A manganese monatomic modified electrode, a preparation method thereof, an electrochemical sensor and application thereof

Abstract

The application belongs to the technical field of electrochemical sensing materials and environmental pollutant detection, and discloses a manganese monatomic modified electrode and a preparation method, an electrochemical sensor and application thereof, which comprises the following steps: (1) manganese acetate and 1,10-phenanthroline are dissolved in a solvent, and stirring is performed to fully carry out complexation reaction, so as to obtain a complex, then carbon black is added, continuous stirring is performed to uniformly disperse the carbon black, and heating is performed at a temperature lower than the boiling point of the solvent, so as to obtain a precursor complex; (2) the precursor complex is heated to remove the solvent, so as to obtain a black solid, after grinding, calcination is performed under a protective atmosphere, so as to obtain a manganese monatomic catalyst; and (3) the manganese monatomic catalyst is loaded on a conductive substrate to prepare a manganese monatomic modified electrode. The electrode exhibits a significant electrocatalytic response to PFOS, has high sensitivity and selectivity, can realize rapid and stable detection of PFOS, and has a detection limit as low as 0.13 nM, and the application has simple process and low cost.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of electrochemical sensing materials and environmental pollutant detection, and particularly relates to a manganese monatomic modified electrode and preparation of an electrochemical sensor and application thereof in detection of perfluorooctane sulfonic acid. BACKGROUND

[0002] Perfluorooctane sulfonic acid (PFOS) is a typical perfluoro / polyfluoroalkyl substance (PFAS). Due to its excellent chemical stability, heat resistance and surface activity, PFOS is widely used in industrial fields such as waterproof coating, fire-fighting foam and semiconductor manufacturing. However, PFOS is difficult to degrade in the environment and is easy to accumulate in water bodies and organisms, belonging to persistent organic pollutants. Studies have shown that PFOS has hepatotoxicity, immunotoxicity and reproductive toxicity, and may interfere with the endocrine system, posing a serious threat to the ecosystem and human health. Electrochemical sensors have great potential in the field of environmental pollutant detection due to their rapid response, low cost, simple operation and easy miniaturization. In particular, in terms of working electrode materials, nano materials with high catalytic activity and strong stability are widely studied to improve detection performance.

[0003] Molecularly imprinted polymer (MIPs) electrochemical sensors have become an effective tool for PFOS detection, which realizes target detection through template imprinting-specific recognition-signal conversion. First, a complex of functional monomers (such as pyrrole, acrylic acid) and template molecules (such as PFOS) is electropolymerized on the electrode surface, and after eluting the template, a MIPs film with complementary cavities is formed. During detection, the target molecules selectively bind to the cavities, changing the electrode interface properties, and the quantification is achieved by differential pulse voltammetry (DPV) or electrochemical impedance spectroscopy (EIS). Although this method has good selectivity and low detection limit, there are some defects that cannot be ignored in this type of sensor: first, the preparation process of MIPs film is complex, and the polymerization conditions and template washing requirements are high, and if the template molecules are not completely removed, it may cause false response; second, the conductivity of the polymer imprinting layer itself is poor, and it needs to be combined with conductive materials to enhance the signal response; finally, due to the complexity of the template molecule introduction and elution process in molecular imprinting polymerization, the performance of batch products varies greatly, and more importantly, the recognition sites of this type of sensor are easy to be deactivated due to pollution, structure collapse or target molecule "occupation" during repeated use, resulting in a decrease in response signal and relatively poor cyclic use performance, which is not suitable for batch production and long-term or high-frequency detection applications.

[0004] Chinese patent application with publication number CN 117538394 A develops an ultra-sensitive voltammetric sensor for detecting perfluorooctane sulfonic acid in tap water by modifying AuNS and MIP thin coating, wherein the AuNS coating is used to enhance the redox probe of the selected FcCOOH for Fe 2+The voltammetric response of the blank signal intensity during oxidation is obtained, and the MIP electropolymerization process is optimized to minimize the potential passivation of the electrode surface and saturation of the analyte, thereby solving the problem of poor reusability of the sensor. However, the preparation process is complicated, and the cost of the nanofunctional modification step is high, resulting in high overall production cost, which seriously restricts the large-scale and industrial application. SUMMARY

[0005] In view of the problems of complex preparation process and poor material stability in the prior art, the primary object of the present application is to provide a manganese single-atom modified electrode material. By constructing a manganese single-atom catalyst with atomically dispersed metal sites, the reaction site utilization rate and electron transport efficiency can be significantly improved, thereby realizing efficient identification and signal amplification of target pollutants. The manganese single-atom catalyst takes Mn-N4 structure as the active center and is loaded on a conductive carbon-based material to form an electrode material layer. Through the high dispersion of single-atom sites and electrochemical activity, the manganese single-atom catalyst can efficiently catalyze the redox process of PFOS.

