltammetry in Example 1; Figure 3 (c) is the current response curve of sample I and sample II measured when the electrochemiluminescence reaction is driven by the chronoamperometry in Example 1; Figure 3 (d) is the linear sweep voltammetry curve of sample I and sample II measured when the electrochemiluminescence reaction is driven by the linear sweep voltammetry method in Example 1;
[0025] Figure 4 (a) is the electrochemiluminescence spectra of sample I and sample II measured when the first cycle reaction is driven by cyclic voltammetry in Example 1; Figure 4 (b) is the electrochemiluminescence spectra of sample I and sample II measured when the second cycle reaction is driven by cyclic voltammetry in Example 1; Figure 4 (c) is the electrochemiluminescence spectra of sample I and sample II measured when the reaction is driven by the chronoamperometry in Example 1; Figure 4 (d) is the electrochemiluminescence spectra of sample I and sample II measured when the linear sweep voltammetry driving reaction is performed in Example 1;
[0026] Figure 5 Cyclic voltammograms of electrochemiluminescence reactions driven by blank boron-doped diamond electrode, i.e., sample I, sample III prepared in Example 2, sample IV prepared in Example 3, sample V prepared in Example 4, and sample VI prepared in Comparative Example 1 in the range of 0.5V to 1.30V. DETAILED DESCRIPTION
[0027] The present invention is described in detail below with reference to the embodiments, but the present invention is not limited thereto.
[0028] The methods described in the examples are all conventional methods unless otherwise specified; the reagents used are all commercially available unless otherwise specified.
[0029] Example 1
[0030] A method for enhancing electrochemiluminescence reaction by in-situ induction of micro-nano bubbles on the surface of boron-doped diamond, the specific steps are as follows:
[0031] (1) Boron-doped diamond (length × width × thickness: 10 × 10 × 0.3 mm) was ultrasonically cleaned in acetone, anhydrous ethanol, and deionized water for 15 min to remove surface contaminants. After drying, one side of the boron-doped diamond (10 × 10 mm) was sealed with insulating tape for insulation treatment to obtain a working electrode.
[0032] (2) Ru(bpy)3Cl2 and TPrA were dissolved in 30 mL of 25 mM (phosphate concentration) PBS buffer to obtain an electrolyte; in the electrolyte, the concentration of Ru(bpy)3Cl2 was 0.5 mmol / L, and the concentration of TPrA was 15 mmol / L.
[0033] Then, the electrode obtained in step (1) is used as a working electrode, a platinum mesh is used as a counter electrode, and an Ag / AgCl electrode is used as a reference electrode, which are immersed in the prepared electrolyte to construct an electrochemical reaction system.
[0034] (3) Electrochemical cyclic voltammetry was used to scan five times in the negative potential range (-1.5 to 0 V) to induce the generation of hydrogen micro-nano bubbles on the surface of boron-doped diamond and construct a three-phase interface microenvironment;
[0035] After five negative scans, the fifth curve is as follows: Figure 1 As shown in the figure, it is explained that within this scanning potential range, only the hydrogen generation reaction occurs on the electrode surface, and no other side reactions occur.
[0036] (4) Using electrochemical cyclic voltammetry (CV), linear sweep voltammetry (LSV) or chronoamperometry (IT) to drive the electrochemiluminescence reaction and simultaneously test the electrochemical reaction current and luminescence spectrum.
[0037] The schematic diagram of the electrochemiluminescence reaction testing device of the present invention is as follows Figure 2 A collimator is fixed on the fiber probe of the fiber spectrometer. The focal length of the collimator lens is F = 15 mm and the diameter is D = 12.7 mm. The lens position is adjusted to be 1.5 cm away from the fiber probe and about 3.5 cm away from the BDD sample surface, so as to focus and collect the light signal diverged from the BDD surface under electrochemical driving conditions, as shown in FIG. Figure 2 shown.
