A solid-state perchlorate ion-selective electrode and preparation and application thereof

Abstract

This invention discloses a solid perchlorate ion-selective electrode, its preparation, and its application, belonging to the field of ion-selective electrode technology. The solid perchlorate ion-selective electrode of this invention includes a shell, within which are disposed a first conductor, a conductive liquid, a conductive substrate, a solid contact layer, and an ion-selective membrane connected in sequence. The ion-selective membrane contains an ion carrier, an ion exchanger, a plasticizer, and a membrane matrix. The solid contact layer contains a carbon material and an ionic liquid. The ion carrier includes a m-tetraphenylporphyrin metal complex, wherein the coordinating metal is iron, cobalt, or nickel. The main application of this invention is to improve the perchlorate ion-selective electrode composition of ClO4. ‑ High selectivity and interference resistance in detection.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ion selective electrode, more particularly, to a solid-state perchlorate ion selective electrode and preparation and application thereof. BACKGROUND

[0002] Perchlorate (ClO4 - ) is an inorganic pollutant, mainly from the production and use of fireworks, space propulsion, ammunition, textile fixative, battery and other products. Because of its high solubility and diffusivity, and not easy to decompose in the environment, it is easy to migrate and diffuse in surface water and groundwater. In some areas of China, the concentration of ClO4 - in the wastewater discharged by the fireworks industry can be as high as several hundred to several thousand mg / L, far exceeding the national standard, which has posed a serious threat to the safety of drinking water quality. Therefore, it is necessary to monitor ClO4 - in the production wastewater in real time in order to control and remove it.

[0003] The detection methods of ClO4 - mainly include complex colorimetric method, ion chromatography, liquid chromatography-mass spectrometry and ion selective electrode method (ISE). Among them, ISE method has the advantages of low testing cost, simple operation and large linear range, and has the greatest potential for online monitoring application. ISE can be divided into traditional liquid ISE and emerging solid ISE (Solid-Contact ISE, SC-ISE). Although the liquid ISE has high sensitivity, its stability and durability are poor and cannot be ignored. Based on the double-layer capacitance theory, the solid ISE does not need internal filling solution, and uses a capacitive material with good conductivity and large specific surface area as an ion-electron conversion layer, which has the advantages of more durable and easy to miniaturize on the basis of inheriting the advantages of liquid ISE. However, the current solid ISE patents mainly focus on the analysis and detection of metal cations such as potassium, sodium, calcium, copper and lead, and anions such as bromide, nitrate and phosphate.

[0004] Therefore, there is an urgent need for a solid ISE electrode to realize the high-selectivity detection of ClO4 - . SUMMARY

[0005] 1. Technical problems to be solved by the application

[0006] The purpose of the present application is to overcome the problems of poor selectivity and anti-interference of the solid-state perchlorate ion selective electrode in the prior art when detecting ClO4 - , and to provide a solid-state perchlorate ion selective electrode and a preparation method thereof.

[0007] 2. Technical solutions

[0008] To achieve the above object, the technical scheme provided by the present application is as follows:

[0009] The solid-state perchlorate ion selective electrode provided by the present application comprises a shell,

[0010] The shell is provided with a first conductor, a conductive liquid, a conductive substrate, a solid-state contact layer and an ion selective membrane connected in sequence.

[0011] The solid-state contact layer contains carbon material and ionic liquid.

[0012] The ion selective membrane contains ion carrier, ion exchanger, plasticizer and membrane matrix; wherein,

[0013] The ion carrier comprises meta-tetraphenylporphyrin metal complex, and the coordinated metal is iron, cobalt or nickel.

[0014] Preferably, the ion carrier is meta-tetraphenylporphyrin metal complex, and the coordinated metal is iron, cobalt or nickel.

[0015] Further, the ion carrier is meta-tetraphenylporphyrin metal complex, and the coordinated metal is iron (III), cobalt (III) or nickel (II).

[0016] Further, the conductive substrate has an A end and a B end,

[0017] The shell has an M end and an N end,

[0018] The distance between the A end of the conductive substrate and the M end of the shell is L, and L ranges from 1 to 2 mm.

