Solid perchlorate ion-selective electrode and preparation and application thereof

Abstract

The invention discloses a solid perchlorate ion-selective electrode as well as preparation and application thereof, and belongs to the technical field of ion-selective electrodes. The solid perchlorate ion selective electrode comprises a shell, and a first conductor, conductive liquid, a conductive substrate, a solid contact layer and an ion selective membrane which are sequentially connected are arranged in the shell; 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 comprises a m-tetraphenyl porphyrin metal complex, and the coordination metal is iron, cobalt or nickel. The main purpose of the invention is to improve the high selectivity and anti-interference performance of ClO4 <-> detection.

Description

Technical Field

[0001] The present invention relates to the technical field of ion selective electrodes, and more specifically to a solid perchlorate ion selective electrode and the preparation and application thereof. Background Art

[0002] Perchlorate (ClO4 - ) is an inorganic pollutant, mainly from the production and use of fireworks, aerospace propellants, munitions, textile fixatives, batteries and other products. Because of its high solubility and diffusivity, and not easy to decompose in the environment, it is easy to migrate and spread in surface water and groundwater. In some areas of my country, in the fireworks and other industries, ClO4 - The concentration can be as high as hundreds or thousands of mg / L, far exceeding the national standard, and has posed a serious threat to the safety of local drinking water quality. Therefore, it is necessary to - Real-time monitoring is performed to facilitate controlled removal.

[0003] ClO4 - The detection methods mainly use complex colorimetry, ion chromatography, liquid phase mass spectrometry and ion selective electrode method (ISE for short). Among them, the ISE method has the advantages of low test cost, simple operation, and large linear range, and has the greatest potential for online monitoring applications. ISE can be divided into traditional liquid ISE and emerging solid-contact ISE (SC-ISE). Liquid ISE has high sensitivity due to the presence of internal filling liquid, but its poor stability and low durability cannot be ignored. Based on the double-layer capacitance theory, solid-state ISE does not require internal filling solution, and uses capacitor materials with good conductivity and large specific surface area as the ion-electron conversion layer. On the basis of inheriting the advantages of liquid ISE, it has the advantages of being more durable and easy to miniaturize. However, the current solid-state ISE patents are mainly concentrated on the analysis and detection of metal cations such as potassium, sodium, calcium, copper, and lead, as well as anions such as bromide, nitrate, and phosphate.

[0004] Therefore, a solid-state ISE electrode is urgently needed to realize the - Highly selective detection. Summary of the invention

[0005] 1. Technical problem to be solved by the invention

[0006] The purpose of the present invention is to overcome the problem that the solid perchlorate ion selective electrode in the prior art is sensitive to ClO4 - In order to solve the problems of poor selectivity and anti-interference during detection, a solid perchlorate ion selective electrode and a preparation method thereof are provided.

[0007] 2. Technical solution

[0008] In order to achieve the above object, the technical solution provided by the present invention is:

[0009] A solid perchlorate ion selective electrode of the present invention comprises a shell,

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

[0011] The solid contact layer contains a carbon material and an ionic liquid;

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

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

[0014] Preferably, the ion carrier is a meta-tetraphenylporphyrin metal complex, wherein the coordination metal is iron, cobalt or nickel.

[0015] Furthermore, the ion carrier is a meta-tetraphenylporphyrin metal complex, wherein the coordination metal is iron (III), cobalt (III) or nickel (II).

[0016] Furthermore, 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 the range of L is 1 to 2 mm.

[0019] Furthermore, the conductive substrate is one, two or more of gold, platinum or glassy carbon (referred to as glassy carbon).

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

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

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

[0023] Furthermore, the ion exchanger is one, two or more of tridodecylmethylammonium chloride, hexadecyltrimethylammonium bromide and trioctylmethylammonium chloride.

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

[0025] Furthermore, the membrane substrate is polyvinyl chloride.

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

[0027] Furthermore, the ionic liquid includes tetradodecyl ammonium tetrakis(4-chlorophenyl)borate.

[0028] Preferably, the ionic liquid is tetradodecyl ammonium tetrakis(4-chlorophenyl)borate.

[0029] Furthermore, 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 used in conjunction with a wiring terminal.

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

[0032] Furthermore, an adhesive layer is provided at the connection between the ion selective membrane and the shell;

[0033] The adhesive layer is formed by an adhesive;

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

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

[0036] Furthermore, the shell is made of plastic.

