Ion-selective membrane, composite liquid perchlorate ion-selective electrode and application

Abstract

The invention discloses an ion-selective membrane, a composite liquid perchlorate ion-selective electrode and application, and belongs to the technical field of ion-selective electrodes. The membrane is prepared from the following raw materials: an ion carrier, an ion exchanger, a plasticizer and a membrane matrix, wherein the ion carrier comprises one, two or more than two of m-tetraphenyl porphyrin ferric chloride, tetra-p-chlorophenyl porphyrin iron and m-tetra (pentafluorophenyl) porphyrin ferric chloride, and the ion selective membrane has better selectivity on ClO4 <->.

Description

Technical Field

[0001] The present invention relates to the technical field of ion selective electrodes, and more specifically to an ion selective membrane, a composite liquid perchlorate ion selective electrode and applications thereof. Background Art

[0002] Perchlorate (ClO4 - ) is a common inorganic pollutant, mainly from the production and use of fireworks, aerospace propellants, military products, textile fixatives, batteries and other products. Due to its high solubility and mobility, and its difficulty in degradation in the environment, it is easy to diffuse and migrate in surface water and groundwater.

[0003] At present, the detection methods of perchlorate mainly include complex colorimetry, ion chromatography, liquid phase mass spectrometry and ion selective electrode method (ISE). Among them, the ion selective electrode method is particularly suitable for online monitoring due to its advantages such as low detection cost, simple operation and wide linear range. Traditional liquid ion selective electrodes usually require an external reference electrode, while the new composite liquid perchlorate ion selective electrode does not require an external reference electrode, realizing the integration of the reference electrode and the working electrode, and the external reference chamber does not contain silver ions, and has strong anti-pollution ability, which further improves its stability and application potential in complex environments. Summary of the invention

[0004] 1. Technical problem to be solved by the invention

[0005] The perchlorate ion selective electrode in the prior art is used for ClO4 - In order to solve the problems of poor selectivity and anti-interference during detection, an ion selective membrane is provided, and at the same time a composite liquid perchlorate ion selective electrode is provided.

[0006] 2. Technical solution

[0007] In order to achieve the above object, the technical solution provided by the present invention is:

[0008] An ion selective membrane of the present invention,

[0009] Contains ion carriers and ion exchangers;

[0010] Wherein, the ion carrier includes one, two or more of m-tetraphenylporphyrin ferric chloride, tetrakis-p-chlorophenylporphyrin ferric chloride and m-tetrakis(pentafluorophenyl)porphyrin ferric chloride.

[0011] Further, it also contains a plasticizer and a film matrix;

[0012] The mass ratio of the membrane matrix, plasticizer, ion carrier and ion exchanger is (30-50):(45-69):(0.5-2.5):(0.5-2.5).

[0013] Furthermore, the ion exchanger includes one, two or more of tridodecylmethylammonium chloride, hexadecyltrimethylammonium bromide and trioctylmethylammonium chloride.

[0014] Furthermore, the plasticizer includes one, two or more of o-nitrophenyl octyl ether, dibutyl phthalate and dioctyl phthalate.

[0015] Furthermore, the film substrate comprises polyvinyl chloride.

[0016] Preferably, the membrane substrate is polyvinyl chloride.

[0017] The present invention also provides a method for preparing the above ion selective membrane, wherein a mixture A containing an ion carrier, an ion exchanger, a plasticizer and a membrane matrix is ​​dried to form the ion selective membrane.

[0018] Furthermore, the solvent of the mixture A is one or both of tetrahydrofuran and cyclohexanone.

[0019] Furthermore, the preparation method of the mixture A is as follows: adding the ion carrier, the ion exchanger, the plasticizer and the membrane matrix into the solvent, and ultrasonicating for 30 to 60 minutes, wherein the ultrasonicating is used for degassing.

[0020] The present invention also provides a composite liquid perchlorate ion selective electrode.