[0019] Further, the conductive substrate is one, two or more than two of gold, platinum or glassy carbon (abbreviated as glassy carbon).

[0020] Further, in the solid-state contact layer, the mass ratio of carbon material to ionic liquid is (1-20):(80-100).

[0021] Further, in the ion selective membrane, the mass ratio of membrane matrix, plasticizer, ion carrier and ion exchanger is (30-50):(45-69):(0.5-2.5):(0.5-2.5).

[0022] Further, the thickness of the solid-state contact layer is 0.1-0.2 mm, and the thickness of the ion selective membrane is 0.15-0.3 mm.

[0023] Further, the ion exchanger is one, two or more than two of dodecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide and trioctylmethylammonium chloride.

[0024] Further, the plasticizer is one, two or more of o-nitrophenyl octyl ether, dibutyl phthalate, dioctyl phthalate.

[0025] Further, the film substrate is polyvinyl chloride.

[0026] Further, the carbon material is one, two or more of single-walled carbon nanotubes, multi-walled carbon nanotubes, mesoporous carbon.

[0027] Further, the ionic liquid includes tetra (4-chlorophenyl) borate tetradodecylammonium.

[0028] Preferably, the ionic liquid is tetra (4-chlorophenyl) borate tetradodecylammonium.

[0029] Further, the first conductor is a silver wire or a gold-plated copper column.

[0030] It should be noted that when the first conductor is a silver wire, the other end of the silver wire needs to be matched with a terminal.

[0031] Further, the conductive liquid is one, two or more of conductive silver paste, conductive gold paste, and conductive platinum paste.

[0032] Further, the connection between the ion-selective membrane and the shell is provided with an adhesive layer.

[0033] The adhesive layer is formed of an adhesive.

[0034] The adhesive is one, two or more of UV glue, epoxy AB glue, and silicone glue.

[0035] The adhesive layer can tightly connect the ion-selective membrane and the shell, and prevent liquid (such as water) from entering the electrode during detection, affecting the selectivity of ClO4 - detection, and the service life of the electrode.

[0036] Further, the material of the shell is plastic.

[0037] The application also provides a preparation method of the above-mentioned solid-state perchlorate ion-selective electrode, comprising the following steps:

[0038] S1. Making a conductive substrate electrode: placing the pretreated conductive substrate into the shell;

[0039] The B end of the conductive substrate is connected with the conductive liquid and the first conductor in sequence, and the first conductor is glued between the conductive substrate and the shell.

[0040] The distance between the A end and the M end of the shell is 1-2 mm.

[0041] S2. Preparing solid contact layer: drop coating mixture A containing carbon material and ionic liquid to the end face of the end of conductive substrate A, after drying, forming solid contact layer;

[0042] S3. Preparing ion selective membrane: drop coating mixture B containing ion carrier, ion exchanger, plasticizer and membrane matrix to the surface of solid contact layer, after drying, forming ion selective membrane.

[0043] Further, in step S3, after forming the ion selective membrane, further including coating adhesive at the connection between the ion selective membrane and the shell.

[0044] Further, in step S2, the mass ratio of carbon material and ionic liquid in mixture A is (1-20):(80-100).

[0045] Further, the carbon material is one, two or more of single-walled carbon nanotubes, multi-walled carbon nanotubes and mesoporous carbon.

[0046] Further, the ionic liquid is tetra (4-chlorophenyl) borate tetradodecylammonium.

[0047] Further, in step S2, the solvent of mixture A is tetrahydrofuran.

[0048] Further, in step S2, the preparation method of mixture A is: adding carbon material and ionic liquid into solvent, and ultrasonicating for more than 30 minutes for degassing and dispersing and dissolving.

[0049] Further, in step S2, the drop coating includes: sucking mixture A and adding it dropwise to the end face of the end of conductive substrate A, and then drying, repeating the sucking and drying operations for 10-15 times, and accumulating drop coating of 80-120 μL.

[0050] It should be noted that the purpose of drying is to volatilize the solvent.

[0051] Further, after drop coating, infrared heating lamp irradiation is adopted.

