A perchlorate-selective electrode based on electronic / ionic dual-channel material and a preparation method thereof

Abstract

The application discloses a perchlorate selective electrode based on an electronic / ion dual-channel material and a preparation method thereof. The application synthesizes an electronic / ion dual-channel material by polymerizing part of polypyrrole on the surface of Mxene and introducing a long-chain alkyl-substituted quaternary ammonium salt. The material combines the dual-channel characteristics of ion enrichment and conductivity, and can significantly improve the detection capability for perchlorate. Experimental results show that the perchlorate selective electrode made of the dual-channel material has extremely strong selectivity and ultra-low detection limit for perchlorate, and the minimum detection limit can reach 12.4 mu g / L. At the same time, the response time is extremely fast (about 4 s), so that the sensitive and rapid detection of perchlorate under complex water conditions can be realized. The perchlorate selective electrode provided by the application has the characteristics of wide detection linear range, low detection limit, strong anti-interference ability, simple operation, high efficiency, fast speed, low cost and the like when detecting perchlorate. Therefore, the application has wide application prospect.

Description

Technical Field

[0001] The present invention belongs to the technical field of electrochemical detection, and in particular relates to a perchlorate selective electrode based on an electron / ion dual-channel material and a preparation method thereof. Background Art

[0002] Perchlorate (ClO⁻), a strongly oxidizing anion, has been widely used in industry, the military, and other fields due to its unique chemical and physical properties. In particular, as a key component in the production and use of high-energy materials such as rocket propellants, fireworks, and explosives, perchlorate plays an irreplaceable role. In recent years, with the rapid development of these technologies and products, the production and use of perchlorate has increased significantly. However, this has also led to a continuous increase in its emissions, becoming a significant environmental concern.

[0003] Perchlorate's exceptional chemical stability and high water solubility make it extremely difficult to degrade under natural conditions. Once it enters the environment through industrial wastewater discharge, propellant leaks, or improper waste disposal, it easily accumulates and spreads in soil and water. Furthermore, perchlorate is widely distributed in the environment worldwide. Surveys have shown that perchlorate has been detected in surface water and groundwater in many regions, with concentrations in some cases exceeding safety limits.

[0004] However, detecting perchlorate in water faces numerous challenges. First, the extremely low threshold requires detection methods with exceptional sensitivity and accuracy. Second, the complex chemical environment in water and interference from other anions make selective identification of perchlorate extremely difficult. Therefore, the development of an efficient, rapid, and low-cost perchlorate detection method is urgently needed.

[0005] Currently, the methods used for perchlorate detection mainly include: electrochemical detection, mass spectrometry, fluorescence sensing and ion chromatography. Among them,

[0006] Electrochemical detection methods have attracted widespread attention due to their advantages, including simple equipment, rapid response, and ease of miniaturization. Using specially modified electrodes, the accumulation of perchlorate on the electrode surface can be accurately detected. However, this detection method is sensitive to interfering ions in complex water bodies and its lack of selectivity limits its application. Therefore, further improving the performance of modified materials is a viable solution to perchlorate sensing.

[0007] Mass spectrometry is also known for its high sensitivity, making it particularly suitable for detecting ultra-trace levels of perchlorate. However, this method is expensive, has high detection costs, and is complex to operate, making it difficult to apply to routine water quality monitoring or resource-constrained areas.

[0008] Fluorescence sensing technology has become a research hotspot for perchlorate detection due to its high sensitivity, rapid response, and visualization. By designing specific fluorescent probes, fluorescence sensing technology can detect perchlorate with high selectivity and has potential for portable applications. However, existing fluorescence sensing methods still face several challenges in practical applications, such as insufficient environmental stability of the probes and limited recognition of interfering ions.

[0009] Ion chromatography is the most commonly used method for analyzing perchlorate ion substances due to its high efficiency, sensitivity and reliability. The detection limit of perchlorate can reach 10μg / L. However, this method has disadvantages such as long detection time (>30min) and the need for sample pretreatment.