[0006] Another object of the present application is to provide an electrochemical sensor composed of a working electrode, a counter electrode, a reference electrode, an electrolytic cell and an electrochemical workstation, wherein the working electrode is the manganese single-atom modified electrode described above.

[0007] Still another object of the present application is to provide the application of the electrode and the electrochemical sensor described above in PFOS detection.

[0008] To achieve the above objects, the technical solutions of the present application are as follows:

[0009] A preparation method of a manganese single-atom modified electrode, comprising the following steps:

[0010] (1) Dissolve manganese acetate and 1,10-phenanthroline in a solvent, stir to fully complex, obtain a complex, then add carbon black, continuously stir to uniformly disperse, and heat at a temperature lower than the boiling point of the solvent to obtain a precursor complex;

[0011] (2) Heat the precursor complex to remove the solvent and obtain a black solid, grind, and calcine under a protective atmosphere to obtain a manganese single-atom catalyst (Mn-SAC) with Mn-N4 as the active site;

[0012] (3) Load the manganese single-atom catalyst on a conductive substrate to prepare a manganese single-atom modified electrode.

[0013] Preferably, the mass ratio of manganese acetate, 1,10-phenanthroline and carbon black in step (1) is 1: (6±4): (70±20); the calcination conditions in step (2) are as follows: heat to 600±200℃ in a programmed temperature mode, time 1-4 hours; the programmed temperature mode is 10±5℃ / min.

[0014] Preferably, the concentration of the manganese acetate in the solvent in step (1) is 0.02-0.06 mol / L; and the calcination conditions in step (2) are: temperature of 600±100℃, and holding time of 2-3 h.

[0015] Preferably, the heating temperature in step (1) is 60±10℃, and the heating time is 4±2 h; the solvent is methanol or ethanol; the stirring time of the complexation reaction is 30±10 min; and the heating conditions in step (2) are: heating at 80-100℃ for 12±2 h.

[0016] Preferably, the preparation of the manganese monatomic modified electrode in step (3) is: dispersing the manganese monatomic catalyst in a mixed solution of ethanol and water, then adding a Nafion solution, ultrasonic dispersion to obtain a suspension, coating the suspension on the surface of a conductive substrate, and drying to obtain the manganese monatomic modified electrode.

[0017] Preferably, the ratio of the manganese monatomic catalyst to the mixed solution of ethanol and water is 0.5-4.0 mg / mL; and the volume ratio of the ethanol to water is 1:2-2:1.

[0018] Preferably, the volume-to-mass ratio of the Nafion solution to the manganese monatomic catalyst is 5-30 μL / mg, and the mass concentration of the Nafion solution is 1-10%.

[0019] Preferably, the ultrasonic dispersion power is 50-100 W, and the time is 1-2 h.

[0020] Preferably, the suspension is coated on the surface of the conductive substrate in an amount of 50-150 μL / cm 2 , and more preferably in an amount of 70-100 μL / cm 2 .

[0021] Preferably, the conductive substrate is a glassy carbon electrode, a conductive glass electrode, or a carbon cloth electrode.

[0022] An electrochemical sensor is prepared by using the manganese monatomic modified electrode prepared by the above method as a working electrode.

[0023] The electrochemical sensor comprises the manganese monatomic modified electrode (working electrode), a counter electrode (platinum wire), a reference electrode (calomel electrode), an electrolytic cell, and an electrochemical workstation.

[0024] The manganese monatomic modified electrode or the electrochemical sensor is used for rapid detection of perfluorinated compounds. Preferably, a PBS buffer with a pH of 5-9 is used as an electrolyte for detection.

[0025] The electrode or electrochemical sensor is used for detecting PFOS. Preferably, a PBS solution with pH of 5-9 is used as an electrolyte, and the concentration is 0.1±0.05 mol / L.

