CN113671006A - Hydrogen ion selective membrane and preparation method thereof - Google Patents
Hydrogen ion selective membrane and preparation method thereof Download PDFInfo
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- CN113671006A CN113671006A CN202110856392.1A CN202110856392A CN113671006A CN 113671006 A CN113671006 A CN 113671006A CN 202110856392 A CN202110856392 A CN 202110856392A CN 113671006 A CN113671006 A CN 113671006A
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- hydrogen ion
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/333—Ion-selective electrodes or membranes
Abstract
The embodiment of the invention relates to the technical field of chemical analysis, in particular to a hydrogen ion selective membrane and a preparation method thereof. The hydrogen ion selective membrane comprises an ionophore comprising at least one of dioctadecylmethylamine and tri-n-dodecylamine; additives including potassium tetrakis (4-chlorophenyl) borate; a polymer matrix; a plasticizer comprising at least one of dioctyl sebacate, 2-nitrophenyloctyl ether and tris (2-ethylhexyl) phosphate. The hydrogen ion selective membrane has good selectivity linearity and sensitivity to hydrogen ions, good repeatability and long service life.
Description
Technical Field
The embodiment of the invention relates to the technical field of chemical analysis, in particular to a hydrogen ion selective membrane and a preparation method thereof.
Background
Detection and measurement of ionic species is of great importance in many fields such as biomedical research, environmental monitoring and control of production processes. For example, the pH value of a human body is an important index, most epidemic diseases can cause the pH value abnormality in the human body, the pH value and the hydrogen ion activity have a certain proportional relation, and the pH value can be scaled by the pH value.
Common methods for detecting pH include pH paper, amperometry, nuclear magnetic resonance, absorption spectroscopy, and fluorescent probe methods. Among other things, pH paper measurements are often not accurate enough because the color transition point is often related to the subjective judgment of the user. The ampere method has the advantages that the method is simple, but the composition of a detected sample has great influence on a measurement result, and in a very strong acid or very strong alkaline solution, the pH value measurement has only small practical value due to the pH glass film effect. Among them, the methods of nuclear magnetic resonance, absorption spectroscopy and fluorescent probe have the disadvantages of requirement on detection environment, complex operation, slow speed and the like.
The method of potentiometry can be used to test the hydrogen ion activity in liquids and avoid these problems. The apparatus for potentiometrically determining hydrogen ions comprises a reference electrode and a hydrogen ion selective electrode, which form a potential therebetween when immersed in a liquid at the same time, the potential being linearly related to the logarithm of the hydrogen ion activity, the potential being determined by a potentiometric measuring device such as a potentiometer, and the hydrogen ion activity being obtained by measuring the potential.
However, in the process of implementing the embodiment of the present invention, the inventors of the present invention found that: the method for measuring the potential requires that the hydrogen ion selective membrane for preparing the hydrogen ion selective electrode has high selectivity and unicity on hydrogen ions and has certain requirements on the strength, toughness, sensitivity, accuracy, repeatability and the like of the hydrogen ion selective membrane, however, the hydrogen ion selective membrane for the potential measuring device and the preparation method thereof are not available at present.
Disclosure of Invention
In view of the above problems, embodiments of the present invention provide a hydrogen ion selective membrane and a method for producing a hydrogen ion selective membrane that overcome or at least partially solve the above problems.
According to an aspect of an embodiment of the present invention, there is provided a hydrogen ion selective membrane including an ionophore including at least one of dioctadecylmethylamine and tri-n-dodecylamine; additives including potassium tetrakis (4-chlorophenyl) borate; a polymer matrix; a plasticizer comprising at least one of dioctyl sebacate, 2-nitrophenyloctyl ether and tris (2-ethylhexyl) phosphate.
In an optional mode, the content of the ionophore is 2% -5%, the content of the additive is 0.2% -1%, the content of the polymer matrix is 12% -15%, and the content of the plasticizer is 8% -14%.
In an alternative embodiment, the ionophore is present in an amount of 5%, the additive is present in an amount of 0.25%, the polymer matrix is present in an amount of 14.75%, and the plasticizer is present in an amount of 10%.
In an alternative form, the ionophore includes tri-n-dodecylamine.
In an alternative form, the polymer matrix comprises polyvinyl chloride.