[0037] The present invention also provides a method for preparing the above-mentioned solid perchlorate ion selective electrode, comprising the following steps:

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

[0039] The B end of the conductive substrate is connected to the conductive liquid and the first conductor in sequence, and glue is poured between the first conductor and the shell;

[0040] The distance between the A end and the M end of the housing is 1 to 2 mm;

[0041] S2. Preparation of a solid contact layer: A mixture containing a carbon material and an ionic liquid is drop-coated onto the end surface of the conductive substrate A, and after drying, a solid contact layer is formed;

[0042] S3. Preparation of ion selective membrane: A mixture B containing an ion carrier, an ion exchanger, a plasticizer and a membrane matrix is ​​drop-coated on the surface of the solid contact layer and, after drying, an ion selective membrane is formed.

[0043] Furthermore, in step S3, after the ion selective membrane is formed, an adhesive is applied to the connection between the ion selective membrane and the shell.

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

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

[0046] Furthermore, the ionic liquid is tetradecyl ammonium tetrakis (4-chlorophenyl) borate.

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

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

[0049] Furthermore, in step S2, the drop coating includes sucking the mixture A and dropping it onto the end surface of the conductive substrate A, and then drying it, and the sucking and drying operations are repeated 10 to 15 times, with a cumulative drop coating of 80 to 120 μL.

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

[0051] Furthermore, after the drop coating, irradiation with an infrared heating lamp is used.

[0052] The melting point of the ionic liquid is about 80° C. Irradiation with an infrared heating lamp can melt the ionic liquid so as to tightly bond and fix the carbon material to the surface of the conductive substrate, which is more conducive to the conduction of electrons, thereby improving the efficiency and sensitivity of detection.

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

[0054] Furthermore, the ion exchanger is one, two or more of tridodecylmethylammonium chloride, hexadecyltrimethylammonium bromide and trioctylmethylammonium chloride.

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

[0056] Furthermore, the membrane substrate is polyvinyl chloride.

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

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

[0059] Furthermore, in step S3, the drop coating is to absorb 15 to 30 μL of the mixture B and evenly drop coat it on the surface of the solid contact layer, and dry it naturally.

[0060] Furthermore, in step S1, the pretreatment includes grinding, polishing and cleaning performed in sequence.

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

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

[0063] Furthermore, in step S1, a glue layer is formed after glue pouring, and the glue layer is used to fix the first conductor.

[0064] The present invention also provides a solid perchlorate ion selective electrode or a solid perchlorate ion selective electrode prepared by the above preparation method for detecting ClO4 - Application in.

[0065] 3. Beneficial effects

[0066] Compared with the prior art, the technical solution provided by the present invention has the following beneficial effects:

[0067] The invention discloses a solid perchlorate ion selective electrode, comprising a shell and a first conductor, a conductive liquid, glassy carbon, a solid contact layer and an ion selective membrane which are sequentially connected in the shell. The ion selective membrane contains an ion carrier, which is a meta-tetraphenylporphyrin metal complex, wherein the coordination metal is iron, cobalt or nickel. When the electrode is used for detection, ClO4 - Better selectivity and anti-interference. BRIEF DESCRIPTION OF THE DRAWINGS

[0068] The technical solution of the present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments, but it should be understood that these drawings are designed only for explanation purposes and are not intended to limit the scope of the present invention. In addition, unless otherwise specified, these drawings are intended only to conceptually illustrate the structural configurations described herein and are not necessarily drawn to scale.

[0069] Figure 1 This is a schematic diagram of the structure of the solid perchlorate ion selective electrode in Example 1 of the present invention;

[0070] Figure 2 ClO4 of the solid perchlorate ion selective electrode of Example 1 of the present invention - 、NO3 - 、CO3 2- PO4 3- , Cl - 、SO4 2- Standard curve graph.

[0071] Figure 3 ClO4 of the solid perchlorate ion selective electrode of Example 2 of the present invention - 、NO3 - 、CO3 2- PO4 3- , Cl - 、SO4 2- Standard curve graph.

[0072] Figure 4 ClO4 of the solid perchlorate ion selective electrode of Example 3 of the present invention - 、NO3 - 、CO3 2- PO4 3- , Cl - 、SO4 2- Standard curve graph.

[0073] Figure 5 ClO4 of the solid perchlorate ion selective electrode of Example 4 of the present invention - 、NO3 - 、CO3 2- PO4 3-, Cl - 、SO4 2- Standard curve graph.