[0026] The present application has unique advantages in the process of preparing the high-efficiency electrochemical sensor with the manganese monatomic catalyst, including: the present application realizes high-sensitivity detection of PFOS by using differential pulse voltammetry (DPV) combined with a manganese monatomic modified electrode. The core of the detection process lies in: adsorption and electron transfer behavior of PFOS molecules on the surface of the working electrode, and high-resolution identification ability of DPV to weak electrochemical signals. Differential pulse voltammetry is a high-sensitivity electrochemical detection technology, and its working principle is: a series of periodic pulse voltages are superimposed on the basis of a certain scanning potential, the current change before and after each pulse is measured, and the interference of non-faradic current (background current) is removed by difference, so that the electrochemical response signal of the target substance is significantly enhanced. DPV responds quickly to weak current changes, and is particularly suitable for quantitative analysis of trace pollutants. In the present application, the surface of the manganese monatomic modified electrode has rich electrochemically active sites, and has good electron conductivity and interface reaction activity. When PFOS molecules are introduced into the solution, the functional groups such as sulfonic acid groups of the PFOS molecules are adsorbed on the surface of the modified electrode by electrostatic interaction or hydrogen bond interaction, so that the concentration of the PFOS molecules at the electrode / solution interface is significantly increased. With the application of pulse voltage, the PFOS molecules undergo electrochemical response at a specific potential, and the electrons are captured or transferred at the active center to form a measurable current signal. Due to the presence of strong electronegative fluorine elements and polar groups in the structure of the PFOS molecules, this electron exchange process can be manifested as oxidation or reduction peaks on the manganese monatomic modified electrode, and the intensity of the response signal has a good linear relationship with the concentration of PFOS. In addition, the high activity, high dispersity and stability of the manganese monatomic catalyst ensure the consistency of the signal output and the repeatability of the detection results, and the prepared electrode has no obvious attenuation in multiple cycle tests, and is suitable for long-period application.

[0027] Compared with the prior art, the present application has the following advantages and beneficial effects:

[0028] (1) Compared with the traditional molecular imprinting electrode, manganese is uniformly distributed in the form of monatomic on the carbon-based carrier to form a stable Mn-N4 coordination structure, which can greatly improve the electron transfer efficiency and the catalytic oxidation ability of the target molecules, and realize rapid identification and detection of PFOS.

[0029] (2) The manganese monatomic modified electrode constructed by the application has efficient electron transmission capacity and rich active sites, can significantly enhance the adsorption and response signal intensity of PFOS on the electrode surface, has high sensitivity and selectivity in combination with DPV accurate identification of current change, realizes sensitive detection of trace PFOS, and the detection limit can be as low as 0.13 nM, which is superior to most existing electrochemical detection technologies.

[0030] (3) The manganese monatomic catalyst of the application has strong thermal stability and good dispersity, is not easy to agglomerate and deactivate, the prepared electrode still has excellent signal reproducibility in multiple cycle tests, is suitable for batch preparation and long-term application, and is particularly suitable for on-site rapid analysis and high-throughput detection tasks. BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 It is a TEM morphology diagram of the manganese monatomic catalyst Mn-SACs prepared in Example 1 (a); and XRD patterns of manganese monatomic catalyst (Mn-SACs) and carbon black (b).

[0032] Figure 2 It is a Mn k-edge XANES spectrum (a) and Fourier transform spectrum (b) of the manganese monatomic catalyst Mn-SACs, manganese foil, MnO and MnO2 prepared in Example 1.

[0033] Figure 3 It is an EXAFS r-space fitting curve of the manganese monatomic catalyst Mn-SACs prepared in Example 1.

[0034] Figure 4 It is a differential pulse voltammetry peak current diagram of the manganese monatomic / boron-doped diamond electrode in Example 1 for detecting PFOS in different pH buffer solutions.

[0035] Figure 5 It is a cyclic voltammetry curve diagram of different electrodes for detecting PFOS.

[0036] Figure 6 It is a differential pulse voltammetry curve diagram of different electrodes for detecting PFOS.

[0037] Figure 7 It is a differential pulse voltammetry curve diagram (a) of the manganese monatomic / boron-doped diamond electrode in Example 1 for detecting different concentrations of PFOS; and a linear relationship diagram (b) thereof.

[0038] Figure 8 It is a repeated use performance test diagram of the manganese monatomic / boron-doped diamond electrode in Example 1.

