Monoatom-regulated chemiluminescence fluorine ion detection sensor, preparation method and application
By using a single-atom-regulated chemiluminescence detection fluoride ion sensor in fluoride detection, the specific reaction between F- and silica is used to generate H2O2 and decompose and generate OH under single-atom copper catalysis, achieving high specificity and high sensitivity The fluoride detection solves the problem of inefficient detection in the prior art.
Patent Information
- Application Number
- CN202411592235.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-08
- Publication Date
- 2025-02-18
AI Technical Summary
Existing fluoride detection methods require complex experimental instruments and professionals to operate, resulting in inefficient analysis.
A single-atom-regulated chemiluminescence detection sensor was used to encapsulate single-atom copper catalysts and calcium oxide nanoparticles through silica microspheres. The specific reaction between F- and silica is used to generate H2O2 and under single-atom copper catalyzed Decomposition produces·OH to realize chemiluminescence detection.
It improves the selectivity and accuracy of the chemiluminescence sensor, realizes high specificity, high sensitivity and rapid detection of F- in the sample, reduces detection costs, and simplifies the operation process.
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Figure CN119470402A_ABST
Abstract
Description
Technical Field
[0001] The present disclosure relates to the technical field of chemiluminescence detection sensors, and in particular to a single-atom regulated chemiluminescence detection fluoride ion sensor, a preparation method and an application thereof. Background Art
[0002] The statements in this section merely provide background information related to the present disclosure and do not necessarily constitute prior art.
[0003] Fluorine is one of the trace elements necessary for human life. Our daily drinking water, food, cosmetics and toothpaste all contain various fluorides to varying degrees. Under normal circumstances, the fluorine in the human body comes directly from drinking water, food and air. The total fluorine content in an adult is about 2.57g, of which more than 96% is accumulated in hard tissues such as bones and teeth. However, although fluorine is an essential trace element for the body, excessive intake can cause serious harm to the body, namely fluorosis. Fluorine is a systemic poison that has a certain damaging effect on various tissues and organs of the body. Studies have confirmed that fluorine has been confirmed as a reproductive poison. Fluoride deficiency is prone to dental caries, and the appropriate concentration of fluoride in drinking water is 0.5-1.0 mg / L (F-). When drinking water with a fluoride content higher than 1-1.5 mg / L for a long time, it is easy to suffer from dental plaque. If the fluoride content in the water is higher than 4 mg / L, it can lead to fluorosis. Fluoride is widely present in natural water bodies, and its distribution in nature is affected by factors such as Cl-, Ca2+, Mg2+, SO42-, pH, and salinity. Fluoride is often found in wastewater from nonferrous metallurgy, steel and aluminum processing, coke, glass, ceramics, electronics, electroplating, fertilizers, pesticide factories, and wastewater from fluorine-containing minerals. Therefore, it is of great significance to carry out and continuously improve the detection of fluoride in water.
[0004] Existing methods for detecting fluoride include fluoride ion spectrophotometry, ion selective electrode method, ion chromatography and atomic fluorescence spectroscopy, but most of them require complex experimental instruments and professional personnel to operate, which greatly affects the analysis efficiency of fluoride ions. Summary of the invention
[0005] In order to solve the above problems, the present disclosure proposes a single-atom regulated chemiluminescence sensor for detecting fluoride ions, a preparation method and an application thereof, wherein a single-atom copper catalyst and calcium oxide nanoparticles are encapsulated in silica microspheres, and the silica shell is etched by utilizing the specific reaction between F- and silica, resulting in the single-atom copper catalyst and calcium oxide nanoparticles encapsulated by silica being exposed to an aqueous solution, and the calcium oxide reacts with water to generate H2O2, which serves as an oxidant in the H2O2-luminol chemiluminescence system. Under the catalysis of the single-atom copper catalyst, H2O2 decomposes to generate ·OH, and ·OH reacts with oxidized luminol to generate chemiluminescence, and F- is detected according to the chemiluminescence intensity.
[0006] According to some embodiments, the present disclosure adopts the following technical solutions:
[0007] A single-atom regulated chemiluminescence sensor for detecting fluoride ions, characterized in that it comprises silica microspheres, wherein a single-atom copper-calcium oxide nanoparticle composite material composed of a single-atom copper catalyst and calcium oxide nanoparticles is encapsulated in the silica microspheres.