[0010] Due to the presence of high concentrations (g / L) of interfering ions in water, traditional detection methods face significant challenges in accurately detecting low concentrations (μg / L) of perchlorate in raw water. Detection of perchlorate in raw water requires not only high selectivity but also an extremely low detection limit, placing extremely high demands on the detection technology. Unlike readily reactive ions, the detection of perchlorate relies on weak interactions due to its inherent non-coordinating and non-reactive properties. Therefore, it is difficult to meet the demand for perchlorate detection, especially in complex real-world water environments. Summary of the Invention

[0011] In view of the problems existing in the above-mentioned prior art, the object of the present invention is to provide a perchlorate selective electrode based on an electron / ion dual-channel material and a preparation method thereof.

[0012] In order to achieve the above object, the present invention adopts the following technical solutions:

[0013] A first aspect of the present invention provides a method for preparing a perchlorate selective electrode based on an electron / ion dual channel material, comprising the following steps:

[0014] S1. Preparation of ISE membrane: dissolve tetraphenylporphyrin dichlorophosphine chloride, tetraoctylammonium chloride, polyvinyl chloride, polytetrafluoroethylene, and dibutyl phthalate in tetrahydrofuran, stir and mix to obtain a clear solution, and drop the clear solution onto the surface of the MXene electrode and dry to obtain an ISE membrane electrode;

[0015] S2. Preparation of Qas-Mx@PPy material, i.e., electron / ion dual-channel material (hereinafter referred to as dual-channel material):

[0016] A monolayer MXene is ultrasonically dispersed in ultrapure water to obtain a monolayer MXene dispersion. A long-chain alkyl-substituted quaternary ammonium salt (denoted as R-Qas, hereinafter referred to as Qas) is added to the monolayer MXene dispersion and reacted at room temperature with stirring to allow the quaternary ammonium salt molecules to intercalate between the MXene layers through electrostatic interaction. Pyrrole monomer is then added and the reaction is continued with stirring to achieve polymerization of pyrrole on the quaternary ammonium salt-modified MXene surface, resulting in the Qas@Mx / PPy material, i.e., a dual-channel material.

[0017] S3. Preparation of perchlorate selective electrode:

[0018] The prepared Qas@Mx / PPy material was dispersed in ultrapure water and thoroughly sonicated to ensure uniform dispersion. Then, the dispersed liquid droplets were applied to the surface of the ISE membrane electrode and allowed to dry at room temperature to obtain the Qas@Mx / PPy / ISE modified electrode, i.e., the perchlorate selective electrode.

[0019] Preferably, in step S1, the dosage ratio of the tetraphenylporphyrin dichlorophosphine chloride, tetraoctylammonium chloride, polyvinyl chloride, polytetrafluoroethylene, dibutyl phthalate, and tetrahydrofuran is 1-1.5 mg: 0.6-0.8 mgs: 30-35 mg: 0.2-0.4 mg: 60-70 mg: 2-3 ml.

[0020] Preferably, in step S1, the stirring time is 2 to 3 hours.

[0021] Preferably, in step S2, the usage ratio of the monolayer Mxene, the long-chain alkyl-substituted quaternary ammonium salt, and the pyrrole monomer is 8-10 mg: 4-5 mg: 1.5-2 mg.

[0022] Preferably, the long-chain alkyl-substituted quaternary ammonium salt is selected from C6-C12 alkyl-substituted quaternary ammonium salts, for example, C6 alkyl quaternary ammonium salt, C8 alkyl quaternary ammonium salt, C10 alkyl quaternary ammonium salt or C12 alkyl quaternary ammonium salt.

[0023] Preferably, in step S2, the stirring reaction time is 6 to 8 h, and the stirring reaction time is continued to be 10 to 12 h.

[0024] Preferably, in step S2, the drying temperature is 55-60° C., and the drying time is 5-6 h.

[0025] Preferably, in step S2, the preparation steps of the single-layer MXene are: placing Ti3AlC2 in a mixed solution of concentrated hydrochloric acid, ultrapure water, and hydrofluoric acid in a volume ratio of 6:3:1, etching at 30-40°C for 20-28 hours, collecting the bottom precipitate, centrifuging, and washing so that the pH of the precipitate is greater than 6; adding lithium chloride to the precipitate for intercalation, shaking by hand until the bottom precipitate expands, centrifuging, and collecting the supernatant, which is the single-layer MXene.