[0038] The electrochemical reaction curve obtained by driving the electrochemiluminescence reaction in the positive potential range is as follows Figure 3 Wherein, the labeled sample I is a blank BDD electrode without surface bubble modification (i.e., step (3) is omitted, and the other steps and conditions are the same as those of this embodiment), and the sample II is a bubble-modified BDD electrode obtained by the method of the present invention (i.e., negative scanning five times in the potential range of -1.5 to 0 V).
[0039] Electrochemical cyclic voltammetry (CV) was used to drive the electrochemiluminescence reaction. Figure 3 (a) It can be seen that in the first cycle of the CV curve (0.5V~1.25V), the peak current density of sample II is 1.8 times that of sample I; Figure 3 (b) It can be seen that in the second cycle of the CV curve (0.5V~1.25V), the peak current density of sample II is 1.6 times that of sample I. The electrochemiluminescence reaction is driven by chronoamperometry (it). Figure 3 (c) It can be seen that when the reaction is carried out at a constant potential of 1.2 V for 20 s, the current density of sample II is 1.7 times that of sample I. The electrochemiluminescence reaction is driven by linear sweep voltammetry (LSV). Figure 3 (d) It can be seen that during the linear scan from 0.5V to 1.3V, the peak current density of sample II is 1.6 times that of sample I. From the above, the electrochemiluminescence reaction current obtained on the bubble-modified boron-doped diamond electrode is generally larger, indicating that the in-situ induction of micro-nano bubbles on the boron-doped diamond surface promotes the electrochemiluminescence reaction.
[0040] While driving the electrochemiluminescence reaction using electrochemical methods (electrochemical cyclic voltammetry, chronoamperometry, and linear sweep voltammetry), the spectrum was collected at the potential E = 0.90 V of the first cycle of CV and the potential E = 0.90 V of the second cycle of CV, and the integration time was set to 10 s; the spectrum was collected at the constant potential E = 1.2 V reaction time t = 20 s, and the integration time was set to 3 s; the spectrum was collected at the potential E = 0.90 V of the LSV scanning curve, and the integration time was set to 10 s. The measured electrochemiluminescence spectrum is shown in Figure 4 As shown. Figure 4 As can be seen from (a), the electrochemiluminescence intensity of the surface of sample II is 1.8 times that of the surface of sample I. Figures (b), (c), and (d) also show that no matter which electrochemical method is used to drive the electrochemical reaction, the electrochemiluminescence intensity of the surface of sample II is significantly higher than that of the surface of sample I, confirming the enhancing effect of surface micro-nano bubbles on the luminescence reaction.
[0041] Example 2
[0042] A method for enhancing electrochemiluminescence reaction by in-situ induction of micro-nano bubbles on the surface of boron-doped diamond, the specific steps are as follows:
[0043] (1) Boron-doped diamond (length × width × thickness: 10 × 10 × 0.3 mm) was ultrasonically cleaned in acetone, anhydrous ethanol, and deionized water for 15 min to remove surface contaminants. After drying, one side of the boron-doped diamond (10 × 10 mm) was sealed with insulating tape for insulation treatment to obtain a working electrode.
[0044] (2) Ru(bpy)3Cl2 and TPrA were dissolved in 30 mL of 25 mM (phosphate concentration) PBS buffer to obtain an electrolyte; in the electrolyte, the concentration of Ru(bpy)3Cl2 was 0.5 mmol / L, and the concentration of TPrA was 15 mmol / L.
[0045] Then, the electrode obtained in step (1) is used as a working electrode, a platinum mesh is used as a counter electrode, and an Ag / AgCl electrode is used as a reference electrode, which are immersed in the prepared electrolyte to construct an electrochemical reaction system.
[0046] (3) Electrochemical cyclic voltammetry was used to scan three times in the negative potential range (-1.5 to 0 V) to induce the generation of hydrogen micro-nano bubbles on the surface of boron-doped diamond and construct a three-phase interface microenvironment.
