Self-powered electrochemiluminescence device and application thereof

Abstract

This invention belongs to the field of electrochemistry, and particularly relates to a self-powered electrochemiluminescence device and its application. The self-powered electrochemiluminescence device provided by this invention includes: a reaction cell, an electrochemiluminescence solution contained in the reaction cell, and a galvanized iron electrode with one end immersed in the electrochemiluminescence solution. The galvanized iron electrode includes a galvanized iron core and an inert material protective layer. The galvanized iron core includes an iron inner core and a zinc coating laminated to the side of the iron inner core. The inert material protective layer at least covers the area of ​​the side of the galvanized iron core below the surface of the electrochemiluminescence solution. The iron inner core and zinc coating at the immersed end of the galvanized iron electrode are exposed on the end face. This invention uses galvanized iron to develop a self-powered electrochemiluminescence device that can eliminate background interference from the driving electrode, does not require an external power supply, and greatly reduces the size of the electrochemical device. Combined with a photomultiplier tube, this device can also be used to detect ascorbic acid.

Description

Technical Field

[0001] This invention belongs to the field of electrochemistry, and particularly relates to a self-powered electrochemiluminescence device and its application. Background Technology

[0002] Existing bipolar electrode electrochemiluminescence systems typically include a bipolar electrode, two driving electrodes, and a power source. When the bipolar electrode is placed in an electrochemiluminescence solution, applying a voltage to the driving electrodes across the solution causes one end of the bipolar electrode in the solution to become the anode and the other the cathode. If the applied electric field is sufficiently large, substances in the solution will undergo oxidation and reduction reactions at the anode and cathode, respectively, thereby exciting electrochemiluminescence, which can be observed using a photomultiplier tube (PMT) or a CMOS sensor.

[0003] Existing bipolar electrode electrochemiluminescence systems often require complex processes for preparing bipolar electrodes and two driving electrodes, resulting in high costs, large instrument size, the need for external power supply, and susceptibility to background luminescence interference generated on the driving electrodes, which hinders the widespread application of bipolar electrodes. Summary of the Invention

[0004] In view of this, the purpose of the present invention is to provide a self-powered electrochemiluminescence device and its application. The present invention uses galvanized iron to develop a self-powered electrochemiluminescence device that can eliminate background interference of the driving electrode, does not require external power supply, and greatly reduces the size of the electrochemical device. The device, combined with a photomultiplier tube, can also be used to detect ascorbic acid.

[0005] This invention provides a self-powered electrochemiluminescence device, comprising: a reaction cell, an electrochemiluminescence solution contained in the reaction cell, and a zinc-plated iron electrode with one end immersed in the electrochemiluminescence solution;

[0006] The galvanized iron electrode includes a galvanized iron core and an inert material protective layer. The galvanized iron core includes an iron inner core and a zinc coating composited on the side of the iron inner core. The inert material protective layer at least covers the area of ​​the side of the galvanized iron core below the surface of the electrochemiluminescence solution. The iron inner core and zinc coating at the immersed end of the galvanized iron electrode are exposed on the end face.

[0007] Preferably, the diameter of the iron core is 1 to 3 mm.

[0008] Preferably, the thickness of the zinc coating is 10–100 μm.

[0009] Preferably, the inert material protective layer includes an inert material shell and an inert encapsulation material filled between the inert material shell and the side of the galvanized iron core.

[0010] Preferably, the inert material shell is a plastic tube; the inert encapsulation material is epoxy resin.

[0011] Preferably, the electrochemiluminescence solution comprises luminol, hydrogen peroxide, pH buffer, and water.

[0012] Preferably, the concentration of luminol in the electrochemiluminescence solution is 20–200 μmol / L; and the concentration of hydrogen peroxide in the electrochemiluminescence solution is 200–2000 μmol / L.

[0013] Preferably, the pH buffer is citric acid, Tris-HCl, acetic acid, or phosphoric acid.

[0014] Preferably, the pH value of the electrochemiluminescence solution is 6 to 8.

[0015] This invention provides a method for detecting ascorbic acid concentration using a self-powered electrochemiluminescence device, comprising the following steps:

[0016] An electrochemiluminescence solution mixed with the ascorbic acid solution to be tested was added to a reaction cell. The reaction cell was then placed in the photomultiplier tube detection chamber. One end of the galvanized iron electrode was immersed in the electrochemiluminescence solution in the reaction cell, and the luminescence intensity was detected. The concentration of the ascorbic acid solution to be tested was calculated based on the luminescence intensity detection result and the pre-established relationship curve between the concentration of the ascorbic acid solution and the luminescence intensity.

[0017] The galvanized iron electrode includes a galvanized iron core and an inert material protective layer. The galvanized iron core includes an iron inner core and a zinc coating composited on the side of the iron inner core. The inert material protective layer at least covers the area of ​​the side of the galvanized iron core below the surface of the electrochemiluminescence solution. The iron inner core and zinc coating at the immersed end of the galvanized iron electrode are exposed on the end face.