[0026] Preferably, the Ti3AlC2 and lithium chloride are used in the same amount by mass.

[0027] Preferably, in step S3, the dosage ratio of the Qas@Mx / PPy material (dual-channel material) and ultrapure water is 1.5-2 mg: 1.5-2 mL.

[0028] The second aspect of the present invention is to provide a perchlorate selective electrode prepared by the above preparation method.

[0029] Detection mechanism:

[0030] This study successfully synthesized an electron / ion dual-channel material by polymerizing polypyrrole (PPy) on the surface of MXene and introducing a long-chain alkyl-substituted quaternary ammonium salt. By controlling the MXene / pyrrole ratio, the PPy polymerization ratio was precisely controlled. This material was then used as an electrode modification material to fabricate a perchlorate-selective electrode, enabling the modulation of the interlayer spacing and hydrophobicity of MXene. The introduction of the long-chain alkyl-substituted quaternary ammonium salt as a pillar effectively modulates the interlayer spacing of MXene, further optimizing the material's hydrophobicity and improving its ion channel structure. Furthermore, the incompletely polymerized PPy forms ion migration channels between the MXene layers, providing pathways for perchlorate ions and further enhancing the material's conductivity. This design significantly improves the material's ion / electron mobility. In the constructed dual-channel structure, PPy not only acts as an electron channel to enhance the longitudinal conductivity of MXene but also provides an effective accumulation space for perchlorate within the ion channel. This dual-channel design significantly enhances both accumulation and conductivity, significantly improving perchlorate detection. The dual-channel material is coated on the electrode surface and integrated into a composite electrode, which can achieve high sensitivity and high selectivity detection of perchlorate in complex water bodies.

[0031] Beneficial effects:

[0032] (1) The present invention provides a perchlorate selective electrode based on an electron / ion dual-channel material and a preparation method thereof. Experimental results show that the perchlorate selective electrode based on an electron / ion dual-channel material exhibits extremely strong selectivity and ultra-low detection limit recognition when detecting perchlorate, with the lowest detection limit reaching 12.4 μg / L. At the same time, the response time is extremely fast (~4 s), thereby enabling sensitive and rapid detection of perchlorate under complex water conditions. This provides a reliable and efficient solution to the technical difficulties of perchlorate detection in complex environments, and therefore has broad application prospects.

[0033] (2) The method for detecting perchlorate of the present invention has the characteristics of wide linear detection range (50 μg / L to 10 g / L), low detection limit, strong anti-interference ability, simple operation, high efficiency and speed, and low cost. It not only overcomes the shortcomings of traditional methods in detection selectivity and sensitivity, but also greatly improves the detection efficiency, providing another new idea for the detection of perchlorate. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0035] Figure 1 : This is the SEM image of C8@Mx / PPy / ISM prepared in Example 1;

[0036] Figure 2 (a) EDS map of C8@Mx / PPy / ISM; (b) mapping of Ti element; (c) mapping of N element;

[0037] Figure 3 XRD patterns of different electrode modification materials (Mxene, C6@Mx / PPy, C8@Mx / PPy, C10@Mx / PPy, C12@Mx / PPy);

[0038] Figure 4 EIS graphs of different electrode modification materials: (a) Mxene; (b) Mx@PPy; (c) C8@Mx / PPy;

[0039] Figure 5 Charge density diagrams of different electrode modification materials: (a) Mxene; (b) C8@Mx / PPy;

[0040] Figure 6Figure 3: (a) LOD and sensitivity of electrode-modified materials prepared at different Mxene:PPy ratios for perchlorate detection; (b) LOD and sensitivity of electrode-modified materials prepared with quaternary ammonium salts of different carbon chain lengths (C6@Mx / PPy, C8@Mx / PPy, C10@Mx / PPy, and C12@Mx / PPy) for perchlorate detection when Mx / PPy=5:1.

[0041] Figure 7 Figures 1 and 2 show: (a) the potential response of the composite electrode assembled with the C8@Mx / PPy / ISM modified electrode as the working electrode when exposed to different concentrations of perchlorate; (b) the fitting curve of the potential response versus perchlorate concentration.