[0074] Figure 6 ClO4 of the solid perchlorate ion selective electrode of Comparative Example 1 of the present invention - 、NO3 - 、CO3 2- PO4 3- , Cl - 、SO4 2- Standard curve graph.

[0075] Figure 7 ClO4 of the solid perchlorate ion selective electrode of Comparative Example 2 of the present invention - 、NO3 - 、CO3 2- PO4 3- , Cl - 、SO4 2- Standard curve graph.

[0076] Explanation of the symbols in the schematic diagram:

[0077] 1. Shell; 2. First conductor; 3. Conductive liquid; 4. Conductive substrate; 5. Solid contact layer; 6. Ion selective membrane; 7. Adhesive layer; 8. Glue layer. DETAILED DESCRIPTION

[0078] The present disclosure may be more easily understood by reference to the following description in conjunction with examples, all of which constitute a part of the present disclosure. It should be understood that the present disclosure is not limited to the specific products, methods, conditions or parameters described and / or illustrated herein. Further, the terms used herein are only used for the purpose of describing specific embodiments by way of example and are not intended to be limiting unless otherwise indicated.

[0079] It should also be understood that, for the sake of clarity, certain features of the present disclosure may be described herein in the context of separate embodiments, but may also be provided in combination with each other in a single embodiment. That is, unless clearly incompatible or specifically not included, each separate embodiment is considered to be combinable with any other embodiment, and the combination is considered to represent another different embodiment. Conversely, for the sake of simplicity, the various features of the present disclosure described in the context of a single embodiment may also be provided individually or in any sub-combination. Finally, although a particular embodiment may be described as part of a series of steps or part of a more general structure, each step or substructure itself may also be considered to be an independent embodiment.

[0080] Unless otherwise indicated, it should be understood that each individual element in a list and each combination of individual elements in the list will be interpreted as a different embodiment. For example, a list of embodiments represented as "A, B, or C" should be interpreted to include embodiments "A", "B", "C", "A or B", "A or C", "B or C", or "A, B, or C".

[0081] In the present disclosure, the singular forms of the articles "a," "an," and "the" also include the corresponding plural references, and a reference to a specific value includes at least that specific value unless the context clearly indicates otherwise. Thus, for example, a reference to "a substance" is a reference to at least one of that substance and equivalents thereof.

[0082] When items are described by using the conjunction terms "... and / or...," etc., the description should be understood to include any one of the associated listed items and all combinations of one or more thereof.

[0083] In general, the use of the term "about" indicates an approximate value that can vary depending on the desired properties obtained by the disclosed subject matter, and will be interpreted in a context-dependent manner based on function. Therefore, one of ordinary skill in the art will be able to interpret a certain degree of difference on a case-by-case basis. In some cases, the number of significant figures used when expressing a particular value can be a representative technique for determining the difference allowed by the term "about". In other cases, a gradient in a range of values ​​can be used to determine the range of differences allowed by the term "about". Further, all ranges in this disclosure are inclusive and combinable, and reference to a value in a range includes each value within that 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 invention belongs; the terms used herein and / or include any and all combinations of one or more of the associated listed items.

[0085] In the following examples, if no specific conditions are specified, the experiments were carried out under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used, if no manufacturer is specified, are all conventional products that can be purchased commercially.

[0086] Among them, multi-walled carbon nanotubes (outer diameter: 8-15 nm, length: ~50 μm) and m-tetraphenylporphyrin iron (III) chloride were purchased from Aladdin; mesoporous carbon (mesopore diameter: ~2.0 nm) was purchased from Myrel;

[0087] Meta-tetraphenylporphyrin cobalt chloride (III) and meta-tetraphenylporphyrin nickel chloride (II) 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] Among them, the preparation of meta-tetraphenylporphyrin nickel (II) chloride is to replace CoCl2·6H2O in the preparation of meta-tetraphenylporphyrin cobalt (III) chloride in the reference with NiCl2·6H2O, and the other conditions remain unchanged.

[0089] The present invention is further described below in conjunction with specific examples, but the examples do not limit the present invention in any form. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art. The essential characteristics and remarkable effects of the present invention can be reflected from the following examples, and the described embodiments are part of the embodiments of the present invention, rather than all the embodiments, and therefore, they do not limit the present invention in any way, and those skilled in the art make some non-essential improvements and adjustments based on the content of the present invention, which all belong to the protection scope of the present invention.