[0047] (4) The electrochemical cyclic voltammetry (CV) method was used to drive the electrochemiluminescence reaction and the electrochemical reaction current and luminescence spectrum were tested simultaneously.
[0048] The electrochemiluminescence reaction testing device is as described in Example 1.
[0049] The electrochemical cyclic voltammetry (CV) method was used to drive the electrochemiluminescence reaction in the positive potential range. The cyclic voltammetry curve obtained by the test was as follows: Figure 5 As shown. Among them, the labeled sample I is a blank BDD electrode without surface bubble modification (i.e. step (3) is omitted, and the other steps and conditions are the same as those of this embodiment), and the sample III is a bubble-modified BDD electrode obtained by the method of this embodiment (i.e., three negative scans in the potential range of -1.5 to 0 V).
[0050] from Figure 5 It can be seen that in the first cycle of the CV curve (0.5V-1.30V), the peak current density of sample III is 1.4 times that of sample I, indicating that the in-situ induction of micro-nano bubbles on the surface of boron-doped diamond promotes the electrochemiluminescence reaction.
[0051] Example 3
[0052] A method for enhancing electrochemiluminescence reaction by in-situ induction of micro-nano bubbles on the surface of boron-doped diamond, the specific steps are as follows:
[0053] (1) Boron-doped diamond (length × width × thickness: 10 × 10 × 0.3 mm) was ultrasonically cleaned in acetone, anhydrous ethanol, and deionized water for 15 min to remove surface contaminants. After drying, one side of the boron-doped diamond (10 × 10 mm) was sealed with insulating tape for insulation treatment to obtain a working electrode.
[0054] (2) Ru(bpy)3Cl2 and TPrA were dissolved in 30 mL of 25 mM (phosphate concentration) PBS buffer to obtain an electrolyte; in the electrolyte, the concentration of Ru(bpy)3Cl2 was 0.5 mmol / L, and the concentration of TPrA was 15 mmol / L.
[0055] Then, the electrode obtained in step (1) is used as a working electrode, a platinum mesh is used as a counter electrode, and an Ag / AgCl electrode is used as a reference electrode, which are immersed in the prepared electrolyte to construct an electrochemical reaction system.
[0056] (3) Electrochemical cyclic voltammetry was used to scan three times in the negative potential range (-2.0 to 0 V) to induce the generation of hydrogen micro-nano bubbles on the surface of boron-doped diamond and construct a three-phase interface microenvironment;
[0057] After three negative scans, the third curve is as follows Figure 1 As shown in the figure, it is explained that within the scanning potential range, in addition to the hydrogen generation reaction on the electrode surface, a partial reduction reaction of Ru(bpy)3Cl2 occurs at around -1.5V. As the applied potential increases, the surface bubble density gradually increases.
[0058] (4) The electrochemical cyclic voltammetry (CV) method was used to drive the electrochemiluminescence reaction and the electrochemical reaction current and luminescence spectrum were tested simultaneously.
[0059] The electrochemiluminescence reaction testing device is as described in Example 1.
[0060] The electrochemical reaction curve obtained by driving the electrochemiluminescence reaction in the positive potential range is as follows Figure 5 As shown. Among them, the labeled sample I is a blank BDD electrode without surface bubble modification (i.e. step (3) is omitted, and the other steps and conditions are the same as those of this embodiment), and the sample IV is a bubble-modified BDD electrode obtained by the method of this embodiment (i.e., three negative scans in the potential range of -2.0 to 0 V).
[0061] from Figure 5 It can be seen that in the first cycle of the CV curve (0.5V-1.30V), the peak current density of sample IV is 1.4 times that of sample I, indicating that the in-situ induction of micro-nano bubbles on the surface of boron-doped diamond promotes the electrochemiluminescence reaction.