In an alternative form, the plasticizer comprises dioctyl sebacate.
According to an aspect of an embodiment of the present application, there is provided a method of manufacturing a hydrogen ion selective membrane, including: sequentially adding a plasticizer, an ionophore, an additive and a polymer matrix into a solvent to form a hydrogen ion selective membrane solution, wherein the plasticizer comprises at least one of dioctyl sebacate, 2-nitrophenyloctyl ether and tri (2-ethylhexyl) phosphate, the ionophore comprises at least one of dioctadecyl methylamine and tri-n-dodecylamine, and the additive comprises potassium tetrakis (4-chlorophenyl) borate; stirring and heating the hydrogen ion selective membrane solution in water bath; and drying the heated hydrogen ion selective membrane solution to form a membrane.
In an alternative form, the solvent comprises cyclohexanone or propiophenone.
In an optional mode, the content of the solvent is 65% -70%, the content of the ionophore is 2% -5%, the content of the additive is 0.2% -1%, the content of the polymer matrix is 12% -15%, and the content of the plasticizer is 8% -14%.
According to an aspect of an embodiment of the present invention, there is provided an electrolyte analysis system including an electrolyte analyzer and the above-described hydrogen ion selective membrane.
Advantageous effects of embodiments of the present invention include providing a hydrogen ion selective membrane including: an ionophore comprising at least one of dioctadecylmethylamine and tri-n-dodecylamine; additives including potassium tetrakis (4-chlorophenyl) borate; a polymer matrix; a plasticizer comprising at least one of dioctyl sebacate, 2-nitrophenyloctyl ether and tris (2-ethylhexyl) phosphate. The hydrogen ion selective membrane provided by the application can be applied to a potential measuring device, so that the activity of hydrogen ions in liquid is measured. The hydrogen ion selective membrane provided by the application is used for detecting the activity of hydrogen ions in liquid, and has the advantages of good linearity, high sensitivity and strong ageing resistance.
Drawings
One or more embodiments are illustrated by way of example in the accompanying drawings, which correspond to the figures in which like reference numerals refer to similar elements and which are not to scale unless otherwise specified.
FIG. 1 is a schematic diagram of the relationship between the potential of a hydrogen ion solution and the logarithm of the hydrogen ion activity in a hydrogen ion selective membrane test provided by an embodiment of the present invention;
FIG. 2 is a test result of the long-term service life of a hydrogen ion selective membrane provided by an embodiment of the present invention;
fig. 3 is a schematic flow chart of a method for producing a hydrogen ion selective membrane according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Embodiments of the present invention provide a hydrogen ion selective membrane, wherein when the hydrogen ion selective membrane and a reference electrode are immersed in a liquid solution at the same time, a potential is formed between the hydrogen ion selective membrane and the reference electrode, the potential is proportional to a logarithm of the activity of hydrogen ions in the solution, and the activity of hydrogen ions in the solution can be obtained by measuring the potential by a potential measuring device, such as a potentiometer.
The hydrogen ion selective membrane includes an ionic carrier, an additive, a polymer matrix, and a plasticizer.
In some embodiments, the ionophore is present in an amount of 2% to 5%, the additive is present in an amount of 0.2% to 1%, the polymer matrix is present in an amount of 12% to 15%, and the plasticizer is present in an amount of 8% to 14%.
In some embodiments, the ionophore is present in an amount of 5%, the additive is present in an amount of 0.25%, the polymer matrix is present in an amount of 14.75%, and the plasticizer is present in an amount of 10%.
As for the above-mentioned ionophore, the ionophore is used to form a neutral or charged complex with hydrogen ions by means of ion exchange, complexation or extraction. The ionophore must be highly selective and specific for hydrogen ions. The ionophore includes at least one of dioctadecylmethylamine and tri-n-dodecylamine. Preferably, the ionophore includes tri-n-dodecylamine. Preferably, the content of the tri-n-dodecylamine is 5%.
For the above additives, the additives need to contribute to the improvement of the conductivity of the hydrogen ion selective membrane, and have three main functions: the hydrogen ion selective membrane has Nernst response, the capability of resisting anion interference is enhanced, the membrane internal resistance is reduced, the requirement on the impedance of an electrolyte analyzer is reduced, and the test stability is improved. Additives of embodiments of the present invention include potassium tetrakis (4-chlorophenyl) borate. Preferably, the content of the potassium tetrakis (4-chlorophenyl) borate is 0.25%.