[0021] It includes an electrode body and an electrode tail end connected in sequence;

[0022] The electrode body comprises a front end cap and an electrode body shell which are connected in sequence;

[0023] An ion-selective working electrode and a reference electrode assembly are arranged in the outer shell of the electrode body;

[0024] The ion-selective working electrode comprises a front end cap, a working electrode tube body and a working electrode tail plug which are connected in sequence;

[0025] An ion selective membrane is arranged between the front end cap and the working electrode tube body;

[0026] The reference electrode assembly includes a second porous material component, a reference electrode tube body, and a reference electrode tail plug that are connected in sequence.

[0027] Furthermore, one end of the working electrode tube protrudes from the front end cap.

[0028] The end of the working electrode tube body connected to the front end cap is provided with a plurality of through holes.

[0029] Furthermore, the ion selective working electrode is filled with 10 -4 ~10 -2 M perchlorate ion solution;

[0030] The electrode body is filled with (NH4)2SO4 solution;

[0031] The reference electrode assembly is filled with a saturated KCl solution.

[0032] For example, the electrode body is filled with (NH4)2SO4 solution with a concentration of 0.1M.

[0033] Furthermore, the concentration of perchlorate ions in the perchlorate ion solution is 10 -2 M.

[0034] Preferably, the saturated KCl solution is a gel-type saturated KCl solution.

[0035] Furthermore, the perchlorate ion comes from one, two or more of NaClO4, KClO4, and Mg(ClO4)2.

[0036] For example, perchlorate ions come from NaClO4.

[0037] Furthermore, the ion-selective working electrode also includes a first reference electrode, and the first reference electrode is inserted through the tail plug of the working electrode.

[0038] Furthermore, the reference electrode assembly also includes a second reference electrode, and the second reference electrode is inserted into the tail plug of the reference electrode.

[0039] Furthermore, a first porous material component is provided on the front end cap.

[0040] Furthermore, the first porous material component is a ceramic filter element;

[0041] The second porous material component is a ceramic filter element.

[0042] The ceramic filter element may be a porous ceramic filter element.

[0043] Further, the working electrode tube body comprises a first connecting tube body and a second connecting tube body connected in sequence;

[0044] The first connecting tube body is inserted into the front end cap, one end of the first connecting tube body is connected to the ion selection membrane, and the front end cap is sleeved on the first connecting tube body.

[0045] Furthermore, the first porous material component is arranged on a fixing member.

[0046] Furthermore, the electrode body also includes a fixed cover plate;

[0047] The fixed cover plate is connected to the electrode main body shell.

[0048] Furthermore, the fixed cover plate is provided with through holes for fixing the ion-selective working electrode and the reference electrode assembly.

[0049] Furthermore, a circuit main board is arranged in the tail end of the electrode;

[0050] The circuit main board comprises a single-chip microcomputer chip and its auxiliary circuits, a power management circuit, an RS485 communication circuit, and an ion selective electrode signal amplifier circuit.

[0051] Furthermore, the first reference electrode and the second reference electrode are connected to a circuit main board.

[0052] The present invention also provides a method for detecting ClO4 by using the above-mentioned ion selective membrane or the above-mentioned composite liquid perchlorate ion selective electrode. - Application in the detection of ClO4 - Application in.

[0053] 3. Beneficial effects

[0054] Compared with the prior art, the technical solution provided by the present invention has the following beneficial effects:

[0055] (1) The ion selective membrane provided by the present invention comprises an ion carrier, an ion exchanger, a plasticizer and a membrane matrix; wherein the ion carrier comprises one, two or more of m-tetraphenylporphyrin ferric chloride, tetra-p-chlorophenylporphyrin ferric chloride and m-tetrakis(pentafluorophenyl)porphyrin ferric chloride, and when the ion carrier is used, the ion selective membrane is resistant to ClO4 - There is better selectivity.

[0056] (2) The composite liquid perchlorate ion selective electrode provided by the present invention has a built-in double salt bridge reference electrode assembly, and utilizes the internal cavity of the electrode main body shell as the external salt bridge part, which can increase the electrolyte reserve, provide a more stable reference potential and a longer electrode service life; it not only overcomes the defects of traditional liquid ion selective electrodes, significantly improves the performance and service life of the electrode, but also provides a more reliable and accurate detection tool for water quality monitoring, and has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] Figure 1 This is a schematic diagram of the structure of a composite liquid perchlorate ion selective electrode in Example 1 of the present invention.