[0062] Example 4
[0063] A method for enhancing electrochemiluminescence reaction by in-situ induction of micro-nano bubbles on the surface of boron-doped diamond, the specific steps are as follows:
[0064] (1) Boron-doped diamond (length × width × thickness: 10 × 10 × 0.3 mm) was ultrasonically cleaned in acetone, anhydrous ethanol, and deionized water for 15 min to remove surface contaminants. After drying, one side of the boron-doped diamond (10 × 10 mm) was sealed with insulating tape for insulation treatment to obtain a working electrode.
[0065] (2) Ru(bpy)3Cl2 and TPrA were dissolved in 30 mL of 25 mM (phosphate concentration) PBS buffer to obtain an electrolyte; in the electrolyte, the concentration of Ru(bpy)3Cl2 was 0.5 mmol / L, and the concentration of TPrA was 15 mmol / L.
[0066] Then, the electrode obtained in step (1) is used as a working electrode, a platinum mesh is used as a counter electrode, and an Ag / AgCl electrode is used as a reference electrode, which are immersed in the prepared electrolyte to construct an electrochemical reaction system.
[0067] (3) The chronoamperometry was used to induce the generation of hydrogen micro-nano bubbles on the surface of boron-doped diamond at a constant potential of -2.0 V for 50 s, thereby constructing a three-phase interface microenvironment.
[0068] (4) The electrochemical cyclic voltammetry (CV) method was used to drive the electrochemiluminescence reaction and the electrochemical reaction current and luminescence spectrum were tested simultaneously.
[0069] The electrochemiluminescence reaction testing device is as described in Example 1.
[0070] The electrochemical reaction curve obtained by driving the electrochemiluminescence reaction in the positive potential range is as follows Figure 5 Wherein, the labeled sample I is a blank BDD electrode without surface bubble modification (i.e., step (3) is omitted, and the other steps and conditions are the same as those of this embodiment), and the sample V is a bubble-modified BDD electrode obtained by the method of this embodiment (i.e., reacting at a constant potential of -2.0 V for 50 s).
[0071] from Figure 5 It can be seen that in the first cycle of the CV curve (0.5V-1.30V), the peak current density of sample V is twice that of sample I, indicating that the in-situ induction of micro-nano bubbles on the surface of boron-doped diamond promotes the electrochemiluminescence reaction.
[0072] Comparative Example 1
[0073] A method for enhancing electrochemiluminescence reaction by in-situ induction of micro-nano bubbles on the surface of boron-doped diamond, the specific steps are as follows:
[0074] (1) Boron-doped diamond (length × width × thickness: 10 × 10 × 0.3 mm) was ultrasonically cleaned in acetone, anhydrous ethanol, and deionized water for 15 min to remove surface contaminants. After drying, one side of the boron-doped diamond (10 × 10 mm) was sealed with insulating tape for insulation treatment to obtain a working electrode.
[0075] (2) Ru(bpy)3Cl2 and TPrA were dissolved in 30 mL of 25 mM (phosphate concentration) PBS buffer to obtain an electrolyte; in the electrolyte, the concentration of Ru(bpy)3Cl2 was 0.5 mmol / L, and the concentration of TPrA was 15 mmol / L.
[0076] Then, the electrode obtained in step (1) is used as a working electrode, a platinum mesh is used as a counter electrode, and an Ag / AgCl electrode is used as a reference electrode, which are immersed in the prepared electrolyte to construct an electrochemical reaction system.
[0077] (3) The chronoamperometry was used to induce the generation of hydrogen micro-nano bubbles on the surface of boron-doped diamond at a constant potential of -2.0 V for 5 min, thus constructing a three-phase interface microenvironment.
[0078] (4) The electrochemical cyclic voltammetry (CV) method was used to drive the electrochemiluminescence reaction and the electrochemical reaction current and luminescence spectrum were tested simultaneously.
[0079] The electrochemiluminescence reaction testing device is as described in Example 1.
[0080] The electrochemical reaction curve obtained by driving the electrochemiluminescence reaction in the positive potential range is as follows Figure 5 As shown. Among them, the labeled sample I is a blank BDD electrode without surface bubble modification (i.e. step (3) is omitted, and the other steps and conditions are the same as those of this embodiment), and the sample VI is a bubble-modified BDD electrode obtained by the comparative example method (i.e. reacting at a constant potential of -2.0 V for 5 min).