[0008] According to some embodiments, the present disclosure adopts the following technical solutions:
[0009] A method for preparing a single-atom controlled chemiluminescence sensor for detecting fluoride ions, comprising:
[0010] A method for preparing a composite material of single-atom copper-calcium oxide nanoparticles wrapped in silicon dioxide, comprising:
[0011] Synthesis of calcium oxide nanoparticles using a coprecipitation method;
[0012] The obtained single-atom copper catalyst and calcium oxide nanoparticles are dispersed in a silicon dioxide precursor solution to prepare a silicon dioxide-wrapped single-atom copper-calcium oxide nanoparticle composite material.
[0013] As an embodiment, the process of preparing a single-atom copper catalyst by high-temperature pyrolysis method includes:
[0014] First, set masses of melamine and cyanuric acid are dispersed in hot water respectively, stirred and mixed to obtain a hot cyanuric acid aqueous solution, then set masses of citric acid and copper acetate are weighed to prepare citric acid and copper acetate aqueous solutions, stirred and mixed to obtain a hot cyanuric acid aqueous solution, citric acid and copper acetate aqueous solutions are added to the hot cyanuric acid aqueous solution and stirred continuously, and then the mixed solution is added to the hot melamine aqueous solution, heated and stirred continuously, and the heating is stopped and stirred continuously. After the reaction is completed, the product is separated by centrifugation and precipitated, washed with water and ethanol in turn, and vacuum dried. The dried product is placed in a tubular furnace, and a programmed temperature is set under the protection of an inert gas, and calcined to obtain a single-atom copper catalyst.
[0015] As an embodiment, the process of synthesizing calcium oxide nanoparticles using a co-precipitation method includes: stirring and mixing a set mass of sodium hyaluronate solution and a set mass of calcium chloride solution at room temperature, adding a set mass of sodium hydroxide solution to continue the reaction, then adding a set mass of H2O2 dropwise, continuing to stir the reaction at room temperature, centrifuging and washing with water, and finally freeze-drying to obtain a light yellow calcium oxide powder.
[0016] As an embodiment, under the protection of inert gas, the rate of programmed temperature rise is set to 2-10(5)℃ / min, the heating time is 50-120(110)min, the reaction is carried out at 600℃ for 2-5(4)h, after the reaction is completed, the temperature is increased to 620℃ at a rate of 1-5(2)℃ / min and the reaction is continued for 1-2(2)h, and the reaction is automatically cooled to room temperature after completion.
[0017] As an example, the mass concentration of the sodium hyaluronate solution is 1-10 (5) mg / mL; the concentration of the calcium chloride solution is 1-5 (2) mol / L.
[0018] According to some embodiments, the present disclosure adopts the following technical solutions:
[0019] The invention discloses an application of a single-atom regulated chemiluminescence sensor for detecting fluorine ions, wherein the single-atom regulated chemiluminescence sensor for detecting fluorine ions is applied in quantitative analysis and measurement of F ions.
[0020] According to some embodiments, the present disclosure adopts the following technical solutions:
[0021] A method for measuring F ions by using a single-atom regulated chemiluminescence detection fluoride ion sensor, comprising:
[0022] (1) dispersing the sensor according to claim 1 into a F-solution to be tested for reaction;
[0023] (2) Place an appropriate amount of reaction solution in a 96-well microplate;
[0024] (3) adding luminol solution;
[0025] (4) The chemiluminescence intensity was measured using a chemiluminescence analyzer.
[0026] As an embodiment, the obtained silica-coated palladium nanoparticle-calcium oxide nanoparticle composite material is dispersed into an aqueous solution containing F- at different concentrations. After heating for a set reaction time, an appropriate amount of the mixed solution is added to a 96-well plate. The 96-well plate is placed in a dark box of a chemiluminescence analyzer, and an appropriate amount of luminol is added to initiate the reaction. The chemiluminescence intensity is recorded by the chemiluminescence analyzer to draw a working curve to achieve quantitative analysis of F-.
[0027] As an example, the amount of luminol used is 20 μL, and the concentration of the luminol solution is 50 mmol / L.