[0042] Figure 8 Figure 2: (a) Selectivity results of the composite electrode assembled with C8@Mx / PPy / ISM modified electrode as the working electrode for perchlorate detection; (b) Stability results. DETAILED DESCRIPTION

[0043] In the following description, specific details such as particular system structures and techniques are provided for purposes of illustration, not limitation, to facilitate a thorough understanding of the embodiments of the present invention. However, it will be apparent to those skilled in the art that the present invention may be practiced in other embodiments without these specific details. In other cases, detailed descriptions of well-known systems, devices, circuits, and methods are omitted so as not to obscure the description of the present invention with unnecessary detail.

[0044] Example 1

[0045] A method for preparing a perchlorate selective electrode based on an electron / ion dual-channel material, comprising the following steps:

[0046] S1. Preparation of ISE membrane: 1 mg of tetraphenylporphyrin dichlorophosphine chloride, 0.6 mg of tetraoctylammonium chloride, 30 mg of polyvinyl chloride, 0.2 mg of polytetrafluoroethylene, and 60 mg of dibutyl phthalate were dissolved in 2 ml of tetrahydrofuran and stirred at room temperature for 2 h to obtain a clear solution. 50 μL of the solution was dropwise applied to the surface of the Mxene electrode and dried to obtain an ISE membrane electrode.

[0047] S2. Synthesis of electron / ion dual-channel materials, specifically C8@Mx / PPy materials:

[0048] (1) Preparation of monolayer MXene: Ti3AlC2 was etched at 30°C for 20 s with concentrated hydrochloric acid: ultrapure water: hydrofluoric acid = 6:3:1. The bottom precipitate was collected and washed by centrifugation multiple times to make the precipitate pH greater than 6. An equal amount of lithium chloride was added for intercalation. The mixture was shaken by hand until the bottom precipitate expanded. The supernatant collected by centrifugation was the monolayer MXene. 10 mg of the prepared monolayer MXene was ultrasonically dispersed in ultrapure water to ensure uniform dispersion to obtain a monolayer MXene dispersion.

[0049] (2) 5 mg of C8 alkyl quaternary ammonium salt was added to the monolayer MXene dispersion and the mixture was stirred at room temperature for 8 h to allow the quaternary ammonium salt molecules to be inserted into the MXene interlayer through electrostatic interaction. Then, 2 mg of pyrrole (Py) monomer was added and the mixture was stirred vigorously for 12 h to achieve the polymerization of pyrrole on the quaternary ammonium salt-modified MXene surface. The obtained reaction product was centrifuged and dried in vacuum at 60 °C for 6 h to obtain C8@MX / PPy material.

[0050] S3. Preparation of C8@Mx / PPy / ISE modified electrode: Weigh 2 mg of C8@Mx / PPy material and disperse it in 2 mL of ultrapure water. Sonicate thoroughly to ensure uniform dispersion, then take 6 μL of the dispersion droplet and apply it to the surface of the ISE membrane electrode. Let it stand and dry at room temperature to finally obtain the C8@Mx / PPy / ISE modified electrode, that is, the target perchlorate selective electrode.

[0051] Example 2

[0052] The method is basically the same as Example 1, except that in step S2, the C8 alkyl quaternary ammonium salt is replaced by a C6 alkyl quaternary ammonium salt, and finally a C6@Mx / PPy / ISE modified electrode is obtained.

[0053] Example 3

[0054] The method is basically the same as Example 1, except that in step S2, the C8 alkyl quaternary ammonium salt is replaced by a C10 alkyl quaternary ammonium salt, and finally a C10@Mx / PPy / ISE modified electrode is obtained.

[0055] Example 4

[0056] The method is basically the same as Example 1, except that in step S2, the C8 alkyl quaternary ammonium salt is replaced by a C12 alkyl quaternary ammonium salt, and finally a C12@Mx / PPy / ISE modified electrode is obtained.

[0057] Example 5

[0058] The process is basically the same as Example 1, except that, in step S2, 4 mg of the prepared single-layer Mxene is weighed and 2 mg of pyrrole (Py) monomer is added.