[0081] from Figure 5 It can be seen that in the first cycle of the CV curve (0.5V~1.30V), the peak current density of sample VI is significantly reduced compared with sample I. This is because the excessive enrichment of bubbles induced in situ on the surface of boron-doped diamond shields some electrode reaction sites, resulting in a weakening of the electrochemiluminescence reaction.
Claims
1. A method for enhancing electrochemiluminescence reaction by in-situ induction of micro-nano bubbles on the surface of boron-doped diamond, comprising the steps of: (1) Using boron-doped diamond electrode as working electrode, platinum mesh as counter electrode, and Ag / AgCl as reference electrode, an electrochemical reaction system was constructed: (2) Using electrochemical cyclic voltammetry (CV) or chronoamperometry (IT) to drive the generation of micro-nano bubbles on the surface of the working electrode to construct a three-phase interface microenvironment; The potential scanning range of electrochemical cyclic voltammetry is -2.5V to 0V or 0V to 2.5V, and the scanning cycle number is 2-8 times; the potential setting range of chronoamperometry is -2.5V to 2.5V, and the reaction time is 20-100s; (3) Using electrochemical cyclic voltammetry (CV), linear sweep voltammetry (LSV) or chronoamperometry (IT) to drive the electrochemiluminescence reaction.
2. The method for enhancing electrochemiluminescence reaction by in-situ induction of micro-nano bubbles on the surface of boron-doped diamond according to claim 1, characterized in that: In step (1), the boron-doped diamond electrode further includes washing and surface insulation treatment steps in sequence before being used as a working electrode; the washing step is: ultrasonically cleaning the boron-doped diamond electrode in acetone, anhydrous ethanol, and deionized water in sequence to remove surface pollutants; the surface insulation treatment step is: insulating one side of the boron-doped diamond electrode with an insulating tape.
3. The method for enhancing electrochemiluminescence reaction by in-situ induction of micro-nano bubbles on the surface of boron-doped diamond according to claim 1, characterized in that: In step (1), the electrolyte used in the electrochemical reaction system is a mixed solution of Ru(bpy)3Cl2, tri-n-propylamine (TPrA), and PBS buffer; in the electrolyte, the concentration of Ru(bpy)3Cl2 is 0.1-5 mmol / L, and the concentration of tri-n-propylamine (TPrA) is 10-200 mmol / L.
4. The method for enhancing electrochemiluminescence reaction by in-situ induction of micro-nano bubbles on the surface of boron-doped diamond according to claim 1, characterized in that: In step (2), the scanning cycle number of the electrochemical cyclic voltammetry is 3-5 times.
5. The method for enhancing electrochemiluminescence reaction by in-situ induction of micro-nano bubbles on the surface of boron-doped diamond according to claim 1, characterized in that: In step (2), the potential scanning range of the electrochemical cyclic voltammetry is -2.0 V to 0 V, and the number of scanning cycles is 3-5 times; the potential of the chronoamperometry is set to -2.0 V, and the reaction time is 50 s.
6. The method for enhancing electrochemiluminescence reaction by in-situ induction of micro-nano bubbles on the surface of boron-doped diamond according to claim 1, characterized in that: In step (3), the potential scanning range of electrochemical cyclic voltammetry or linear sweep voltammetry is 0 to 1.4 V, and the potential setting range of chronoamperometry is 1.0 to 1.4 V.
7. The method of enhancing electrochemiluminescence reaction by in-situ induction of micro-nano bubbles on the surface of boron-doped diamond according to claim 1, characterized in that: In step (3), electrochemical cyclic voltammetry (CV), linear sweep voltammetry (LSV) or chronoamperometry (IT) is used to drive the electrochemiluminescence reaction, and the electrochemical reaction current and luminescence spectrum are tested simultaneously.