[0018] Compared with existing technologies, this invention provides a self-powered electrochemiluminescence device and its application. The self-powered electrochemiluminescence device provided by this invention includes: a reaction cell, an electrochemiluminescence solution contained in the reaction cell, and a galvanized iron electrode with one end immersed in the electrochemiluminescence solution. The galvanized iron electrode includes a galvanized iron core and an inert material protective layer. The galvanized iron core includes an iron inner core and a zinc coating laminated to the side of the iron inner core. The inert material protective layer at least covers the area of ​​the side of the galvanized iron core below the surface of the electrochemiluminescence solution. The iron inner core and zinc coating at the immersed end of the galvanized iron electrode are exposed on the end face. This invention utilizes readily available and inexpensive galvanized iron to develop a self-powered electrochemiluminescence device. When the exposed surface of the galvanized iron electrode core is immersed in the electrochemiluminescence solution, the more reducing zinc reacts with the electrochemiluminescence solution, generating electron transfer, thereby driving the electrochemical reaction of the electrochemiluminescence solution and producing electrochemiluminescence. The self-powered electrochemiluminescence device provided by this invention can eliminate background interference of the driving electrode, does not require external power supply, and greatly reduces the size of the electrochemical device; in addition, the device, combined with a photomultiplier tube, can also be used to detect ascorbic acid. Attached Figure Description

[0019] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.

[0020] Figure 1 This is a schematic diagram of the structure of the self-powered electrochemiluminescence device provided in the embodiments of the present invention;

[0021] Figure 2 This is a schematic diagram of the end face structure of the immersion end of the galvanized iron electrode provided in an embodiment of the present invention;

[0022] Figure 3 This is a physical image of the galvanized iron electrode provided in Embodiment 1 of the present invention;

[0023] Figure 4 This is the luminous intensity detection diagram provided in Embodiment 1 of the present invention;

[0024] Figure 5 This is a graph showing the luminescence intensity under different pH buffer conditions provided in Example 2 of the present invention;

[0025] Figure 6 This is a graph showing the relationship between the concentration of ascorbic acid solution and the luminescence intensity provided in Example 3 of the present invention.

[0026] Appendix Figure 1The markings are as follows: 1 is galvanized iron core material, 2 is inert material protective layer, 3 is reaction cell, and 4 is electrochemiluminescence solution. Detailed Implementation

[0027] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0028] This invention provides a self-powered electrochemiluminescence device, see [link to related document]. Figure 1 It includes: a reaction cell 3, an electrochemiluminescence solution 4 contained in the reaction cell 3, and a zinc-plated iron electrode with one end immersed in the electrochemiluminescence solution 4;

[0029] The galvanized iron electrode includes a galvanized iron core 1 and an inert material protective layer 2; wherein, the galvanized iron core 1 includes an iron inner core and a zinc coating composite on the side of the iron inner core; the inert material protective layer 2 at least covers the area of ​​the side of the galvanized iron core 1 below the surface of the electrochemiluminescence solution 4, and is used to prevent the side of the galvanized iron core from contacting and reacting with the electrochemiluminescence solution; the iron inner core and zinc coating at the immersed end of the galvanized iron electrode are exposed on the end face.

[0030] In the self-powered electrochemiluminescence device provided by the present invention, the diameter of the iron core material 1 is preferably 1 to 3 mm, specifically 1 mm, 1.1 mm, 1.2 mm, 1.3 mm, 1.4 mm, 1.5 mm, 1.6 mm, 1.7 mm, 1.8 mm, 1.9 mm, 2 mm, 2.1 mm, 2.2 mm, 2.3 mm, 2.4 mm, 2.5 mm, 2.6 mm, 2.7 mm, 2.8 mm, 2.9 mm or 3 mm.

[0031] In the self-powered electrochemiluminescence device provided by the present invention, the thickness of the zinc coating in the galvanized iron core material 1 is 10-100 μm, specifically 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm or 100 μm.

[0032] In the self-powered electrochemiluminescence device provided by this invention, see [link to invention]. Figure 2 The inert material protective layer 2 preferably includes an inert material shell and an inert encapsulation material filled between the inert material shell and the side of the galvanized iron core; wherein the inert material shell is preferably a plastic tube; and the inert encapsulation material is preferably epoxy resin.