[0059] Example 6

[0060] The process is basically the same as Example 1, except that, in step S2, 4 mg of the prepared single-layer Mxene is weighed and 2 mg of pyrrole (Py) monomer is added.

[0061] Example 7

[0062] The process is basically the same as Example 1, except that, in step S2, 8 mg of the prepared single-layer Mxene is weighed and 1 mg of pyrrole (Py) monomer is added.

[0063] Example 8

[0064] The process is basically the same as Example 1, except that, in step S2, 10 mg of the prepared single-layer Mxene is weighed and 1 mg of pyrrole (Py) monomer is added.

[0065] 1. Characterization of materials

[0066] (1) SEM characterization

[0067] The C8@Mx / PPy / ISM material prepared in Example 1 was characterized by SEM. Figure 1 .

[0068] Figure 1 The results show that in the C8@Mx / PPy / ISM material, the surface Mxene still retains the layered structure of Mxene after adding quaternary ammonium salt (QAS) and polypyrrole (PPy), which indicates that the process of adding alkyl quaternary ammonium salt (QAS) and polypyrrole (PPy) does not destroy the basic morphology of Mxene. At the same time, it was also found that the space between the Mxene layers was not completely filled, which proves the successful synthesis of C8@Mx / PPy / ISM material and verifies the feasibility of the strategy of partially polymerizing pyrrole between the Mxene layers.

[0069] (2) Energy dispersive X-ray spectroscopy (EDS) characterization

[0070] The C8@Mx / PPy material prepared in Example 1 was characterized by EDS. Figure 2 .

[0071] Depend on Figure 2 (b) and Figure 2 (c) The results show that in C8@Mx / PPy material,

[0072] The Ti element (characteristic element of Mxene) mapping map and the N element (characteristic element of quaternary ammonium salt) mapping map can be clearly observed. This result proves that the C8 alkyl quaternary ammonium salt is uniformly loaded on the Mxene surface and forms a composite structure with polypyrrole, ensuring the uniformity and effectiveness of the charge transfer path and ion migration channel on the surface and between layers of the C8@Mx / PPy material.

[0073] (3) XRD characterization of electrode modified materials prepared by quaternary ammonium salts substituted with alkyl groups of different chain lengths (C6-C12) is shown in Figure 3 .

[0074] Depend on Figure 3 The results show that through the analysis of the characteristic peak near 6°, it can be inferred that the interlayer spacing of MXene gradually increases with the increase of the chain length of the alkyl-substituted quaternary ammonium salt, and the characteristic peak decreases from 6.24° to 5.78°. This change indicates the successful insertion of the alkyl quaternary ammonium salt into the MXene interlayer and further verifies the technical feasibility of achieving controllable adjustment of the MXene interlayer spacing by adjusting the chain length of the alkyl-substituted quaternary ammonium salt.

[0075] (4) EIS characterization of different electrode modified materials (Mxene, Mx / PPy and C8@Mx / PPy materials) is shown in Figure 4 (The diameter of the semicircle in the EIS graph represents the resistance of the material).

[0076] Depend on Figure 4 The results show that compared to Mxene, the resistance of the Mx / PPy composite (PPy) and the C8@Mx / PPy composite (PPy and C8 alkyl quaternary ammonium salt) materials were significantly reduced. This indicates that the addition of PPy (polypyrrole) improves the longitudinal conductivity of the material, while the introduction of C8 alkyl quaternary ammonium salt further optimizes the ion migration pathway by regulating the interlayer spacing. This multi-layered composite strategy helps improve the overall conductivity and interfacial ion exchange properties of the resulting material.

[0077] (5) By constructing different material models (Mxene, C8@Mx / PPy materials), the charge density of the materials is calculated. The results are shown in Figure 5 .

[0078] Depend on Figure 5 The results clearly show the charge density distribution of different atoms. Compared with Mxene, the atomic charge density between the Mxene interfaces is significantly increased in the C8@Mx / PPy material obtained by adding quaternary ammonium salt and polypyrrole between its layers. This phenomenon proves that electron transfer between interfaces is achieved through the construction process of the composite material.