[0028] Compared with the prior art, the present invention has the following beneficial effects:
[0029] The present invention discloses a single-atom regulated chemiluminescence fluoride ion sensor, which synthesizes a single-atom copper catalyst and utilizes the reaction between calcium oxide and water to generate H2O2 in situ. The generated H2O2 can effectively generate hydroxyl radicals under the action of the single-atom copper catalyst, thereby greatly improving the luminous efficiency of the chemiluminescence system, avoiding the introduction of oxidants in the chemiluminescence system, and reducing the detection cost.
[0030] The disclosed single-atom regulated chemiluminescence sensor for detecting fluoride ions utilizes the specific chemical reaction between F- and silicon dioxide to improve the selectivity and accuracy of the chemiluminescence sensor; it can achieve high specificity, high sensitivity, and rapid detection of F- in samples; the detection of F- is fast and simple, and the reaction and results are automatically completed and recorded by the instrument, avoiding the influence of subjective factors and ensuring good repeatability, which is convenient for on-site detection. BRIEF DESCRIPTION OF THE DRAWINGS
[0031] The accompanying drawings constituting a part of the present disclosure are used to provide a further understanding of the present disclosure. The illustrative embodiments of the present disclosure and their descriptions are used to explain the present disclosure and do not constitute an improper limitation on the present disclosure.
[0032] Figure 1 This is a schematic diagram of the working principle of the chemiluminescent sensor detecting F- according to an embodiment of the present disclosure;
[0033] Figure 2 is a working curve of an embodiment of the present disclosure;
[0034] Figure 3 It is a selective comparison schematic diagram of an embodiment of the present disclosure. DETAILED DESCRIPTION
[0035] The present disclosure is further described below in conjunction with the accompanying drawings and embodiments.
[0036] It should be noted that the following detailed descriptions are all illustrative and are intended to provide further explanation of the present disclosure. Unless otherwise specified, all technical and scientific terms used herein have the same meanings as those commonly understood by those skilled in the art to which the present disclosure belongs.
[0037] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present disclosure. As used herein, unless the context clearly indicates otherwise, the singular form is also intended to include the plural form. In addition, it should be understood that when the terms "comprising" and / or "including" are used in this specification, it indicates the presence of features, steps, operations, devices, components and / or combinations thereof.
[0038] Example 1
[0039] In one embodiment of the present disclosure, a single-atom-regulated chemiluminescence sensor for detecting fluoride ions is provided, comprising silica microspheres, wherein a single-atom copper-calcium oxide nanoparticle composite material composed of a single-atom copper catalyst and calcium oxide nanoparticles is encapsulated in the silica microspheres.
[0040] As an embodiment, the preparation method of the silicon dioxide-encapsulated single-atom copper-calcium oxide nanoparticle composite material disclosed in the present invention comprises the following steps:
[0041] Synthesis of calcium oxide nanoparticles using a coprecipitation method;
[0042] The obtained single-atom copper catalyst and calcium oxide nanoparticles are dispersed in a silicon dioxide precursor solution to prepare a silicon dioxide-wrapped single-atom copper-calcium oxide nanoparticle composite material.
[0043] Specifically, the preparation process of the silica-encapsulated single-atom copper-calcium oxide nanoparticle composite material is as follows: a certain amount of single-atom copper catalyst and calcium oxide nanoparticles are dispersed in a certain volume of a mixed solution of water and ethanol, stirred and mixed, and then a certain amount of ammonia solution is added and continued to be stirred for a period of time, and finally a certain amount of tetraethyl orthosilicate is added and continued to be stirred and reacted for a period of time, and finally centrifuged and washed with ethanol, and then dried to obtain the silica-encapsulated single-atom copper-calcium oxide nanoparticle composite material.
[0044] Furthermore, the process of preparing the single-atom copper catalyst by high-temperature pyrolysis method includes:
[0045] First, set masses of melamine and cyanuric acid are dispersed in hot water respectively, stirred and mixed to obtain a hot cyanuric acid aqueous solution, then set masses of citric acid and copper acetate are weighed to prepare citric acid and copper acetate aqueous solutions, stirred and mixed to obtain a hot cyanuric acid aqueous solution, citric acid and copper acetate aqueous solutions are added to the hot cyanuric acid aqueous solution and stirred continuously, and then the mixed solution is added to the hot melamine aqueous solution, heated and stirred continuously, and the heating is stopped and stirred continuously. After the reaction is completed, the product is separated by centrifugation and precipitated, washed with water and ethanol in turn, and vacuum dried. The dried product is placed in a tubular furnace, and a programmed temperature is set under the protection of an inert gas, and calcined to obtain a single-atom copper catalyst.