[0039] Figure 9 It is a performance test diagram of four manganese monatomic modified electrodes prepared in the repeated Example 1.

[0040] Figure 10 Figure 2 shows the DPV peak current chart of Example 1 for detecting PFOS in the presence of different interfering ions. DETAILED DESCRIPTION

[0041] The present application will be further described in conjunction with the examples and the accompanying drawings, but the embodiments of the present application are not limited thereto. The room temperature described in the present application is 20-30°C.

[0042] Example 1

[0043] (1) 19.8 mg of manganese (II) acetate tetrahydrate and 101.9 mg of 1,10-phenanthroline monohydrate were dissolved in 2 mL of ethanol, and stirred at room temperature for 20 min to allow sufficient complexation reaction to occur, to obtain a complex. Then 69.6 mg of conductive carbon black was added, and stirred at 600 rpm for 20 min to allow uniform dispersion, and then the obtained mixture was placed in an oil bath at 60°C for heating reaction for 4 h to form a stable precursor complex. After the reaction, the precursor complex was heated at 80°C for 12 h to remove the solvent, to obtain a black solid. The dried black solid was gently ground and transferred to a ceramic crucible, and placed in a tube furnace, and heated to 600°C at a rate of 10°C / min under an argon atmosphere, and reacted at this temperature for 2 h. After natural cooling to room temperature, a manganese single-atom catalyst was obtained.

[0044] (2) 4 mg of the manganese single-atom catalyst was dispersed in 2 mL of a mixed solution of water and ethanol in a volume ratio of 1:1, 40 μL of a 5% mass concentration Nafion solution was added, and a uniform black suspension was obtained after 100 W ultrasonic dispersion for 1 h. 7 μL of the suspension was dropped on the surface of a glassy carbon electrode (diameter 3 mm) using a 10 μL microinjector, and the coating amount of the suspension was about 100 μL / cm 2 at room temperature, to obtain a manganese single-atom / glassy carbon electrode.

[0045] In Example 1, the TEM morphology chart and XRD spectrum of the manganese single-atom catalyst are shown in Figure 1 It can be clearly seen that the manganese single atoms exhibit irregular granular particles, and no metal or clusters are observed on the surface, indicating that the manganese ions exist in the form of single atoms in the Mn-SAC. Figure 1 (b) in Figure 1 is the XRD spectrum of carbon black (CB) and manganese single atoms (i.e. catalyst Mn-SAC), and the diffraction peaks of Mn-SAC are almost the same as those of CB. No additional peaks are generated in Mn-SAC on the basis of the CB curve, only the change that the peak value at the original peak of the CB curve becomes larger, which represents the successful preparation of Mn-SAC, without the influence of other impurities.

[0046] Figure 2The electronic structure and coordination environment of Mn-SACs were analyzed using XANES and EXAFS. Figure 2 As shown in (a), Mn-SACs exhibit a higher absorption edge than the Mn foil, indicating an enhanced oxidation state of manganese atoms. The absorption edge of Mn-SACs falls between that of the Mn foil and MnO, indicating the presence of Mn(II). Figure 2 As shown in (b), Mn-SACs do not show a peak at 2.3 Å corresponding to the Mn-Mn bonds in the Mn foil, indicating that Mn is dispersed in a single-atom form. Similarly, comparison with MnO and MnO2 shows that Mn-O bonds are absent in Mn-SACs. Mn-SACs show a peak at around 1.6 Å, indicating the presence of Mn-N bonds.

[0047] Figure 3 Structural features were further extracted through quantitative EXAFS fitting of the Mn K-side. The fitting results showed that the first coordination shell of Mn is mainly composed of 4 N atoms, further confirming the Mn-N4 configuration.

[0048] The application of the electrode prepared in Example 1 in the detection of PFOS is as follows: The detection was performed in a conventional three-electrode system, using a platinum wire electrode as the counter electrode, a calomel electrode as the reference electrode, and the manganese single-atom / glassy carbon electrode prepared in Example 1 as the working electrode. 0.1 mol / L PBS buffer solutions containing 10 nmol / L PFOS at different pH values ​​were used as the electrolyte solution, and an electrochemical workstation was used as the detection instrument. The working electrode was first polished on α-alumina polishing powder with a particle size of 50 nm, and then ultrasonically washed sequentially with anhydrous ethanol and deionized water. During the detection of PFOS, the manganese single-atom modified electrochemical sensor used differential pulse voltammetry to scan the redox reaction of PFOS and record the voltage-current curves of this process.