[0079] (6) The LOD and sensitivity of the electrode modified materials prepared at different ratios of Mxene and PPy for perchlorate detection were studied. Figure 6 .

[0080] Depend on Figure 6 (a) The results show that when Mx / pyrrole = 5:1, the obtained material has the lowest LOD and the highest sensitivity for the detection of perchlorate.

[0081] (7) The LOD and sensitivity of electrode modified materials (C6@Mx / PPy, C8@Mx / PPy, C10@Mx / PPy, C12@Mx / PPy) prepared under the conditions of quaternary ammonium salts with different carbon chain lengths for perchlorate detection were studied when Mxene / pyrrole = 5:1. The results are shown in Figure 6 .

[0082] Depend on Figure 6 (b) The results show that the C8@Mx / PPy material has the lowest detection limit and the highest sensitivity for perchlorate, that is, C8 is the optimal carbon chain length of the alkyl-substituted quaternary ammonium salt.

[0083] Therefore, subsequent experiments used C8@Mx / PPy material as the final electrode modification material for perchlorate detection.

[0084] (8) Analytical performance of modified electrodes

[0085] The C8@Mx / PPy / ISE modified electrode was used as the working electrode to assemble a composite electrode. - 6.3 M, 10 -6 M, 10 -5 M, 10 -4 M, 10 -3 M, 10 -2 M, 10 -1 M) perchlorate solution, record the electrode potential corresponding to different perchlorate concentrations, and detect perchlorate by fitting the potential data under different perchlorate concentrations. Figure 7 .

[0086] Depend on Figure 7 (a) The results show that the electrode surface potential gradually decreases with the increase of perchlorate concentration, which may be attributed to the decrease in electrode surface potential caused by the adsorption of more perchlorate on the electrode surface. The results also show that the potential response of the C8@Mx / PPy / ISE modified electrode as a working electrode for the detection of perchlorate has a good linear relationship in the concentration range of 50 μg / L~10 g / L.

[0087] The potential response at different perchlorate concentrations was plotted against the corresponding perchlorate concentration to obtain a linear fitting curve (see Figure 7 (b)), y=-58.01x+73.4, R 2 =0.995, with a minimum detection limit of 12.4 μg / L. This indicates that the C8@Mx / PPy / ISE modified electrode has a wide linear range and a low detection limit. This is likely due to the high electrochemical activity of Mxene, the precise control of interlayer spacing by the quaternary ammonium salt, and the dual optimization of electron and ion channels by the partial polymerization of polypyrrole.

[0088] (9) Selectivity of modified electrodes for perchlorate, i.e., anti-interference analysis

[0089] Since various interfering substances may exist in the water detection process, which may affect the detection results, the present invention adds 5 equivalents of Br - 、NO3 - 、NO2 - 、H2PO4 - , HCO3, HSO3 - 、CH3COO - 、CO3 2- 、SO4 2- 、Cl - , ClO - 、ClO2 - 、ClO3 - , I - 、SCN - The anti-interference performance of the C8@Mx / PPy / ISM modified electrode was tested by measuring the potential difference before and after adding interfering ions. Figure 8 .

[0090] Depend on Figure 8 (a) The results show that the presence of 5 equivalents of the above different interfering ions has no significant effect on the electrode surface potential, which is much lower than that of ClO4 - This indicates that the C8@Mx / PPy / ISM modified electrode has a strong effect on ClO4 - It has excellent selectivity and anti-interference performance, which may be attributed to the interlayer hydrophobicity and ion channel properties regulated by alkyl-substituted quaternary ammonium salts.

[0091] (10) Stability of modified electrode for perchlorate detection

[0092] Depend on Figure 8(b) The results show that after 30 days of long-term storage, the potential change difference of the C8@Mx / PPy / ISM modified electrode to perchlorate is very small, which proves that the C8@Mx / PPy / ISM modified electrode has good stability. This improvement in stability may be attributed to the quaternary ammonium salt increasing the interlayer spacing and inhibiting the agglomeration of Mxene, as well as the polymerization of polypyrrole on the Mxene surface for protection against oxidation.