[0052] The melting point of the ionic liquid is about 80℃, and the infrared heating lamp irradiation can melt the ionic liquid, so as to tightly bond and fix the carbon material on the surface of the conductive substrate, which is more conducive to the conduction of electrons, so as to improve the efficiency, sensitivity and the like of detection.

[0053] Further, in step S3, the mass ratio of membrane matrix, plasticizer, ion carrier and ion exchanger in mixture B is (30-50):(45-69):(0.5-2.5):(0.5-2.5).

[0054] Further, the ion exchanger is one, two or more of dodecylmethylammonium chloride, hexadecyltrimethylammonium bromide, trioctylmethylammonium chloride.

[0055] Further, the plasticizer is one, two or more of o-nitrophenyl octyl ether, dibutyl phthalate, dioctyl phthalate.

[0056] Further, the film matrix is polyvinyl chloride.

[0057] Further, in step S3, the solvent of mixture B is one or both of tetrahydrofuran and cyclohexanone.

[0058] Further, in step S3, the preparation method of mixture B is: adding the ion carrier, the ion exchanger, the plasticizer and the film matrix into the solvent, and ultrasonicating for 30-60 minutes, wherein the ultrasonicating is for degassing.

[0059] Further, in step S3, the drop coating is that 15-30 μL of mixture B is uniformly drop coated on the surface of the solid contact layer, and naturally air dried.

[0060] Further, in step S1, the pretreatment comprises polishing and cleaning which are sequentially performed.

[0061] For example, the polishing is performed by sequentially using diamond sandpaper and γ-Al2O3 slurry, wherein the γ-Al2O3 slurry is 0.3 μm γ-Al2O3; wherein the diamond sandpaper with small mesh number is used first, and then the diamond sandpaper with large mesh number is used;

[0062] The cleaning is ultrasonic cleaning by sequentially using deionized water, anhydrous ethanol and acetone.

[0063] Further, in step S1, a glue layer is formed after the glue is filled, and the glue layer is used for fixing the first conductor.

[0064] The application further provides application of the solid-state perchlorate ion selective electrode or the solid-state perchlorate ion selective electrode prepared by the preparation method in detection of ClO4 - .

[0065] 3. Beneficial effects

[0066] Compared with the prior art, the technical scheme provided by the application has the following beneficial effects:

[0067] The solid-state perchlorate ion selective electrode of the present application comprises a shell and a first conductor, conductive liquid, glass carbon, solid-state contact layer and ion selective membrane connected in sequence in the shell, wherein the ion selective membrane contains an ion carrier, and the ion carrier is a metal complex of m-tetraphenylporphyrin, and the coordination metal is iron, coben or nickel. - The selectivity and anti-interference are better. BRIEF DESCRIPTION OF DRAWINGS

[0068] The technical solutions of the present application will be further described in detail below in combination with the drawings and examples, but it should be understood that the drawings are only designed for the purpose of explanation, and therefore do not limit the scope of the present application. In addition, unless specifically indicated, these drawings are only intended to conceptually illustrate the structural configuration described herein, and are not necessarily drawn to scale.

[0069] Figure 1 It is a structural schematic diagram of the solid-state perchlorate ion selective electrode in Example 1 of the present application.

[0070] Figure 2 It is a standard curve diagram of ClO4 - , NO3 - , CO3 2- , PO4 3- , Cl - , SO4 2- of the solid-state perchlorate ion selective electrode in Example 1 of the present application.

[0071] Figure 3 It is a standard curve diagram of ClO4 - , NO3 - , CO3 2- , PO4 3- , Cl - , SO4 2- of the solid-state perchlorate ion selective electrode in Example 2 of the present application.

[0072] Figure 4 It is a standard curve diagram of ClO4 - , NO3 - , CO3 2- , PO4 3- , Cl - , SO4 2- of the solid-state perchlorate ion selective electrode in Example 3 of the present application.