[0090] Example 1

[0091] A solid perchlorate ion selective electrode in this 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, a conductive silver paste 3, a cylindrical glassy carbon 4 with a diameter and a height of 3 mm, a solid contact layer 5 and an ion selective membrane 6, wherein the raw materials of the solid contact layer 5 are single-walled carbon nanotubes and tetradecyl ammonium tetrakis(4-chlorophenyl)borate, and the mass ratio of the single-walled carbon nanotubes to tetradecyl ammonium tetrakis(4-chlorophenyl)borate is 1:10; the raw materials of the ion selective membrane 6 are polyvinyl chloride, o-nitrophenyl octyl ether, m-tetraphenylporphyrin ferric chloride, and tridecylmethylammonium chloride, and the mass ratio of polyvinyl chloride, o-nitrophenyl octyl ether, m-tetraphenylporphyrin ferric chloride, and tridecylmethylammonium chloride is 49:49:1:1.

[0092] The specific preparation method of the solid perchlorate ion selective electrode of this embodiment is:

[0093] S1. Making glassy carbon electrodes: grind and polish the plane of the cylindrical glassy carbon 4 with 400 mesh, 800 mesh and 1200 mesh diamond sandpaper and 0.3 μm γ-Al2O3 slurry in turn, and then ultrasonically clean the cylindrical glassy carbon 4 with deionized water, anhydrous ethanol and acetone in turn; insert the treated glassy carbon 4 cylinder into the plastic cylindrical shell so that it is recessed by 2 mm, apply conductive silver paste on one end of the gold-plated copper column 2, insert it from the other end of the plastic cylindrical shell 1 and bond it to the glassy carbon 4, and use glue to form a glue layer 8 between the gap between the gold-plated copper column 2 and the shell 1 to seal it.

[0094] S2. Preparation of solid contact layer 5: Add 1 mg of single-walled carbon nanotubes and 10 mg of tetrakis(4-chlorophenyl)ammonium tetrakis(4-chlorophenyl)borate to 1.5 mL of tetrahydrofuran solvent, and perform ultrasonic treatment for more than 30 minutes to fully disperse or dissolve them. Then, invert the glassy carbon electrode so that its glassy carbon surface faces upward, and use a pipette to pipette 10 μL and drop it onto the surface of the glassy carbon 4. After the solvent is dried, repeat the pipetting and drying operations for a total of 10 times, with a cumulative drop application of 100 μL. Then, use an infrared heating lamp to irradiate, so that the tetrakis(4-chlorophenyl)ammonium tetrakis(4-chlorophenyl)borate melts, thereby tightly bonding and fixing the single-walled carbon nanotubes to the surface of the glassy carbon 4 to form a solid contact layer 5.

[0095] S3. Preparation of 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 tridodecylmethylammonium chloride are dissolved in 2.5 mL of tetrahydrofuran solvent, and ultrasonically degassed for 30 minutes. 20 μL of the mixture is slowly and evenly applied on the surface of the solid contact layer 5 with a pipette, and the electrode is placed in a ventilated place to dry naturally to form an ion selective membrane 6; UV glue is then coated around the ion selective membrane 6 and cured by ultraviolet light, so that the ion selective membrane 6 is tightly bonded to the plastic shell.

[0096] Example 2

[0097] A solid perchlorate ion selective electrode comprises a plastic shell 1 with an inner diameter of 3 mm, a silver wire 2 with a diameter of 0.5 mm in the plastic shell 1, a glassy carbon 4 with a diameter and a height of 3 mm, a solid contact layer 5 and an ion selective membrane 6, wherein one end of the silver wire 2 is connected with a wiring terminal, the raw materials of the solid contact layer 5 are multi-walled carbon nanotubes and tetradecyl ammonium tetrakis(4-chlorophenyl)borate, and the mass ratio of the multi-walled carbon nanotubes to the tetradecyl ammonium tetrakis(4-chlorophenyl)borate is 1:10; the raw materials of the ion selective membrane 6 are polyvinyl chloride, o-nitrophenyl octyl ether, m-tetraphenylporphyrin cobalt (III) chloride and tridecyl methyl ammonium chloride, and the mass ratio of the polyvinyl chloride, o-nitrophenyl octyl ether, m-tetraphenylporphyrin cobalt (III) chloride and tridecyl methyl ammonium chloride is 49:50:0.5:0.5.