For the polymer matrix, the polymer matrix has stronger chemical stability and non-polarity and can contain more organic solvents. The polymer matrix is required to provide mechanical strength to the hydrogen ion selective membrane and provide a glass transition temperature below room temperature, and must be capable of allowing a flux of particles to pass through the hydrogen ion selective membrane, and is typically used in combination with the additives, and in the present embodiment, the polymer matrix comprises polyvinyl chloride, preferably, the polyvinyl chloride is present in an amount of 14.75%.
For the above plasticizers, the use of a plasticizer provides elasticity and toughness to the polymer matrix and enables the flow of particles through the hydrogen ion selective membrane, while at the same time the plasticizer should be an organic solvent that is hydrophobic, highly viscous, and capable of dissolving relatively large amounts of ionophores. The plasticizers of the embodiments of the present invention include at least one of dioctyl sebacate, 2-nitrophenyloctyl ether, and tris (2-ethylhexyl) phosphate, considering that the plasticizer also has a certain selectivity for specific ions, and that both the plasticizer and ionophore are lost to some extent as the hydrogen ion selective membrane is in contact with the solution for a long time, which may cause the hydrogen ion selective membrane to age. Preferably, the plasticizer comprises dioctyl sebacate. Preferably, the content of the dioctyl sebacate is 10%.
In order to facilitate a reader to intuitively and better understand the performance and the effect of the hydrogen ion selection membrane in the embodiment of the invention, the hydrogen ion selection membrane is subjected to linearity and sensitivity test, repeatability test and long-term service life test.
(1) Linear and sensitivity testing
And placing the electrode made of the hydrogen ion selective membrane on an electrolyte analyzer to perform linearity and sensitivity tests. Respectively configuring 8 hydrogen ion solutions with different activities, wherein the pH value of the hydrogen ion solution is between 6.6 and 8.0, specifically 6.6, 6.8, 7.0, 7.2, 7.4, 7.6, 7.8 and 8.0, each activity level is respectively tested on the electrolyte analyzer for 3 times, recording the potential and respectively averaging the potential, and recording the relation between the potential and the logarithm of the hydrogen ion activity (namely-pH) in figure 1.
As can be seen from FIG. 1, when the pH value of the hydrogen ion solution is between 6.6 and 8.0, the activity of the hydrogen ion solution is detected by the hydrogen ion selective membrane, and the logarithm log [ H ] of the detected potential and the activity of the hydrogen ion is detected+](i.e., -pH) is linear with a slope of 55.23, R2The results show that the hydrogen ion selective membrane has good linearity and sensitivity, 0.9997.
(2) Repeatability test
And placing the electrode made of the hydrogen ion selective membrane on an electrolyte analyzer for repeated test. Solutions of 3 different activity values were selected. Placing the electrode made of the hydrogen ion selective membrane in the solution for repeatability test, testing each solution for 10 times, and performing statistical calculation on the test results, wherein the calculation results are shown in the following table 1:
TABLE 1 Hydrogen ion-selective membrane repeatability test results
| pH value | Standard deviation SD (mmol/L) | Coefficient of variation CV | |
| Solution 1 | 7.09 | 0.02 | 0.25％ |
| Solution 2 | 7.52 | 0.01 | 0.15％ |
| Solution 3 | 8.01 | 0.03 | 0.33％ |
As can be seen from Table 1, the test results show that the standard deviation SD of each solution is less than 0.05 and the coefficient of variation CV of each solution is less than 1.5 percent after 10 times of test, and the hydrogen ion selective membrane meets the industrial standard, so that the repeatability of the hydrogen ion selective membrane is good.