[0046] The temperature was raised at a rate of 5°C / min under inert gas protection, and the reaction was continued at 600°C for 4 hours. After the reaction was completed, the temperature was raised to 620°C at a rate of 2°C / min and the reaction was continued for 2 hours. After the reaction was completed, the temperature was automatically cooled to room temperature.
[0047] Furthermore, the process of synthesizing calcium oxide nanoparticles using the co-precipitation method includes: stirring and mixing a set mass of sodium hyaluronate solution and a set mass of calcium chloride solution at room temperature, adding a set mass of sodium hydroxide solution to continue the reaction, then adding a set mass of H2O2 dropwise, continuing to stir the reaction at room temperature, centrifuging and washing with water, and finally freeze-drying to obtain a light yellow calcium oxide powder.
[0048] Among them, the mass concentration of sodium hyaluronate solution is 5 mg / mL; the concentration of calcium chloride solution aqueous solution is 2 mol / L.
[0049] As an embodiment, an application method of a single-atom regulated chemiluminescence sensor for detecting fluoride ions includes: dispersing the obtained silica-wrapped palladium nanoparticle-calcium oxide nanoparticle composite material into an aqueous solution containing F- at different concentrations, heating the reaction for a set time, adding an appropriate amount of the mixed solution to a 96-well plate, placing the 96-well plate in a dark box of a chemiluminescence analyzer, adding an appropriate amount of luminol to initiate the reaction, and recording the chemiluminescence intensity through the chemiluminescence analyzer to draw a working curve to achieve quantitative analysis of F-.
[0050] Example 2
[0051] In one embodiment of the present disclosure, a method for preparing a sensor for detecting fluoride ions by regulating chemiluminescence with a single atom is provided, wherein a single atom copper catalyst is prepared by a high temperature pyrolysis method.
[0052] As an embodiment, a method for preparing a composite material of single-atom copper-calcium oxide nanoparticles wrapped in silicon dioxide comprises the following steps:
[0053] Synthesis of calcium oxide nanoparticles using a coprecipitation method;
[0054] The obtained single-atom copper catalyst and calcium oxide nanoparticles are dispersed in a silicon dioxide precursor solution to prepare a silicon dioxide-wrapped single-atom copper-calcium oxide nanoparticle composite material.
[0055] As an embodiment, the high temperature cracking method for preparing a single-atom copper catalyst is as follows: first, 3.784 g of melamine and 3.098 g of cyanuric acid are dissolved and dispersed in 100 mL of 85°C water, 1.216 g of citric acid and 0.363 g of copper acetate are weighed and stirred to dissolve in 30 mL of water, the mixed solution of citric acid and copper acetate is added dropwise to the cyanuric acid solution, and stirring is continued at 85°C for 2 hours, and then the mixed solution obtained above is added dropwise to the 85°C melamine solution and stirring is continued for 30 minutes to mix evenly, and then the temperature of the mixed solution is lowered to room temperature and stirring is continued for 12 hours. After the reaction is completed, centrifuge at 9000 rpm for 10 minutes, wash with water and ethanol three times respectively, and place at 60°C for vacuum drying to obtain a single-atom copper catalyst precursor. Weigh 1.5 g of the single-atom copper catalyst precursor prepared above and place it in a porcelain boat. Put the porcelain boat into a tubular furnace, select argon as the protective gas, set the heating rate to 5°C / min and react at 600°C for 4 hours. After the reaction is completed, the temperature is increased to 620°C at 2°C / min and the reaction is continued for 2 hours. After the reaction is completed, it is automatically cooled to room temperature to obtain a black product, which is the single-atom copper catalyst.
[0056] Furthermore, the preparation process of the calcium oxide nanoparticles is as follows: 5 mL of a sodium hyaluronate solution with a mass concentration of 5 mg / mL and 2.5 mL of a 2 mol / L calcium chloride solution are stirred and mixed evenly at room temperature, and after stirring for 10 minutes, 5 mL of a 0.25 mol / L sodium hydroxide solution is added to continue the reaction, and then 200 μL of a 30% H2O2 is added dropwise, and the reaction is continued at room temperature for 30 minutes by stirring, centrifuged at 10000 rpm for 10 minutes, washed with water 3 times, and finally freeze-dried to obtain a light yellow powder, which is the calcium oxide nanoparticles.