[0098] The specific preparation method of the solid perchlorate ion selective electrode of this embodiment is:

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

[0100] S2. Preparation of solid contact layer 5: Add 1 mg of multi-walled carbon nanotubes and 10 mg of tetrakis(4-chlorophenyl)ammonium tetrakis(4-chlorophenyl)borate to 1.5 mL of tetrahydrofuran solvent, and perform ultrasonic treatment for more than 30 min to fully disperse or dissolve them. Then, invert the glassy carbon electrode so that its glassy carbon surface faces upward, and use a pipette to pipette 10 μL and drop it onto the surface of the glassy carbon 4. After the solvent is dried, repeat the pipetting and drying operations for a total of 10 times, with a cumulative drop application of 100 μL. Then, use an infrared heating lamp to irradiate to melt the tetrakis(4-chlorophenyl)ammonium tetrakis(4-chlorophenyl)borate, so that the multi-walled carbon nanotubes are tightly bonded and fixed to the surface of the glassy carbon 4 to form a solid contact layer 5.

[0101] S3. Preparation of 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 tridodecylmethylammonium chloride are dissolved in 2.5 mL of tetrahydrofuran solvent, and ultrasonically degassed for 30 minutes. 20 μL of the mixture is slowly and evenly applied on the surface of the solid contact layer 5 with a pipette, and the electrode is placed in a ventilated place to dry naturally to form an ion selective membrane 6; silica gel is then 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 method is basically the same as Example 2, except that the raw materials of the solid contact layer 5 in the solid perchlorate ion selective electrode are mesoporous carbon and tetradecyl ammonium tetra(4-chlorophenyl)borate, and the mass ratio of the mesoporous carbon to tetradecyl ammonium tetra(4-chlorophenyl)borate is 1:10; the raw materials of the ion selective membrane 6 are polyvinyl chloride, o-nitrophenyl octyl ether, m-tetraphenylporphyrin cobalt (III) chloride, and tridecyl methyl ammonium chloride, and the mass ratio of the polyvinyl chloride, o-nitrophenyl octyl ether, m-tetraphenylporphyrin cobalt (III) chloride, and tridecyl methyl ammonium chloride is 50:49:0.5:0.5.

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

[0105] Example 4

[0106] The method is basically the same as Example 2, except that the raw materials of the ion selective membrane 6 are polyvinyl chloride, o-nitrophenyl octyl ether, m-tetraphenylporphyrin nickel (II) chloride, and tridecyl methyl ammonium chloride, and the mass ratio of polyvinyl chloride, o-nitrophenyl octyl ether, m-tetraphenylporphyrin nickel (II) chloride, and tridecyl methyl ammonium chloride is 49:49:1.5:0.5.

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

[0108] Comparative Example 1

[0109] The method is basically the same as Example 3, except that the ion carrier in the raw material of the ion selective membrane 6 of the solid perchlorate ion selective electrode of this comparative example is di(dibenzoylmethaneyl)cobalt(II).

[0110] Comparative Example 2

[0111] The method is basically the same as Example 4, except that the ion carrier in the raw material of the ion selective membrane 6 of the solid perchlorate ion selective electrode of this comparative example is di(dibenzoylmethaneyl)nickel(II).

[0112] Performance Testing

[0113] The solid perchlorate ion selective electrodes prepared in the above examples and comparative examples were placed in a -8 mol / L and 10 -3 mol / LClO4 - Solution activated for 12h, then prepared for 10 -5 mol / L、10 -4 mol / L、10 -3 mol / L、10 -2 mol / L、10 -1 mol / LClO4 -The gradient solution adopts a three-electrode system, with a solid perchlorate ion selective electrode as the working electrode, an Ag / AgCl electrode as the reference electrode, and a platinum electrode as the counter electrode. The ClO4 - The potential value under the concentration gradient solution is then measured with ClO4 - The standard curve was drawn by plotting the concentration logarithm and potential value. -5 mol / L、10 -4 mol / L、10 -3 mol / L、10 -2 mol / L、10 -1 mol / L NO3 - 、CO3 2- PO4 3- , Cl - 、SO4 2- Gradient solution, and draw the standard curve of each ion according to the above method. The selectivity of the solid perchlorate ion selective electrode was tested by the separate solution method. The main response ion i(ClO4 - ) and interfering ions j(NO3 - 、CO3 2- PO4 3- , Cl - 、SO4 2- ) and extrapolate the potential value of the main response ion i with a concentration of 1M through the standard curve. and other common ion j potential values According to the formula (Where: Z i The charge number of the main response ion i, F is the Faraday constant, R is the ideal gas constant, T is the temperature) to calculate lgK ij The specific results are shown in Table 1.