[0033] In the self-powered electrochemiluminescence device provided by the present invention, the electrochemiluminescence solution 4 preferably comprises luminol, hydrogen peroxide, a pH buffer, and water; wherein, the concentration of luminol in the electrochemiluminescence solution is preferably 20–200 μmol / L, specifically 20 μmol / L, 30 μmol / L, 40 μmol / L, 50 μmol / L, 60 μmol / L, 70 μmol / L, 80 μmol / L, 90 μmol / L, 100 μmol / L, 110 μmol / L, 120 μmol / L, 130 μmol / L, 140 μmol / L, 150 μmol / L, 160 μmol / L, 170 μmol / L, 180 μmol / L, 190 μmol / L, or 200 μmol / L; the concentration of hydrogen peroxide in the electrochemiluminescence solution is preferably 200–2000 μmol / L, specifically 200 μmol / L. ol / L, 300μmol / L, 400μmol / L, 500μmol / L, 600μmol / L, 700μmol / L, 800μmol / L, 900μmol / L, 1000 μmol / L, 1100μmol / L, 1200μmol / L, 1300μmol / L, 1400μmol / L, 1500μmol / L, 1600μmol / L, 1700μmo The concentration of the pH buffer in the electrochemiluminescence solution is preferably 0.05–0.2 mol / L, specifically 0.1 mol / L; the pH buffer is preferably citric acid, Tris-HCl, acetic acid, or phosphoric acid, more preferably citric acid; the concentration of the pH buffer in the electrochemiluminescence solution is preferably 0.05–0.2 mol / L, specifically 0.1 mol / L; the pH value of the electrochemiluminescence solution 4 is preferably 6–8, specifically 6, 6.5, 7, 7.5, or 8.

[0034] This invention also provides a method for detecting ascorbic acid concentration using a self-powered electrochemiluminescence device. The structure of the self-powered electrochemiluminescence device is described below. Figure 1 The detection method includes the following steps:

[0035] The electrochemiluminescence solution 4, which is mixed with the ascorbic acid solution to be tested, is added to the reaction cell 3. Then, the reaction cell 3 is placed in the photomultiplier tube (PMT) detection chamber. One end of the zinc-plated iron electrode is immersed in the electrochemiluminescence solution in the reaction cell 3, and the luminescence intensity is detected. The concentration of the ascorbic acid solution to be tested is calculated based on the luminescence intensity detection result and the pre-established relationship curve between the concentration of the ascorbic acid solution and the luminescence intensity.

[0036] The galvanized iron electrode includes a galvanized iron core 1 and an inert material protective layer 2; wherein, the galvanized iron core 1 includes an iron inner core and a zinc coating composite on the side of the iron inner core; the inert material protective layer 2 at least covers the area of ​​the side of the galvanized iron core 1 below the surface of the electrochemiluminescence solution 4, and is used to prevent the side of the galvanized iron core from contacting and reacting with the electrochemiluminescence solution; the iron inner core and zinc coating at the immersed end of the galvanized iron electrode are exposed on the end face.

[0037] The relevant content concerning the self-powered electrochemiluminescence device in the method provided by this invention has been described above and will not be repeated here.

[0038] The technical solution provided by this invention utilizes readily available and inexpensive galvanized iron to develop a self-powered electrochemiluminescence device. When the exposed surface of the galvanized iron electrode core is immersed in the electrochemiluminescence solution, the more reducing zinc reacts with the solution, generating electron transfer, thereby driving the electrochemical reaction in the solution and producing electrochemiluminescence. The self-powered electrochemiluminescence device provided by this invention can eliminate background interference from the driving electrode, requires no external power supply, and significantly reduces the size of the electrochemical device. Furthermore, when combined with a photomultiplier tube, this device can also be used to detect ascorbic acid.

[0039] For clarity, the following examples will be used to provide a detailed description.

[0040] Example 1

[0041] (1) Preparation of galvanized iron electrode: Coat a galvanized iron wire (with a 2mm iron core and a 30μm galvanized layer) with epoxy resin, insert it into a plastic tube, and let it dry. Grind one end of the electrode with sandpaper to expose the iron core on the end face to obtain the galvanized iron electrode. The actual object is shown in the figure. Figure 3 As shown; rinse the electrode surface with ultrapure water and set aside for use.

[0042] (2) According to Figure 1 The structure shown is assembled into a self-powered electrochemiluminescence device, and the luminescence intensity is detected: at room temperature, a mixed solution of luminol (50 μmol / L), hydrogen peroxide (500 μmol / L), and citric acid pH buffer (0.1 mol / L, pH=7) is added to the reaction cell 3 as electrochemiluminescence solution 4, with an addition volume of 500 μL; then the reaction cell 3 is placed in the photomultiplier tube (PMT) detection chamber, and one end of the galvanized iron electrode is immersed in the electrochemiluminescence solution 4 in the reaction cell 3, and the luminescence intensity is detected immediately.

[0043] In this embodiment, after the galvanized iron electrode is inserted into the reaction cell 3, the electrochemiluminescent solution 4 undergoes an electrochemical reaction on the exposed iron core surface of the galvanized iron electrode, thereby exciting luminol to produce strong electrochemiluminescence. The luminescence intensity detection results are as follows: Figure 4As shown, Figure 4 This is a luminous intensity detection diagram provided in Embodiment 1 of the present invention. (Through...) Figure 4 It can be seen that the complete signal peak can be observed within 5 seconds.