[0058] Figure 2 This is a partial exploded view of a composite liquid perchlorate ion selective electrode in Example 1 of the present invention.

[0059] Figure 3 This is an overall exploded view of an electrode body in Example 1 of the present invention.

[0060] Figure 4 This is a partial exploded view of an electrode body in Example 1 of the present invention.

[0061] Figure 5 For the present invention Figure 4 A schematic cross-sectional view of a connection structure of a front end cap, a first connecting tube body and a front end cap.

[0062] Figure 6 For the present invention Figure 5 A partially enlarged schematic diagram of the connection structure between the middle and front end cap and the first connecting tube body.

[0063] Figure 7 ClO4 of the liquid perchlorate ion selective electrode of Application Example 1 of the present invention - 、NO3 - 、CO3 2- PO4 3- , Cl - 、SO4 2- Standard curve graph.

[0064] Figure 8 ClO4 of the liquid perchlorate ion selective electrode of Application Example 2 of the present invention - 、NO3 - 、CO3 2- PO4 3- , Cl - 、SO4 2- Standard curve graph.

[0065] Fig. 9 ClO4 of the liquid perchlorate ion selective electrode of Application Example 3 of the present invention - 、NO3 - 、CO3 2- PO4 3- , Cl - 、SO4 2- Standard curve graph.

[0066] Explanation of the symbols in the schematic diagram:

[0067] 100. Electrode body;

[0068] 110. Electrode main body shell; 111. First porous material component;

[0069] 120, ion selective working electrode; 121, front end cap; 122, working electrode tube body; 1221, first connecting tube body; 1222, second connecting tube body; 123, working electrode tail plug; 124, first reference electrode; 125, ion selective membrane;

[0070] 130. Reference electrode assembly; 131. Second porous material component; 132. Reference electrode tube; 133. Reference electrode tail plug; 134. Second reference electrode;

[0071] 140. Fixing cover plate;

[0072] 150, front end cap; 151, fixing piece; 152, snap ring; 153, connecting ring body; 154, snap groove;

[0073] 200, electrode tail end; 210, circuit main board. DETAILED DESCRIPTION

[0074] 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.

[0075] 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.

[0076] 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".

[0077] 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.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] An ion selective membrane 126 in the present invention is made of the following raw materials: containing ion carriers, ion exchangers, plasticizers and membrane substrates; wherein the ion carriers include one, two or more of m-tetraphenylporphyrin ferric chloride, tetra-p-chlorophenylporphyrin ferric chloride and m-tetrakis (pentafluorophenyl) porphyrin ferric chloride. The ion exchangers include one, two or more of tridodecylmethylammonium chloride, hexadecyltrimethylammonium bromide and trioctylmethylammonium chloride; the plasticizers include one, two or more of o-nitrophenyl octyl ether, dibutyl phthalate and dioctyl phthalate; and the membrane substrate includes polyvinyl chloride. As a preferred embodiment, the membrane substrate is polyvinyl chloride.

[0084] Furthermore, 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).

[0085] The preparation method of the ion selective membrane 126 is as follows: drying the mixture A containing the ion carrier, the ion exchanger, the plasticizer and the membrane matrix to form the ion selective membrane 126. As a specific implementation, the mixture A containing the ion carrier, the ion exchanger, the plasticizer and the membrane matrix can be poured into a glass culture dish and then placed in an oven for drying.

[0086] Further, the preparation method of mixture A is: adding ion carrier, ion exchanger, plasticizer and membrane matrix to a solvent, and ultrasonicating for 30 to 60 minutes, and the ultrasonication is used for degassing; the solvent of mixture A is one or two of tetrahydrofuran and cyclohexanone. As a specific embodiment, the solvent of mixture A can be tetrahydrofuran, which is removed by drying after being used as a solvent, and the specific usage amount can be adjusted to facilitate dissolving the raw materials and drying and removal.