[0093] (11) Detection and analysis of actual water samples

[0094] In order to test the application potential of the material in actual water bodies, the C8@Mx / PPy / ISM modified electrode was integrated into an ion-selective electrode sensor, and tap water, Xiangjiang River water and fireworks factory wastewater (diluted 1000 times) were selected for testing. The test results are shown in Table 1 below.

[0095] Table 1

[0096]

[0097] As shown in Table 1, the recovery rate of the C8@Mx / PPy / ISM modified electrode in actual water bodies is between 97.90% and 102.20%. After repeated tests, the RSD of the test results is lower than 6.89%, which indicates that the material has good actual detection stability. This shows that the ability of the C8@Mx / PPy / ISM modified electrode to detect perchlorate in highly complex actual water samples has been fully verified and has broad application prospects.

[0098] The present invention is not limited to the above-mentioned specific implementation methods. Various changes made by ordinary technicians in this field based on the above-mentioned concept without creative work are all within the scope of protection of the present invention.

Claims

1. A method for preparing a perchlorate selective electrode based on an electron / ion dual channel material, characterized in that: The following steps are involved: S1. Preparation of ISE membrane: dissolve tetraphenylporphyrin dichlorophosphine chloride, tetraoctylammonium chloride, polyvinyl chloride, polytetrafluoroethylene, and dibutyl phthalate in tetrahydrofuran, stir and mix to obtain a clear solution, and drop the clear solution onto the surface of the MXene electrode and dry to obtain an ISE membrane electrode; S2. Synthesis of electron / ion dual-channel materials: Ultrasonic dispersion of a monolayer of MXene in ultrapure water to obtain a monolayer of MXene dispersion; adding a long-chain alkyl-substituted quaternary ammonium salt to the monolayer of MXene dispersion, stirring and reacting at room temperature; then adding a pyrrole monomer, and continuing to stir and react to obtain an electron / ion dual-channel material; S3. Preparation of perchlorate selective electrode: The prepared electron / ion dual-channel material is dispersed in ultrapure water to obtain a dispersion, and then the dispersion is dropwise coated on the surface of an ISE membrane electrode and allowed to stand and dry at room temperature to obtain a perchlorate selective electrode.

2. The method for preparing a perchlorate selective electrode based on an electron / ion dual channel material according to claim 1, characterized in that: In step S1, the dosage ratio of tetraphenylporphyrin dichlorophosphine chloride, tetraoctylammonium chloride, polyvinyl chloride, polytetrafluoroethylene, dibutyl phthalate, and tetrahydrofuran is 1-1.5 mg: 0.6-0.8 mgs: 30-35 mg: 0.2-0.4 mg: 60-70 mg: 2-3 ml; and the stirring time is 2-3 h.

3. The method for preparing a perchlorate selective electrode based on an electron / ion dual channel material according to claim 1, characterized in that: The long-chain alkyl-substituted quaternary ammonium salt is selected from C6-C12 alkyl-substituted quaternary ammonium salts.

4. The method for preparing a perchlorate selective electrode based on an electron / ion dual channel material according to claim 1, characterized in that: In step S2, the usage ratio of the monolayer Mxene, the long-chain alkyl-substituted quaternary ammonium salt, and the pyrrole monomer is 8-10 mg: 4-5 mg: 1.5-2 mg.

5. The method for preparing a perchlorate selective electrode based on an electron / ion dual channel material according to claim 1, characterized in that: In step S2, the stirring reaction time is 6 to 8 hours, and the stirring reaction time is continued for 10 to 12 hours.

6. The method for preparing a perchlorate selective electrode based on an electron / ion dual channel material according to claim 1, characterized in that: In step S1, the drying temperature is 55-60°C and the drying time is 5-6 hours.

7. The method for preparing a perchlorate selective electrode based on an electron / ion dual channel material according to claim 1, characterized in that: In step S3, the electron / ion dual-channel material and ultrapure water are used in a ratio of 1.5-2 mg:1.5-2 mL.

8. A perchlorate selective electrode based on an electron / ion dual-channel material, characterized in that: Prepared by the preparation method according to any one of claims 1 to 7.

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