[0044] Example 2

[0045] Relationship between different buffer solutions and luminescence intensity

[0046] Referring to Example 1, the difference is that citric acid, Tris-HCl, acetic acid, and phosphoric acid are used as pH buffers in the electrochemiluminescence solution 4, respectively.

[0047] The luminescence intensity test results are as follows Figure 5 As shown, Figure 5 This is a luminescence intensity detection graph provided in Example 2 of the present invention under different pH buffer conditions, where a is citric acid, b is Tris-HCl, c is acetic acid, and d is phosphoric acid. Figure 5 It can be seen that the luminescence effect is best when citric acid is used as a pH buffer.

[0048] Example 3

[0049] Relationship between ascorbic acid concentration and luminescence intensity

[0050] Referring to Example 1, the difference is that different concentrations of ascorbic acid are mixed into the electrochemiluminescent solution 4, and the concentration gradient of ascorbic acid in the electrochemiluminescent solution 4 is 0.5 μmol / L, 1 μmol / L, 5 μmol / L, 10 μmol / L, 50 μmol / L, and 100 μmol / L.

[0051] In this embodiment, the electrochemiluminescence intensity of luminol is inhibited by ascorbic acid. The luminescence intensity detection results are as follows: Figure 6 As shown, Figure 6 This is a graph showing the relationship between the concentration of ascorbic acid solution and the luminescence intensity provided in Example 3 of the present invention. Figure 6 It can be seen that the degree of inhibition of luminol electrochemiluminescence by ascorbic acid is linearly related to the concentration of ascorbic acid. Therefore, this property can be used to quantitatively detect the concentration of ascorbic acid.

[0052] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A self-powered electrochemiluminescence device, characterized in that, include: A reaction cell containing an electrochemiluminescence solution and a zinc-plated iron electrode with one end immersed in the electrochemiluminescence solution; The galvanized iron electrode includes a galvanized iron core and an inert material protective layer. The galvanized iron core includes an iron inner core and a zinc coating composited on the side of the iron inner core. The inert material protective layer at least covers the area of ​​the side of the galvanized iron core below the surface of the electrochemiluminescence solution. The iron inner core and zinc coating at the immersed end of the galvanized iron electrode are exposed on the end face.

2. The self-powered electrochemiluminescence device according to claim 1, characterized in that, The diameter of the iron inner core is 1 to 3 mm.

3. The self-powered electrochemiluminescence device according to claim 1, characterized in that, The thickness of the zinc coating is 10–100 μm.

4. The self-powered electrochemiluminescence device according to claim 1, characterized in that, The inert material protective layer includes an inert material shell and an inert encapsulation material filled between the inert material shell and the side of the galvanized iron core.

5. The self-powered electrochemiluminescence device according to claim 4, characterized in that, The inert material outer shell is a plastic tube; the inert encapsulation material is epoxy resin.

6. The self-powered electrochemiluminescence device according to claim 1, characterized in that, The electrochemiluminescence solution comprises luminol, hydrogen peroxide, pH buffer, and water.

7. The self-powered electrochemiluminescence device according to claim 6, characterized in that, The concentration of luminol in the electrochemiluminescent solution is 20–200 μmol / L; the concentration of hydrogen peroxide in the electrochemiluminescent solution is 200–2000 μmol / L.

8. The self-powered electrochemiluminescence device according to claim 6, characterized in that, The pH buffer is citric acid, Tris-HCl, acetic acid, or phosphoric acid.

9. The self-powered electrochemiluminescence device according to claim 6, characterized in that, The pH value of the electrochemiluminescent solution is 6-8.

10. A method for detecting ascorbic acid concentration using a self-powered electrochemiluminescence device, characterized in that, Includes the following steps: An electrochemiluminescence solution mixed with the ascorbic acid solution to be tested was added to a reaction cell. The reaction cell was then placed in the photomultiplier tube detection chamber. One end of the galvanized iron electrode was immersed in the electrochemiluminescence solution in the reaction cell, and the luminescence intensity was detected. The concentration of the ascorbic acid solution to be tested was calculated based on the luminescence intensity detection result and the pre-established relationship curve between the concentration of the ascorbic acid solution and the luminescence intensity. The galvanized iron electrode includes a galvanized iron core and an inert material protective layer. The galvanized iron core includes an iron inner core and a zinc coating composited on the side of the iron inner core. The inert material protective layer at least covers the area of ​​the side of the galvanized iron core below the surface of the electrochemiluminescence solution. The iron inner core and zinc coating at the immersed end of the galvanized iron electrode are exposed on the end face.

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