[0087] Example 1

[0088] Combination Figure 1-Figure 4 A composite liquid perchlorate ion selective electrode of this embodiment includes an electrode body 100 and an electrode tail end 200 connected in sequence; the electrode body 100 includes a front end cap 150 and an electrode body shell 110 connected in sequence, and an ion selective working electrode 120 and a reference electrode assembly 130 are arranged in the electrode body shell 110;

[0089] The ion-selective working electrode 120 includes a front end cap 121, a working electrode tube body 122 and a working electrode tail plug 123 which are connected in sequence; one end of the working electrode tube body 122 protrudes from the front end cap 150, and an ion-selective membrane 125 is arranged between the front end cap 121 and the working electrode tube body 122; a plurality of through holes are arranged at one end of the working electrode tube body 122 connected to the front end cap 121; the reference electrode assembly 130 includes a second porous material component 131, a reference electrode tube body 132, and a reference electrode tail plug 133 which are connected in sequence, and the reference electrode assembly 130 is located in the electrode main body shell 110, and one end does not protrude from the front end cap 150. The composite liquid perchlorate ion selective electrode has a built-in double salt bridge reference electrode assembly 130, and utilizes the internal cavity of the electrode main body shell 110 as the external salt bridge part, which can increase the electrolyte reserve, provide a more stable reference potential and a longer electrode service life; it not only overcomes the defects of traditional liquid ion selective electrodes, significantly improves the performance and service life of the electrode, but also provides a more reliable and accurate detection tool for water quality monitoring, and has broad application prospects.

[0090] As a specific implementation, the working electrode tube body 122 can be a round tube, and can be made of polyvinyl chloride plastic or glass. The second porous material component 131 in the reference electrode assembly 130 can be a ceramic filter element, and can be cylindrical in shape; the reference electrode tube body 132 can be a round tube, and can be made of polyvinyl chloride plastic or glass; the ceramic filter element can be inserted into the reference electrode tube body 132. The size and shape of the working electrode tail plug 123 and the reference electrode tail plug 133 can be determined according to the diameter of the connected pipe.

[0091] One end of the working electrode tube body 122 protruding from the front end cap 150 is provided with annularly arranged small holes, on which the ion selective membrane 125 is bonded and covered. As a specific embodiment, UV glue is coated around the ion selective membrane 125 and cured by ultraviolet light, so that the ion selective membrane 125 is tightly bonded to the working electrode tube body 122, and then the ion selective membrane 125 is fixed by the front end cap 121. On the other hand, the ion selective membrane 125 obtained by drying can be obtained to obtain an ion selective membrane 125 of appropriate size, for example, by using a puncher to obtain an ion selective membrane 125 of appropriate size, and then put into the ion selective working electrode 120.

[0092] Furthermore, the working electrode tube 122 in the ion-selective working electrode 120 is filled with a perchlorate ion solution; the reference electrode tube 132 of the reference electrode assembly 130 is filled with a saturated KCl solution; and the electrode body housing 110 of the electrode body 100 is filled with a (NH4)2SO4 solution. As an optional embodiment, the perchlorate ions come from one, two or more of NaClO4, KClO4, and Mg(ClO4)2. For example, the perchlorate ions come from NaClO4. The saturated KCl solution is a gel-type saturated KCl solution. The working electrode tail plug 123 is connected to the working electrode tube 122 to prevent the perchlorate ion solution from leaking from the end of the working electrode tube 122; the reference electrode tube 132 is connected to the reference electrode tail plug 133 to prevent the saturated KCl solution from leaking from the end of the reference electrode tube 132.

[0093] Furthermore, the ion-selective working electrode 120 also includes a first reference electrode 124, which is inserted into the working electrode tail plug 123. After the first reference electrode 124 is led out through the working electrode tail plug 123, the rear end of the working electrode tube 122 is sealed by an adhesive such as silicone or epoxy resin glue, including the connection between the working electrode tail plug 123 and the working electrode tube 122, and the connection between the first reference electrode 124 and the working electrode tail, so as to improve the sealing of the ion-selective working electrode 120. The reference electrode assembly 130 also includes a second reference electrode 134, which is inserted into the reference electrode tail plug 133. After the second reference electrode 134 is led out through the reference electrode tail plug 133, the rear end of the reference electrode tube 132 is sealed by an adhesive such as silicone or epoxy resin glue, including the connection between the reference electrode tail plug 133 and the reference electrode tube 132, and the connection between the first reference electrode 124 and the tail of the reference electrode assembly 130, so as to improve the sealing of the reference electrode assembly 130. As a specific embodiment, the first reference electrode 124 and the second reference electrode 134 are both Ag / AgCl electrode wires, and the Ag / AgCl electrode wire is specifically electroplated silver chloride silver wire. The working electrode tail plug 123 and the reference electrode tail plug 133 can be provided with a wire hole for passing the Ag / AgCl electrode wire, and the connection between the wire hole and the Ag / AgCl electrode wire is also sealed with silicone or epoxy resin glue.