[0073] Figure 5 It is a standard curve diagram of ClO4 - , NO3 - , CO3 2- , PO4 3-Cl - SO4 2- standard curve of ClO4

[0074] Figure 6 standard curve of ClO4 - NO3 - CO3 2- PO4 3- Cl - SO4 2- standard curve of ClO4

[0075] Figure 7 standard curve of ClO4 - NO3 - CO3 2- PO4 3- Cl - SO4 2- standard curve of ClO4

[0076] Reference Signs List:

[0077] 1. housing; 2. first conductor; 3. conducting liquid; 4. conducting substrate; 5. solid state contact layer; 6. ion selective membrane; 7. adhesive layer; 8. adhesive layer. DETAILED DESCRIPTION

[0078] The present disclosure can be more easily understood by reference to the following description in conjunction with the examples included herein. It should be understood that the present disclosure is not limited to the particular products, methods, conditions or parameters described and / or shown herein, unless otherwise specified. Further, the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting, unless otherwise specified.

[0079] It should also be understood that certain features of the disclosure, which are, for clarity, described in the context of separate embodiments, can also be provided in combination in a single embodiment. That is, each individual embodiment can be combined with any other embodiment or embodiments unless specifically noted otherwise. Conversely, various features of the disclosure, which are, for brevity, described in the context of a single embodiment, can also be provided separately or in any sub-combination. Finally, while the

[0080] Unless otherwise indicated, it is to be understood that each individual element of a list and every combination of individual elements in that list is to be construed as a separate embodiment. For example, a list of embodiments represented as "A, B, or C" is to be construed as including the embodiments of "A," "B," "C," "A or B," "A or C," "B or C," or "A, B, or C."

[0081] In this disclosure, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a substance" is a reference to at least one of such a substance and equivalents thereof.

[0082] When describing items by using the conjunctive term "and / or," and the like, the description is to be construed to include any one of the associated listed items as well as all combinations of one or more of the items.

[0083] Generally, the use of the term "about" indicates an approximation that can vary depending on the desired characteristics obtained by the disclosed subject matter and will be interpreted based on functionality in a context-dependent manner. Thus, a person of ordinary skill in the art will be able to interpret a degree of variance on a case-by-case basis. In some cases, the number of significant digits used in expressing a particular value can be representative of the degree of precision intended for determining the value allowed by the term "about." In other cases, a range of values can be determined using a progression of values between a lower limit and an upper limit, the range of values being determined by the term "about." Further, all ranges in the present disclosure are inclusive and combinable, and a reference to a value in a range includes each value in the range.

[0084] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs; the terminology used herein and / or any and all combinations of the listed items are intended to include any and all equivalents thereof.

[0085] In the following examples, the specific conditions not noted are performed according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used, when the manufacturer is not noted, are all conventional products that can be obtained by commercial purchase.

[0086] Among them, multi-walled carbon nanotubes (outer diameter: 8~15 nm, length: ~50 μm), meso-tetraphenylporphyrin iron (III) chloride were purchased from Aldrich; mesoporous carbon (mesoporous pore size: ~2.0 nm) was purchased from Merck;

[0087] meso-tetraphenylporphyrin cobalt (III) chloride and meso-tetraphenylporphyrin nickel (II) chloride were prepared according to the reference [Alternating Copolymerization of Carbon Dioxide and Cyclohexene Oxide Catalyzed by Cobalt Tetraphenylporphyrin Complexes. Journal of South-Central University for Nationalities (Natural Science Edition), December 2015, Vol. 34, No. 4];

[0088] The meso-tetraphenylporphyrin nickel (II) chloride was prepared by replacing CoCl2·6H2O in the preparation of meso-tetraphenylporphyrin cobalt (III) chloride in the reference with NiCl2·6H2O, and the other conditions were unchanged.

[0089] The present application will be further described in conjunction with specific examples, but the examples do not limit the present application in any form. Unless otherwise specified, the reagents, methods and equipment used in the present application are conventional reagents, methods and equipment in the technical field. The essential features and significant effects of the present application can be embodied in the examples described below, and the described examples are part of the examples, not all examples. Therefore, they do not limit the present application in any way, and those skilled in the art can make some non-essential improvements and adjustments based on the content of the present application, which are within the scope of protection of the present application.