(3) Long term service life test
After the hydrogen ion selective membrane is prepared into an electrode, ionic carriers and plasticizers in the hydrogen ion selective membrane can be lost along with the use of the electrode, and the sensitivity of the hydrogen ion selective membrane, namely the logarithm log [ H ] of the potential and the activity of hydrogen ions, can be influenced+]The slope of (a) is reduced, and poor repeatability is expressed, so that the slope is selected as a judgment index to track the service life of the hydrogen ion selective membrane of the embodiment of the invention. And placing the electrode made of the hydrogen ion selective membrane in an electrolyte analyzer, ensuring the test quantity of 50-70 samples every day, and recording the slope of the electrode made of the hydrogen ion selective membrane at irregular intervals. The slope results for a period of 300 days are recorded in figure 2.
As can be seen from fig. 2, the slope of the electrode prepared from the hydrogen ion selective membrane is mostly higher than 55, and the lowest value of the slope is not lower than 50 in the test time of 300 days, so that the long-term service life of the hydrogen ion selective membrane is good.
The embodiment of the invention provides a hydrogen ion selective membrane, which comprises an ion carrier, a hydrogen ion selective membrane and a hydrogen ion selective membrane, wherein the ion carrier comprises at least one of dioctadecylmethylamine and tri-n-dodecylamine; additives including potassium tetrakis (4-chlorophenyl) borate; a polymer matrix; a plasticizer comprising at least one of dioctyl sebacate, 2-nitrophenyloctyl ether and tris (2-ethylhexyl) phosphate. The hydrogen ion selective membrane provided by the application can be applied to a potential measuring device, so that the activity of hydrogen ions in liquid is measured. The hydrogen ion selective membrane provided by the application is used for detecting the activity of hydrogen ions in liquid, and has good linearity and high sensitivity. The hydrogen ion selective membrane provided by the embodiment of the invention has good strength and toughness, can be suitable for preparing various hydrogen ion selective electrodes, and has long service life under the condition of ensuring the performance.
An embodiment of the present invention provides a method for preparing a hydrogen ion selective membrane, referring to fig. 3, the method includes the following steps:
and step S101, sequentially adding the plasticizer, the ionophore, the additive and the polymer matrix into a solvent to form a hydrogen ion selective membrane solution.
Wherein the plasticizer comprises at least one of dioctyl sebacate, 2-nitrophenyloctyl ether and tri (2-ethylhexyl) phosphate, the ionophore comprises at least one of dioctadecylmethylamine and tri-n-dodecylamine, and the additive comprises potassium tetrakis (4-chlorophenyl) borate.
Wherein the solvent comprises cyclohexanone or propiophenone, and preferably, the solvent is cyclohexanone.
Wherein, the content of the solvent is 65-70%, the content of the ionophore is 2-5%, the content of the additive is 0.2-1%, the content of the polymer matrix is 12-15%, and the content of the plasticizer is 8-14%.
Wherein, in some embodiments, the solvent is present in an amount of 70%, the ionophore is present in an amount of 5%, the additive is present in an amount of 0.25%, the polymer matrix is present in an amount of 14.75%, and the plasticizer is present in an amount of 10%.
And step S102, stirring and heating the hydrogen ion selective membrane solution in a water bath.
In some embodiments, the water bath temperature is 50 ℃ and the heating time is 30 minutes.
And step S103, drying the heated hydrogen ion selective membrane solution to form a membrane.
Wherein the drying time is generally 72 hours.
The heated hydrogen ion selective membrane solution may be dried into a membrane in a variety of ways, for example, by being introduced into an electrode chamber and dried. For another example, the hydrogen ion selective membrane can also be made into a tubular shape, specifically, the heated hydrogen ion selective membrane solution is coated on the surface of a stainless steel needle, the hydrogen ion selective membrane solution is continuously coated after the solvent is volatilized, the process is repeated for 2 to 9 times until the thickness reaches about 0.6mm, the stainless steel needle is extracted, a tubular hydrogen ion selective membrane is formed, and the tubular hydrogen ion selective membrane can be assembled in an electrode shell to form a complete electrode.
It should be noted that, in some embodiments, the hydrogen ion selective membrane may also be made into a membrane electrode, specifically, the heated hydrogen ion selective membrane solution is poured into a flat-bottom container with a suitable size, the container material may be glass cup or stainless steel, the container containing the hydrogen ion membrane solution is placed in a dry environment, and after the solvent naturally volatilizes for 72 hours, a membrane electrode with a membrane thickness of about 0.5mm is formed. Furthermore, the membrane electrode can be adhered to an electrode shell, and a complete hydrogen ion measuring system is formed after the corresponding solution and the reference electrode are installed.