[0114] Table 1 IgK of solid perchlorate ion selective electrodes prepared in different embodiments and comparative examples ij data

[0115] <![CDATA[PO4 3- ]]> <![CDATA[SO4 2- ]]> <![CDATA[CO3 2- ]]> <![CDATA[NO3 - ]]> <![CDATA[Cl - <!-- 7 -->]]> Example 1 -4.39 -4.97 -4.26 -3.55 -4.83 Example 2 -4.12 -4.91 -4.14 -3.09 -4.27 Example 3 -4.01 -4.89 -4.11 -3.15 -4.33 Example 4 -4.21 -4.82 -4.20 -3.48 -4.62 Comparative Example 1 -3.87 -5.98 -3.76 -3.13 -5.33 Comparative Example 2 -3.97 -6.11 -3.83 -3.21 -5.46

[0116] It can be seen from Table 1 that the interference ion pair electrode detects ClO4 - The order of interference from strong to weak is: NO3 - >CO3 2- >PO4 3- (Cl - )>Cl - (PO4 3- )>SO4 2- , it can be seen that SO4 2- The interference to the electrode is the weakest, NO3- The interference to the electrode is the strongest. 2- and Cl - Counter electrode detection ClO4 - The interference of SO4 is weaker than that of the embodiment, but in embodiments 1-4, SO4 2- and Cl - The interference of PO4 to the electrode is relatively weak compared with other interfering ions. 3- 、NO3 - 、CO3 2- The interference to the electrode in the embodiment is weaker than that in the comparative example, so the effect and performance of the embodiment are the best. Moreover, the selectivity and anti-interference of the electrode in embodiment 1 are better than those in embodiments 2-4.

Claims

1. A solid perchlorate ion selective electrode, characterized in that: comprising a housing (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) which are connected in sequence; The solid contact layer (5) contains carbon material and ionic liquid; The ion selective membrane (6) contains an ion carrier, an ion exchanger, a plasticizer and a membrane matrix; wherein: The ion carrier comprises a meta-tetraphenylporphyrin metal complex, and the coordination metal is iron, cobalt or nickel.

2. The solid perchlorate ion selective electrode according to claim 1, characterized in that: The conductive substrate (4) has an A end and a B end, The shell (1) has an M end and an N end, The distance between the end A of the conductive substrate and the end M of the shell is L, and the range of L is 1-2 mm.

3. The solid perchlorate ion selective electrode according to any one of claims 1 to 2, characterized in that: In the solid contact layer (5), the mass ratio of carbon material to ionic liquid is (1-20):(80-100).

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

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

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

7. The solid perchlorate ion selective electrode according to claim 3, characterized in that: The ionic liquid includes tetradodecyl ammonium tetrakis(4-chlorophenyl)borate.

8. The method for preparing a solid perchlorate ion selective electrode according to any one of claims 1 to 7, characterized in that: The following steps are involved: S1. Making a conductive substrate electrode: placing 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 glue is poured between the first conductor (2) and the housing (1); The distance between the end A of the conductive substrate and the end M of the shell is 1 to 2 mm; S2. Preparation of a solid contact layer (5): A mixture containing a carbon material and an ionic liquid is drop-coated onto the end surface of the conductive substrate (4) at the end A, and after drying, a solid contact layer (5) is formed; S3. Preparation of ion selective membrane (6): A mixture B containing an ion carrier, an ion exchanger, a plasticizer and a membrane matrix is ​​drop-coated on the surface of the solid contact layer (5) and, after drying, an ion selective membrane (6) is formed.

9. The method for preparing a solid perchlorate ion selective electrode according to claim 8, characterized in that: In step S2, the drop coating includes sucking the mixture A and dropping it onto the end surface of the end A of the conductive substrate (4), and then drying it. The sucking and drying operations are repeated 10 to 15 times, and the cumulative drop coating is 80 to 120 μL.

10. The solid perchlorate ion selective electrode according to any one of claims 1 to 7 or the solid perchlorate ion selective electrode prepared by the preparation method according to any one of claims 8 to 9 is used for detecting ClO4 - Application in.

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