[0094] Furthermore, a first porous material component 111 is disposed on the front end cap 150. As an optional embodiment, the first porous material component 111 is a ceramic filter element, which may be cylindrical in shape. The (NH4)2SO4 solution filled in the electrode body housing 110 may leak into the ambient water through the ceramic filter element.

[0095] Combination Figure 4As an optional embodiment, the working electrode tube body 122 includes a first connecting tube body 1221 and a second connecting tube body 1222 connected in sequence; the first connecting tube body 1221 is inserted into the front end cap 150, and can be detachably connected to the second connecting tube body 1222 by threaded connection or slot connection. One end of the first connecting tube body 1221 is connected to the ion selective membrane 125, and the front end cap 121 is sleeved on the first connecting tube body 1221 to further fix the ion selective membrane 125. The first connecting tube body 1221 is detachably connected, so that the first connecting tube body 1221 can be removed to install the ion selective membrane 125.

[0096] Combination Figure 5 , Figure 6 As an optional embodiment, the front end cap 150 includes a fixing member 151, a clamping ring 152 and a connecting ring body 153. The first connecting tube body 1221 is inserted into the fixing member 151; the clamping ring 152 and the connecting ring body 153 are arranged on the same side of the fixing member 151. The first connecting tube body 1221, the fixing member 151, the clamping ring 152 and the connecting ring body 153 can be an integrated structure to improve the sealing performance.

[0097] The first connecting tube body 1221 can be a round tube with one end closed, and the end surface of the closed end, i.e., the membrane attachment, is provided with an annularly arranged through holes, on which the ion selective membrane 125 can be bonded and covered, and the size of the ion selective membrane 125 can be the same as the size of the end surface; the other end cooperates with the clamping ring 152 to form a clamping groove 154, and is connected to the second connecting tube body 1222 by means of a clamping groove. The fixing member 151 is a circular fixing plate, and the first connecting tube body 1221 protrudes from the fixing member 151 so that the ion selective membrane 125 protrudes outside the fixing member 151. The outer periphery of the connecting ring body 153 is provided with protrusions and grooves, which can be detachably connected to the electrode main body shell 110 by means of a clamping engagement, and can also be disassembled to facilitate the installation of the ion selective membrane 125. The first porous material component 111 is inserted in the fixing member 151. On the other hand, the clamping ring 152 and the first porous material component 111 are both arranged in the area surrounded by the connecting ring body 153.

[0098] The front end cap 121 is sleeved on the first connecting tube body 1221 to further fix the ion selective membrane 125. A through hole is provided at one end of the front end cap 121 that contacts the ion selective membrane 125, so that the ion selective membrane 125 can normally contact and detect the water body.

[0099] Further, the electrode body 100 further includes a fixed cover plate 140, which is connected to the electrode body shell 110. For example, the outer edge of the fixed cover plate 140 may be provided with a thread to connect to the electrode body shell 110, or a connecting ring body 153 with protrusions and grooves on the outer periphery may be provided to connect to the electrode body shell 110. After the front end cap 150, the fixed cover plate 140 and the electrode body shell 110 are connected, a closed cavity is formed, and the electrode body shell 110 may be filled with a (NH4)2SO4 solution. As a specific embodiment, the fixing member 151 in the front end cap 150 and the fixed cover plate 140 are connected to the electrode body shell 110 to form a closed cavity.