It is understood that the hydrogen ion selective membrane can also be made into other forms of electrodes, such as card electrodes, and the like, and the description of the preparation method of the card electrodes and the like is omitted here.
The embodiment of the invention provides an electrolyte analysis system which comprises an electrolyte analyzer and the hydrogen ion selective membrane. The electrolyte analyzer cooperates with the hydrogen ion selective membrane to test the activity of hydrogen ions in solution.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; within the idea of the invention, also technical features in the above embodiments or in different embodiments may be combined, steps may be implemented in any order, and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A hydrogen ion selective membrane, comprising:
an ionophore comprising at least one of dioctadecylmethylamine and tri-n-dodecylamine;
additives including potassium tetrakis (4-chlorophenyl) borate;
a polymer matrix;
a plasticizer comprising at least one of dioctyl sebacate, 2-nitrophenyloctyl ether and tris (2-ethylhexyl) phosphate.
2. The hydrogen ion selective membrane of claim 1, wherein the ionophore is present in an amount of 2% to 5%, the additive is present in an amount of 0.2% to 1%, the polymer matrix is present in an amount of 12% to 15%, and the plasticizer is present in an amount of 8% to 14%.
3. The hydrogen ion selective membrane of claim 2, wherein the ionophore is present in an amount of 5%, the additive is present in an amount of 0.25%, the polymer matrix is present in an amount of 14.75%, and the plasticizer is present in an amount of 10%.
4. The hydrogen ion selective membrane of claim 1, wherein the ionophore comprises tri-n-dodecylamine.
5. The hydrogen ion selective membrane of claim 1, wherein the polymer matrix comprises polyvinyl chloride.
6. The hydrogen ion selective membrane of claim 1, wherein the plasticizer comprises dioctyl sebacate.
7. A method of producing a hydrogen ion selective membrane, comprising:
sequentially adding a plasticizer, an ionophore, an additive and a polymer matrix into a solvent to form a hydrogen ion selective membrane solution, wherein the plasticizer comprises at least one of dioctyl sebacate, 2-nitrophenyloctyl ether and tri (2-ethylhexyl) phosphate, the ionophore comprises at least one of dioctadecyl methylamine and tri-n-dodecylamine, and the additive comprises potassium tetrakis (4-chlorophenyl) borate;
stirring and heating the hydrogen ion selective membrane solution in water bath;
and drying the heated hydrogen ion selective membrane solution to form a membrane.
8. The method of claim 7, wherein the solvent comprises cyclohexanone or propiophenone.
9. The method of claim 7, wherein the solvent is 65% to 70%, the ionophore is 2% to 5%, the additive is 0.2% to 1%, the polymer matrix is 12% to 15%, and the plasticizer is 8% to 14%.
10. An electrolyte analysis system comprising an electrolyte analyzer and a hydrogen ion selective membrane according to any one of claims 1 to 6.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114235928A (en) * | 2021-12-09 | 2022-03-25 | 铂恩医疗科技(深圳)有限公司 | Calcium ion selective electrode induction membrane solution, preparation method and application thereof |
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2021
- 2021-07-28 CN CN202110856392.1A patent/CN113671006A/en active Pending
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| EP0074198A1 (en) * | 1981-08-21 | 1983-03-16 | EASTMAN KODAK COMPANY (a New Jersey corporation) | Hydrogen ion-selective membranes and electrodes containing same |
| US5401377A (en) * | 1993-08-06 | 1995-03-28 | Biomedix, Inc. | Ion-selective sensor with polymeric membrane having phospholipid dispersed therein |
| TW201512654A (en) * | 2013-08-27 | 2015-04-01 | Organo Corp | Hydrogen ion selective electrode, pH measuring method, and sensitive membrane |
| CN111751422A (en) * | 2020-07-01 | 2020-10-09 | 深圳市锦瑞生物科技有限公司 | Magnesium ion selective membrane, preparation method and electrolyte analysis system |
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| CN114235928A (en) * | 2021-12-09 | 2022-03-25 | 铂恩医疗科技(深圳)有限公司 | Calcium ion selective electrode induction membrane solution, preparation method and application thereof |
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