[0057] Furthermore, the preparation process of the silica-encapsulated single-atom copper-calcium oxide nanoparticle composite material is as follows: 5 mg of single-atom copper catalyst and 20 mg of calcium oxide nanoparticles are dispersed in 30 mL of a mixed solution of water and ethanol with a volume ratio of 1:2, stirred for 10 minutes to disperse evenly, then 1.5 mL of ammonia solution with a mass concentration of 25% is added and stirring is continued for 30 minutes, and finally 5 mL of tetraethyl orthosilicate is added and stirring is continued for 2 hours, and finally centrifuged at 8000 rpm for 10 minutes and washed with ethanol 3 times, and dried at 60°C to obtain the silica-encapsulated single-atom copper-calcium oxide nanoparticle composite material.
[0058] Furthermore, the process of F-analysis and detection is as follows: first, 10 mg of the above-mentioned silica-wrapped single-atom copper-calcium oxide nanoparticle composite material is distributed into 10 mL of F-containing aqueous solution of different concentrations, and the solution is reacted at 60°C for 30 minutes. 500 μL of the reacted solution is taken into a 96-well microplate with a pipette, and the 96-well plate is placed in a dark box of a chemiluminescence analyzer, and 20 μL of 50 mmol / L luminol is added to initiate the reaction. The chemiluminescence intensity is recorded by the chemiluminescence analyzer to draw a working curve, thereby realizing the quantitative analysis of F-.
[0059] Example 3
[0060] In one embodiment of the present disclosure, an application of a single-atom-regulated chemiluminescence sensor for detecting fluorine ions is provided. The single-atom-regulated chemiluminescence sensor for detecting fluorine ions is applied in quantitative analysis and measurement of F ions.
[0061] Example 4
[0062] In one embodiment of the present disclosure, a method for measuring F ions using a single-atom controlled chemiluminescence detection fluoride ion sensor is provided, comprising:
[0063] (1) dispersing the sensor according to claim 1 into a F-solution to be tested for reaction;
[0064] (2) Place an appropriate amount of reaction solution in a 96-well microplate;
[0065] (3) adding luminol solution;
[0066] (4) The chemiluminescence intensity was measured using a chemiluminescence analyzer.
[0067] Specifically, the obtained silica-coated palladium nanoparticle-calcium oxide nanoparticle composite material is dispersed into aqueous solutions containing F- at different concentrations. After heating for a set reaction time, an appropriate amount of the mixed solution is added to a 96-well plate. The 96-well plate is placed in a dark box of a chemiluminescence analyzer, and an appropriate amount of luminol is added to initiate the reaction. The chemiluminescence intensity is recorded by the chemiluminescence analyzer to draw a working curve, thereby achieving quantitative analysis of F-.
[0068] Specifically, first, 10 mg of the above-obtained silica-wrapped single-atom copper-calcium oxide nanoparticle composite material was distributed into 10 mL of F-containing aqueous solution of different concentrations, and the solution was reacted at 60°C for 30 min. 500 μL of the reacted solution was taken into a 96-well microplate with a pipette, and the 96-well plate was placed in a dark box of a chemiluminescence analyzer. 20 μL of 50 mmol / L luminol was added to initiate the reaction. The chemiluminescence intensity was recorded by the chemiluminescence analyzer to draw a working curve, thereby achieving quantitative analysis of F-.
[0069] Although the above describes the specific implementation methods of the present disclosure in conjunction with the accompanying drawings, it is not intended to limit the scope of protection of the present disclosure. Technical personnel in the relevant field should understand that on the basis of the technical solution of the present disclosure, various modifications or variations that can be made by those skilled in the art without creative work are still within the scope of protection of the present disclosure.
Claims
1. A single-atom chemiluminescence sensor for detecting fluoride ions, characterized in that: The invention comprises silicon dioxide microspheres, wherein a single-atom copper-calcium oxide nanoparticle composite material composed of a single-atom copper catalyst and calcium oxide nanoparticles is encapsulated in the silicon dioxide microspheres.