[0100] The fixed cover plate 140 is provided with a through hole for fixing the ion selective working electrode 120 and the reference electrode assembly 130. As an optional embodiment, the fixed cover plate 140 may be provided with two through holes, which are respectively the same as the outer diameters of the working electrode tube body 122 and the reference electrode tube body 132, so as to fix the ion selective working electrode 120 and the reference electrode assembly 130. As another optional embodiment, the two through holes on the fixed cover plate 140 may be connected to further reduce the volume.

[0101] Furthermore, a circuit main board 210 is provided in the electrode tail end 200; the circuit main board 210 includes a single-chip microcomputer chip and its auxiliary circuits, a power management circuit, an RS485 communication circuit, and an ion selective electrode signal amplifier circuit. The ion selective electrode signal amplifier circuit is used to collect, transmit, and amplify the signal generated by the ion selective working electrode 120. The first reference electrode 124 and the second reference electrode 134 are connected to the circuit main board 210. Specifically, the first reference electrode 124 and the second reference electrode 134 can be welded to the circuit main board 210.

[0102] Application Example 1

[0103] Preparation of ion selective membrane 125: 176.4 mg of polyvinyl chloride, 176.4 mg of o-nitrophenyl octyl ether, 3.6 mg of m-tetraphenylporphyrin iron (III) chloride (purchased from Aladdin, CAS No.: 16456-81-8) and 3.6 mg of tridodecylmethylammonium chloride are dissolved in 2.5 mL of tetrahydrofuran solvent, and ultrasonic degassing is performed for 30 minutes. The mixed solution is poured into a glass culture dish with a diameter of 4 cm, and then placed in a 40°C oven for drying to form an ion selective membrane 125 with a thickness of about 0.2 mm; using the liquid perchlorate ion selective electrode in Example 1, a puncher is used to take an ion selective membrane 125 with a diameter of 8 mm, and it is bonded to the first connecting tube body 1221. Specifically, UV glue is coated around the ion selective membrane 125 and cured by ultraviolet light, so that the ion selective membrane 125 is tightly bonded to the film-attaching part of the first connecting tube body 1221, and then the ion selective membrane 125 is fixed by the front end cap 121; wherein, the working electrode tube body 122 of the ion selective working electrode 120 is filled with a 10 -2 mol / L NaClO4 solution, the electrode main body shell 110 is filled with a (NH4)2SO4 solution with a concentration of 0.1 mol / L, and the reference electrode tube 132 of the reference electrode assembly 130 is filled with a gel-type saturated KCl solution; the ion-selective electrode signal amplifier circuit has a chip model of LM358 (purchased from: https: / / item.taobao.com / item.htm?_u=q2osq1scb7c7&id=562928076498&spm=a1z09.2.0.0.589d2e8dO0Rj5x).

[0104] Application Example 2

[0105] The method is basically the same as Application Example 1, except that the ion carrier in the raw material of the ion selective membrane 126 of the liquid perchlorate ion selective electrode of this application example is tetrakis-p-chlorophenylporphyrin iron (III) (purchased from Aladdin, CAS No.: 36965-70-5).

[0106] Application Example 3

[0107] The method is basically the same as Application Example 1, except that the ion carrier in the raw material of the ion selective membrane 126 of the liquid perchlorate ion selective electrode of this application example is m-tetrakis(pentafluorophenyl)porphyrin iron (III) chloride (purchased from Merck, CAS No.: 36965-71-6).

[0108] Performance Testing

[0109] The composite liquid perchlorate ion selective electrode prepared in the above application example was placed in 10 -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 - Gradient solution, composite liquid perchlorate ion selective electrode is directly connected to the potentiometer, and the potentiometer records the ClO4 - The potential value under the concentration gradient solution is then measured with ClO4 - The standard curve is drawn by the logarithmic concentration value and the potential value. The selectivity of the liquid perchlorate ion selective electrode is tested by the separate solution method. The main response ion i(ClO4 - ) and interfering ions j(NO3 - 、CO3 2- PO4 3- , Cl - 、SO4 2- ) potential standard curve, where the interfering ion j(NO3 - 、CO3 2- PO4 3- , Cl - 、SO4 2- ) is determined by measuring each ion individually, and each ion is configured with 10 -5 mol / L、10 -4 mol / L、10 -3 mol / L、10 -2 mol / L、10 -1 mol / L gradient solution, and the potential value of the main response ion i with a concentration of 1M was extrapolated 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.