[0090] Example 1

[0091] A solid-state perchlorate ion-selective electrode in the present example comprises a plastic shell 1 with an inner diameter of 3 mm, a gold-plated copper column 2 with a diameter of 2 mm in the plastic shell 1, conductive silver paste 3, a cylindrical glass 4 with a diameter and height of 3 mm, a solid-state contact layer 5, and an ion-selective membrane 6. The raw material of the solid-state contact layer 5 is single-walled carbon nanotubes and tetra (4-chlorophenyl) borate tetradodecylammonium, and the mass ratio of single-walled carbon nanotubes to tetra (4-chlorophenyl) borate tetradodecylammonium is 1:10. The raw material of the ion-selective membrane 6 is polyvinyl chloride, o-nitrophenyl octyl ether, meso-tetraphenylporphyrin iron chloride, and chlorinated thirty-two alkyl methyl ammonium, and the mass ratio of polyvinyl chloride, o-nitrophenyl octyl ether, meso-tetraphenylporphyrin iron chloride, and chlorinated thirty-two alkyl methyl ammonium is 49:49:1:1.

[0092] The specific preparation method of the solid-state perchlorate ion-selective electrode of the present example is as follows:

[0093] S1. Making glassy carbon electrode: the plane of the cylindrical glassy carbon 4 is polished by using 400 mesh, 800 mesh and 1200 mesh diamond sandpaper and 0.3 μm γ-Al2O3 slurry in turn, and then the cylindrical glassy carbon 4 is cleaned by ultrasonic wave with deionized water, anhydrous ethanol and acetone in turn; the treated glassy carbon 4 is inserted into the plastic cylindrical shell, making it concave 2 mm, the end of the gold-plated copper column 2 is coated with conductive silver paste, the other end of the plastic cylindrical shell 1 is inserted and bonded with the glassy carbon 4, and the glue layer 8 is formed between the gold-plated copper column 2 and the shell 1 gap to seal.

[0094] S2. Preparing solid contact layer 5: 1 mg of single-walled carbon nanotube and 10 mg of tetra (4-chlorophenyl) borate tetradodecylammonium are added to 1.5 mL of tetrahydrofuran solvent, and ultrasonic treatment is performed for more than 30 min to make them fully dispersed or dissolved, then the glassy carbon electrode is inverted with the glassy carbon facing up, 10 μL is taken by a pipette and dropped on the surface of the glassy carbon 4, after the solvent is dried, the operation of taking and drying is repeated for a total of 10 times, and 100 μL is accumulated by dropping, then infrared heating lamp is used for irradiation, so that tetra (4-chlorophenyl) borate tetradodecylammonium is melted to tightly bond and fix the single-walled carbon nanotube on the surface of the glassy carbon 4, forming a solid contact layer 5.

[0095] S3. Preparing ion selective membrane 6: 176.4 mg of polyvinyl chloride, 176.4 mg of o-nitrophenyl octyl ether, 3.6 mg of m-tetraphenylporphyrin iron (III) chloride and 3.6 mg of chloro-dodecylmethylammonium are dissolved in 2.5 mL of tetrahydrofuran solvent, ultrasonic degassing is performed for 30 min, 20 μL of the mixture is taken by a pipette and slowly and uniformly dropped on the surface of the solid contact layer 5, the electrode is placed in a ventilated place for natural drying, forming an ion selective membrane 6; then UV glue is coated around the ion selective membrane 6 and cured by ultraviolet light, so that the ion selective membrane 6 is tightly bonded on the plastic shell.

[0096] Example 2

[0097] A solid-state perchlorate ion selective electrode, comprising a plastic shell 1 with an inner diameter of 3 mm and a silver wire 2 with a diameter of 0.5 mm in the plastic shell 1, a glassy carbon 4 with a diameter and height of 3 mm, a solid contact layer 5 and an ion selective membrane 6, one end of the silver wire 2 is connected with a terminal, the raw material of the solid contact layer 5 is multi-walled carbon nanotube and tetra (4-chlorophenyl) borate tetradodecylammonium, and the mass ratio of the multi-walled carbon nanotube and the tetra (4-chlorophenyl) borate tetradodecylammonium is 1:10; the raw material of the ion selective membrane 6 is polyvinyl chloride, o-nitrophenyl octyl ether, m-tetraphenylporphyrin cobalt (III) chloride and chloro-dodecylmethylammonium, and the mass ratio of the polyvinyl chloride, o-nitrophenyl octyl ether, m-tetraphenylporphyrin cobalt (III) chloride and chloro-dodecylmethylammonium is 49:50:0.5:0.5.