[0049] from Figure 4 It can be seen that the current density of PFOS detection by differential pulse voltammetry is significantly affected by the pH value of the PBS buffer. The current density measured by differential pulse voltammetry is much higher at pH 7 and 9. Considering the actual pH value of the human body, a PBS buffer with pH=7 was chosen for subsequent experiments.

[0050] Figure 5 Cyclic voltammetry curves of 10 nmol / L PFOS were obtained for a three-electrode system under different working electrode conditions (glassy carbon electrode, carbon black / glassy carbon electrode, and manganese single atom / glassy carbon electrode of Example 1) in 0.1 mol / L PBS buffer (pH=7). The carbon black / glassy carbon electrode was prepared by first preparing a carbon black suspension (method as described in Example 1), which was then drop-coated onto a bare glassy carbon electrode. Figure 5As can be seen from the figure, the peak current of the manganese monatomic / glassy carbon electrode is significantly increased compared with the glassy carbon electrode (GCE) and the carbon black / glassy carbon electrode, indicating that Mn-SAC can promote faster electron transfer and significantly enhance the redox peak current signal.

[0051] Figure 6 The differential pulse voltammograms of the glassy carbon electrode, the carbon black / glassy carbon electrode and the manganese monatomic / glassy carbon electrode in a solution of 10 nmol / L PFOS+0.1 mol / L PBS (pH=7) are shown in the figure. The specific detection steps are as follows: in a three-electrode system, a platinum wire electrode is used as the counter electrode, a calomel electrode is used as the reference electrode, and a glassy carbon electrode, a carbon black / glassy carbon electrode and the manganese monatomic / glassy carbon electrode of Example 1 are used as the working electrode. A 0.1 mol / L PBS buffer solution containing 10 nmol / L PFOS is used as the electrolyte solution, and an electrochemical workstation is used as the detection instrument. The differential pulse voltammetry potential scanning detection is performed. Figure 6 As can be seen from the figure, the glassy carbon electrode and the carbon black / glassy carbon electrode alone have no response to PFOS, and the manganese monatomic / glassy carbon electrode has an obvious detection peak of PFOS at about-0.4 V. This phenomenon may be attributed to the fact that the manganese monatomic has excellent photogenerated carrier separation efficiency, so the manganese monatomic modified electrode has excellent differential pulse voltammetry detection signal.

[0052] Figure 7 The differential pulse voltammograms of the manganese monatomic / glassy carbon electrode of Example 1 for detecting PFOS with different concentrations are shown in the figure. The specific detection steps are as follows: in a three-electrode system, a platinum wire electrode is used as the counter electrode, a calomel electrode is used as the reference electrode, and a glassy carbon electrode, a carbon black / glassy carbon electrode and the manganese monatomic / glassy carbon electrode are used as the working electrode. A 0.1 mol / L PBS buffer solution (pH=7) is used as the electrolyte solution, and the electrolyte solution contains PFOS with different concentrations (0-50 nmol / L). An electrochemical workstation is used as the detection instrument, and the differential pulse voltammetry potential scanning detection is performed. Figure 7 As shown in (a) of the figure, the manganese monatomic / glassy carbon electrode shows a stable and clear differential pulse voltammetry response peak of the oxidation of PFOS in the electrolyte solution, and the peak current of the detection peak is gradually increased with the increase of the concentration of PFOS, and different linear relationships are shown in different concentration ranges. As shown in (b) of the figure, Figure 7 The linear regression equations of PFOS are I1=25.671+13.696lgC (R 2 =0.991) and I2=25.318+2.755lgC (R 2 =0.991); wherein C (nmol / L) is the concentration of PFOS, and I (μA) is the peak current of different concentrations. Based on the signal-to-noise ratio S / N=3 of PFOS detection as the standard of the detection limit, the detection limit is calculated by the following formula:

[0053] Detection limit = 3.3σ / S

[0054] Where σ is the noise standard deviation of the response of the blank sample, and S is the slope of the calibration curve, that is, the rate of change of the response signal of the measured substance with its concentration. S takes the slope of I1, σ = 0.536, and the detection result is calculated according to the formula, and the detection limit of PFOS is 0.13 nM.