2. A method for preparing a single-atom controlled chemiluminescence sensor for detecting fluoride ions as claimed in claim 1, characterized in that: The preparation process of the single-atom copper-calcium oxide nanoparticle composite material composed of single-atom copper catalyst and calcium oxide nanoparticles includes the following steps: Synthesis of calcium oxide nanoparticles using a coprecipitation method; The single-atom copper catalyst and the obtained calcium oxide nanoparticles are dispersed in a silicon dioxide precursor solution to prepare a silicon dioxide-wrapped single-atom copper-calcium oxide nanoparticle composite material.
3. The method for preparing a single-atom controlled chemiluminescence sensor for detecting fluoride ions as claimed in claim 2, characterized in that: The single-atom copper catalyst is prepared by high-temperature pyrolysis method, and the process includes: First, melamine and cyanuric acid are dispersed in hot water respectively, and stirred to mix evenly to obtain a hot cyanuric acid aqueous solution. Subsequently, citric acid and copper acetate are configured to form a citric acid and copper acetate aqueous solution, and stirred to mix evenly. The citric acid and copper acetate aqueous solutions are added to the hot cyanuric acid aqueous solution and continue to be stirred. The mixed solution is then added to the hot melamine aqueous solution, heated and continued to be stirred, and the heating is stopped and then continued to be stirred. After the reaction is completed, centrifugal separation and precipitation are performed, and the product is washed with water and ethanol in turn, and vacuum dried. The dried product is placed in a tubular furnace, and a programmed temperature is set under the protection of an inert gas, and calcined to obtain a single-atom copper catalyst.
4. The method for preparing a single-atom controlled chemiluminescence sensor for detecting fluoride ions as claimed in claim 2, characterized in that: The process of synthesizing calcium oxide nanoparticles using the coprecipitation method includes: stirring and mixing the sodium hyaluronate solution and the calcium chloride solution at room temperature, adding the sodium hydroxide solution to continue the reaction, then adding H2O2 dropwise, continuing to stir the reaction at room temperature, centrifuging and washing with water, and finally freeze-drying to obtain a light yellow calcium oxide powder.
5. The method for preparing a single-atom controlled chemiluminescence sensor for detecting fluoride ions as claimed in claim 3, characterized in that: Under the protection of inert gas, the program temperature rise rate is set to 2-10℃ / min, the heating time is 50-120min, the reaction is carried out at 600℃ for 2-5h, after the reaction is completed, the temperature is increased to 620℃ at 1-5℃ / min and the reaction is continued for 1-2h, and the reaction is automatically cooled to room temperature after completion.
6. The method for preparing a single-atom controlled chemiluminescence sensor for detecting fluoride ions as claimed in claim 4, characterized in that: The mass concentration of the sodium hyaluronate solution is 1-10 mg / mL; the concentration of the calcium chloride solution is 1-5 mol / L.
7. An application of a single-atom regulated chemiluminescence sensor for detecting fluoride ions, characterized in that: The single-atom regulated chemiluminescence fluoride ion detection sensor described in claim 1 is used in the quantitative analysis and measurement of F ions.
8. A method for measuring F ions by using a single-atom chemiluminescence sensor to detect fluoride ions, characterized in that: (1) dispersing the sensor according to claim 1 into a F-solution to be tested for reaction; (2) Place an appropriate amount of reaction solution in a 96-well microplate; (3) adding luminol solution; (4) The chemiluminescence intensity was measured using a chemiluminescence analyzer.
9. The method for measuring F ions by using a single-atom controlled chemiluminescence detection fluoride ion sensor as claimed in claim 8, characterized in that: The obtained silica-coated palladium nanoparticle-calcium oxide nanoparticle composite material is dispersed into aqueous solutions containing F- at different concentrations. After heating for a set reaction time, an appropriate amount of the mixed solution is added to a 96-well plate. The 96-well plate is placed in a dark box of a chemiluminescence analyzer, and an appropriate amount of luminol is added to initiate the reaction. The chemiluminescence intensity is recorded by the chemiluminescence analyzer to draw a working curve to achieve quantitative analysis of F-.
10. The method for measuring F ions by using a single-atom controlled chemiluminescence detection fluoride ion sensor as claimed in claim 9, characterized in that: The amount of luminol used is 20 μL, and the concentration of the luminol solution is 50 mmol / L.