[0098] The specific preparation method of the solid-state perchlorate ion selective electrode of the embodiment is as follows:

[0099] S1. Making a glassy carbon electrode: The surface of the cylindrical glassy carbon 4 is polished by using diamond sandpaper with mesh sizes of 400, 800 and 1200 and 0.3 μm γ-Al2O3 slurry in sequence, and then the cylindrical glassy carbon 4 is ultrasonically cleaned with deionized water, anhydrous ethanol and acetone in sequence; the polished glassy carbon 4 electrode is connected with the silver wire 1 through the conductive silver paste 3, the glassy carbon 4 electrode is inserted into one end of the plastic cylindrical shell 1 and is recessed by 1 mm, at the same time, the silver wire 2 is passed through the plastic cylindrical shell 1 to the other end and is welded to the terminal, and then the glue is poured to form a glue layer 8 to fix and seal the silver wire 2 and the terminal.

[0100] S2. Preparing the solid-state contact layer 5: 1 mg of multi-walled carbon nanotubes and 10 mg of tetra (4-chlorophenyl) borate tetradodecylammonium are added to 1.5 mL of tetrahydrofuran solvent, and ultrasonic treatment is performed for more than 30 min to make them fully dispersed or dissolved, then the glassy carbon electrode is inverted with the glassy carbon surface facing upward, 10 μL of the mixture is dropped onto the surface of the glassy carbon 4 by using a pipette, after the solvent is dried, the operation of sucking and drying is repeated for a total of 10 times, and 100 μL of the mixture is accumulated and dropped, then an infrared heating lamp is used for irradiation to make the tetra (4-chlorophenyl) borate tetradodecylammonium melt so as to tightly bond and fix the multi-walled carbon nanotubes on the surface of the glassy carbon 4, thereby forming the solid-state contact layer 5.

[0101] S3. Preparing the ion selective membrane 6: 176.4 mg of polyvinyl chloride, 180 mg of o-nitrophenyl octyl ether, 1.8 mg of m-tetraphenylporphyrin cobalt (III) chloride and 1.8 mg of chlorotriacontylmethylammonium chloride are dissolved in 2.5 mL of tetrahydrofuran solvent, ultrasonic degassing is performed for 30 min, 20 μL of the mixture is slowly and uniformly dropped on the surface of the solid-state contact layer 5 by using a pipette, and the electrode is placed in a ventilated place for natural drying, thereby forming the ion selective membrane 6; then silica gel is coated around the ion selective membrane 6, so that the ion selective membrane 6 is tightly bonded to the plastic shell.

[0102] Example 3

[0103] The preparation method is basically the same as that of Example 2, except that the raw material of the solid-state contact layer 5 in the solid-state perchlorate ion selective electrode is mesoporous carbon and tetra (4-chlorophenyl) borate tetradodecylammonium, and the mass ratio of the mesoporous carbon and the tetra (4-chlorophenyl) borate tetradodecylammonium is 1:10; the raw material of the ion selective membrane 6 is polyvinyl chloride, o-nitrophenyl octyl ether, m-tetraphenylporphyrin cobalt (III) chloride and chlorotriacontylmethylammonium chloride, and the mass ratio of the polyvinyl chloride, the o-nitrophenyl octyl ether, the m-tetraphenylporphyrin cobalt (III) chloride and the chlorotriacontylmethylammonium chloride is 50:49:0.5:0.5.

[0104] In the specific preparation method of the solid perchlorate ion-selective electrode of the embodiment, S2. Preparing the solid contact layer 5: using 1 mg mesoporous carbon and 10 mg tetra (4-chlorophenyl) borate dodecylammonium as raw materials; S3. Preparing the ion-selective membrane 6: using 180 mg polyvinyl chloride, 176.4 mg o-nitrophenyl octyl ether, 1.8 mg m-tetraphenylporphyrin cobalt (III) chloride, and 1.8 mg chlorinated dodecylmethylammonium as raw materials.