[0110] Table 1 lgK of liquid perchlorate ion selective electrodes prepared in different application examples ij data

[0111]

[0112] 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 - >CO32- >PO4 3- >Cl - >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. The order of selectivity and anti-interference of application examples is: application example 3> application example 1> application example 2.

Claims

1. An ion selective membrane, characterized in that: Contains ion carriers and ion exchangers; Wherein, the ion carrier includes one, two or more of m-tetraphenylporphyrin ferric chloride, tetrakis-p-chlorophenylporphyrin ferric chloride and m-tetrakis(pentafluorophenyl)porphyrin ferric chloride.

2. The ion selective membrane according to claim 1, characterized in that: It also contains a plasticizer and a film matrix; The mass ratio of the membrane matrix, plasticizer, ion carrier and ion exchanger is (30-50):(45-69):(0.5-2.5):(0.5-2.5).

3. The ion selective membrane according to claim 2, characterized in that: The ion exchanger comprises one, two or more of tridodecylmethylammonium chloride, hexadecyltrimethylammonium bromide and trioctylmethylammonium chloride; and / or, The plasticizer includes one, two or more of o-nitrophenyl octyl ether, dibutyl phthalate and dioctyl phthalate; and / or, The film substrate includes polyvinyl chloride.

4. A composite liquid perchlorate ion selective electrode, characterized in that: It comprises an electrode main body (100) and an electrode tail end (200) which are connected in sequence; The electrode body (100) comprises a front end cap (150) and an electrode body shell (110) which are connected in sequence; An ion-selective working electrode (120) and a reference electrode assembly (130) are arranged in the electrode main body shell (110); The ion-selective working electrode (120) comprises a front end cap (121), a working electrode tube body (122) and a working electrode tail plug (123) which are connected in sequence; An ion selective membrane (125) as claimed in any one of claims 1 to 3 is arranged between the front end cap (121) and the working electrode tube (122); The reference electrode assembly (130) comprises a second porous material component (131), a reference electrode tube body (132), and a tail plug of the reference electrode assembly (130) which are connected in sequence.

5. The composite liquid perchlorate ion selective electrode according to claim 4, characterized in that: The ion selective working electrode (120) is filled with a perchlorate ion solution; The electrode body (100) is filled with (NH4)2SO4 solution; The reference electrode assembly (130) is filled with a saturated KCl solution.

6. The composite liquid perchlorate ion selective electrode according to claim 5, characterized in that: The ion-selective working electrode (120) further comprises a first reference electrode (124), wherein the first reference electrode (124) is disposed through the tail plug (123) of the working electrode; The reference electrode assembly (130) further comprises a second reference electrode (134), wherein the second reference electrode (134) is inserted through a plug at the tail end of the reference electrode assembly (130); The front end cap (150) is provided with a first porous material component (111).

7. The composite liquid perchlorate ion selective electrode according to claim 6, characterized in that: The working electrode tube body (122) comprises a first connecting tube body (1221) and a second connecting tube body (1222) which are connected in sequence; The first connecting tube body (1221) is inserted into the front end cap (150), one end of the first connecting tube body (1221) is connected to the ion selective membrane (125), and the front end cap (121) is sleeved on the first connecting tube body (1221).

8. The composite liquid perchlorate ion selective electrode according to any one of claims 4 to 7, characterized in that: The electrode body (100) further includes a fixed cover plate (140); The fixed cover plate (140) is connected to the electrode main body shell (110); The fixed cover plate (140) is provided with through holes for fixing the ion-selective working electrode (120) and the reference electrode assembly (130).

9. The composite liquid perchlorate ion selective electrode according to claim 8, characterized in that: A circuit main board (210) is disposed in the electrode tail end (200); The first reference electrode (124) and the second reference electrode (134) are connected to the circuit main board (210).

10. An ion selective membrane as claimed in any one of claims 1 to 3 or a composite liquid perchlorate ion selective electrode as claimed in any one of claims 4 to 9 for detecting ClO4 - Application in.

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