[0055] The detection range corresponding to the first linear equation (I1) is 0.15-1nM, and the detection range corresponding to the second linear equation (I2) is 1-50nM.

[0056] From Figure 8 It can be seen that after 20 continuous operations using the same electrode, the peak current of PFOS shows a weak change. Therefore, the manganese monatomic working electrode has good recycling performance.

[0057] Figure 9 The four manganese monatomic modified electrodes prepared in Example 1 were used to detect 10 nmol / L PFOS, and the peak current of PFOS showed a weak change. Therefore, the preparation method of the electrode of the present application has good reproducibility and is suitable for batch production.

[0058] From Figure 10 It can be seen that after adding 100 times the concentration of interfering ions to the PFOS with a concentration of 10 nmol / L, there is no obvious change in current response, and therefore the manganese monatomic working electrode has good anti-interference ability.

[0059] In summary, by constructing a manganese monatomic modified electrode combined with DPV detection technology, the present application realizes efficient adsorption, selective recognition and sensitive response of PFOS, and establishes a rapid, stable and low-cost electrochemical sensor for environmental pollutants.

[0060] The above examples are the preferred embodiments of the present application, but the embodiments of the present application are not limited by the above examples, and any changes, modifications, substitutions, combinations and simplifications made without departing from the spirit and principles of the present application shall be equivalent replacement modes and shall be included in the protection scope of the present application.

Claims

1. Use of a manganese monoadatom-modified electrode for rapid detection of perfluorinated compounds, characterized in that, The preparation method of the manganese monatomic modified electrode comprises the following steps: (1) manganese acetate and 1,10-phenanthroline are dissolved in a solvent, and stirred to fully complex, to obtain a complex, then carbon black is added, continuously stirred to uniformly disperse, and heated at a temperature lower than the boiling point of the solvent to obtain a precursor complex; (2) the precursor complex is heated to remove the solvent to obtain a black solid, which is ground and calcined in a protective atmosphere to obtain a manganese monatomic catalyst; (3) the manganese monatomic catalyst is loaded on a conductive substrate to prepare a manganese monatomic modified electrode.

2. Use according to claim 1, characterized in that, In step (1), the mass ratio of manganese acetate, 1,10-phenanthroline and carbon black is 1:(6±4):(70±20); in step (2), the calcination condition is: temperature 600±200℃, time 1-4 hours.

3. Use according to claim 2, characterized in that, In step (1), the concentration of manganese acetate in the solvent is 0.02-0.06 mol / L; in step (2), the calcination condition is: temperature 600±100℃, time 2-3 hours.

4. Use according to claim 3, characterized in that, In step (1), the heating temperature is 60±10℃, and the heating time is 4±2 hours; the solvent is methanol or ethanol; the stirring time of the complex reaction is 30±10 minutes; in step (2), the heating condition is heating at 80-100℃ for 12±2 hours.

5. The use according to any one of claims 1 to 4, characterized in that, In step (3), the preparation of the manganese monatomic modified electrode: the manganese monatomic catalyst is dispersed in a mixed solution of ethanol and water, then a Nafion solution is added, ultrasonic dispersion is performed to obtain a suspension, the suspension is coated on the surface of a conductive substrate, and a manganese monatomic modified electrode is obtained after drying.

6. Use according to claim 5, characterized in that, The solid-liquid ratio of the manganese monatomic catalyst to the mixed solution of ethanol and water is 0.5-4.0 mg / mL; the volume ratio of ethanol to water is 1:2-2:1; the volume-mass ratio of the Nafion solution to the manganese monatomic catalyst is 5-30 μL / mg, and the mass concentration of the Nafion solution is 1-10%; The power of the ultrasonic dispersion is 50-100 W, and the time is 1-2 h; the suspension is coated on the surface of the conductive substrate in an amount of 50-150 μL / cm 2 . The conductive substrate is a glassy carbon electrode, conductive glass or carbon cloth electrode.

7. Use of an electrochemical sensor for the rapid detection of perfluorinated compounds, characterized in that, An electrochemical sensor is prepared by taking the manganese monatomic modified electrode prepared by any one of claims 1-6 as a working electrode.

8. The use according to any one of claims 1 to 4, characterized in that, A PBS buffer with pH 5-9 is used as an electrolyte for detection.

9. Use according to claim 5, characterized in that, A PBS buffer with pH 5-9 is used as an electrolyte for detection.

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