[0105] Example 4

[0106] The basic difference between the embodiment and the comparative example is that the raw materials of the ion-selective membrane 6 of the solid perchlorate ion-selective electrode of the comparative example are polyvinyl chloride, o-nitrophenyl octyl ether, m-tetraphenylporphyrin nickel (II) chloride, and chlorinated dodecylmethylammonium, and the mass ratio of polyvinyl chloride, o-nitrophenyl octyl ether, m-tetraphenylporphyrin nickel (II) chloride, and chlorinated dodecylmethylammonium is 49:49:1.5:0.5.

[0107] In the specific preparation method of the solid perchlorate ion-selective electrode of the embodiment, S3. Preparing the ion-selective membrane 6: using 176.4 mg polyvinyl chloride, 176.4 mg o-nitrophenyl octyl ether, 5.4 mg m-tetraphenylporphyrin nickel (II) chloride, and 1.8 mg chlorinated dodecylmethylammonium as raw materials.

[0108] Comparative Example 1

[0109] The basic difference between the embodiment and the comparative example is that the raw materials of the ion-selective membrane 6 of the solid perchlorate ion-selective electrode of the comparative example are polyvinyl chloride, o-nitrophenyl octyl ether, m-tetraphenylporphyrin nickel (II) chloride, and chlorinated dodecylmethylammonium, and the mass ratio of polyvinyl chloride, o-nitrophenyl octyl ether, m-tetraphenylporphyrin nickel (II) chloride, and chlorinated dodecylmethylammonium is 49:49:1.5:0.5.

[0110] Comparative Example 2

[0111] The basic difference between the embodiment and the comparative example is that the raw materials of the ion-selective membrane 6 of the solid perchlorate ion-selective electrode of the comparative example are polyvinyl chloride, o-nitrophenyl octyl ether, m-tetraphenylporphyrin nickel (II) chloride, and chlorinated dodecylmethylammonium, and the mass ratio of polyvinyl chloride, o-nitrophenyl octyl ether, m-tetraphenylporphyrin nickel (II) chloride, and chlorinated dodecylmethylammonium is 49:49:1.5:0.5.

[0112] Performance test

[0113] The solid perchlorate ion-selective electrodes prepared in the above examples and comparative examples were successively placed in 10 -8 mol / L and 10 -3 mol / L ClO4 - solution for 12 h, and then 10 -5 mol / L, 10 -4 mol / L, 10 -3 mol / L, 10 -2 mol / L, 10 -1 mol / L ClO4- The gradient solution adopts a three-electrode system, a solid-state perchlorate ion selective electrode as a working electrode, an Ag / AgCl electrode as a reference electrode, and a platinum sheet electrode as a counter electrode. The potential value under the concentration gradient solution is recorded by a potentiometer, and then the potential value of ClO4 - under the concentration gradient solution is recorded by a potentiometer. - The standard curve is drawn by the logarithmic value of the concentration and the potential value. 10 -5 mol / L, 10 - mol / L, 10 4 mol / L, 10 -3 mol / L, 10 -2 mol / L, 10 -1 mol / L of NO3 - , CO3 2- , PO4 3- , Cl - , SO4 2- gradient solution are configured, and the standard curve of each ion is drawn by testing according to the above method. The selectivity of the solid-state perchlorate ion selective electrode is tested by the respective solution method. The potential standard curve of the main response ion i (ClO4 - ) and the interfering ion j (NO3 - , CO3 2- , PO4 3- , Cl - , SO4 2- ) is determined, and the potential value of the main response ion i with a concentration of 1 M and the potential value of other common ions j are extrapolated by the standard curve . According to the formula K ij =exp{ } (in the formula: Z i is the charge number of the main response ion i, F is the Faraday constant, R is the ideal gas constant, and T is the temperature), the lgK ij is calculated.

[0114] Table 1 shows the lgK ij data of the solid-state perchlorate ion selective electrode prepared in different examples and comparative examples.

[0115]

[0116] As can be seen from Table 1, the interference degree of the interfering ion on the electrode detection of ClO4 - from strong to weak is in the order of: NO3 - > CO3 2- > PO4 3- (Cl - )> Cl - (PO4 3- )> SO42- SO4 2- The interference to the electrode was the weakest. SO4 - The interference to the electrode was the strongest. SO4 2- and Cl - The interference to the electrode for detecting ClO4 - was weaker than that of the examples, but the interference to the electrode for SO4 2- and Cl - was relatively weak compared to other interfering ions. Meanwhile, the interference to the electrode for other interfering ions PO4 3- , NO3 - , CO3 2- was weaker than that of the comparative examples, so the effect performance of the examples was the best. Furthermore, the selectivity and interference resistance of the electrode in Example 1 were better than those of Examples 2-4.

Claims

1. A solid-state perchlorate ion-selective electrode, characterized in that: Including the shell (1), The housing (1) is provided with a first conductor (2), a conductive liquid (3), a conductive substrate (4), a solid contact layer (5), and an ion-selective membrane (6) connected in sequence. The conductive substrate (4) has an A end and a B end. The solid contact layer (5) contains carbon material and ionic liquid, wherein the mass ratio of carbon material to ionic liquid is (1-20):(80-100). The method for preparing the solid contact layer (5) includes the following steps: A mixture A containing carbon material and ionic liquid is drop-coated onto the end face of the conductive substrate (4) at end A. After drying, a solid contact layer (5) is formed. The drop coating includes taking the mixture A and dropping it onto the end face of the conductive substrate (4) at end A, then drying it. The taking and drying operations are repeated 10 to 15 times, and a total of 80 to 120 μL of the mixture is dropped. The ion-selective membrane (6) contains an ion carrier, an ion exchanger, a plasticizer, and a membrane substrate; The ion support includes a meta-tetraphenylporphyrin metal complex, wherein the coordinating metal is iron, cobalt, or nickel.

2. The solid-state perchlorate ion-selective electrode according to claim 1, characterized in that: The housing (1) has an M end and an N end. The distance between the conductive substrate A end and the shell M end is L, and the range of L is 1 to 2 mm.

3. The solid-state perchlorate ion-selective electrode according to claim 2, characterized in that: The carbon material is one or more of single-walled carbon nanotubes, multi-walled carbon nanotubes, and mesoporous carbon.

4. The solid-state perchlorate ion-selective electrode according to claim 3, characterized in that: In the ion-selective membrane (6), the mass ratio of membrane substrate, plasticizer, ion carrier and ion exchanger is (30-50):(45-69):(0.5-2.5):(0.5-2.5).

5. The solid-state perchlorate ion-selective electrode according to claim 4, characterized in that: An adhesive layer (7) is provided at the connection between the ion-selective membrane (6) and the shell (1).

6. The solid-state perchlorate ion-selective electrode according to claim 2, characterized in that: The ionic liquid comprises tetra(4-chlorophenyl)borate tetradodecylammonium.

7. The method for preparing a solid perchlorate ion-selective electrode according to any one of claims 1 to 6, characterized in that, Includes the following steps: S1. Fabrication of conductive substrate electrode: Place the pretreated conductive substrate (4) into the housing (1); The B end of the conductive substrate (4) is connected to the conductive liquid (3) and the first conductor (2) in sequence, and potting is performed between the first conductor (2) and the shell (1); The distance between end A of the conductive substrate and end M of the shell is 1-2 mm; S2. Preparation of solid contact layer (5): A mixture A containing carbon material and ionic liquid is drop-coated onto the end face of the conductive substrate (4) at end A. After drying, a solid contact layer (5) is formed. S3. Preparation of ion-selective membrane (6): A mixture B containing ion carrier, ion exchanger, plasticizer and membrane substrate is drop-coated onto the surface of solid contact layer (5) and dried to form ion-selective membrane (6).

8. The solid perchlorate ion selective electrode according to any one of claims 1 to 6 or the solid perchlorate ion selective electrode prepared by the preparation method according to claim 7, in detecting ClO4 - Applications in [the field].

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