CN113008965B - Preparation method and application of solid film phosphate radical ion selective electrode based on cobalt/pyrrole/mesoporous carbon - Google Patents
Preparation method and application of solid film phosphate radical ion selective electrode based on cobalt/pyrrole/mesoporous carbon Download PDFInfo
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- CN113008965B CN113008965B CN202110239624.9A CN202110239624A CN113008965B CN 113008965 B CN113008965 B CN 113008965B CN 202110239624 A CN202110239624 A CN 202110239624A CN 113008965 B CN113008965 B CN 113008965B
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Abstract
The invention discloses a preparation method and application of a solid film phosphate radical ion selective electrode based on cobalt/pyrrole/mesoporous carbonThe application is as follows. The method comprises the following steps: mixing cobalt chloride hexahydrate, pyrrole monomer and mesoporous carbon according to a certain proportion to prepare a deposition solution; then, depositing a solid film on the surface of the pretreated glassy carbon electrode by one step by using a constant current method to prepare a phosphate ion selective electrode; the obtained electrode is activated to a stable potential by a phosphate solution and then used for detecting phosphate. The detection range of the invention for phosphate radical is 10‑5～10‑1mol/L, response time reaches 6.4 s. The invention has the advantages of simple preparation, wide detection range, high response speed and the like, and is suitable for detecting phosphate in water.
Description
Technical Field
The invention relates to the technical field of electrochemical sensors, in particular to a preparation method and application of a solid film phosphate radical ion selective electrode based on cobalt/pyrrole/mesoporous carbon.
Background
The chemical sensor is an independent device capable of providing analysis information of a tested sample in real time, and is widely applied to engineering industries such as processing, process control, product preparation, mining, petrochemical industry, safety, environmental monitoring, food, biomedicine and the like. From the information given by the sensor, one can understand the qualitative or quantitative information related to one or more chemical substances in the sample to be analyzed, including organic and inorganic small molecules, enzymes, viruses, nucleic acids and other biological component substances, which is not provided by a physical sensor relying on only temperature, pressure, speed and other information. As research progresses, certain physical or chemical properties of the sensing element change with analyte concentration due to the interaction of the analyte with the sensing element. In order to be able to evaluate this change, chemical sensors convert the above-mentioned change into a measurable physical quantity, a process known as signal transduction or signal transduction.
Phosphorus is one of the limiting nutrient elements causing water eutrophication. When the phosphorus content of water is far higher than that normally required by aquatic plants due to excessive use of chemical fertilizers in agriculture, discharge pollution of industrial waste water and waste pollution of human and other animal wastes, excessive propagation of the aquatic plants, particularly explosive growth of algae, is caused. In ocean waters, excessive propagation of algae consumes a large amount of oxygen and produces a large amount of metabolites (including biotoxins harmful to humans), thereby causing damage to the ecological balance of oceans, damage to marine fisheries and aquatic resources, human poisoning and the like, and finally causing ecological environmental problems such as red tides and the like.
Currently, methods for detecting phosphate in water include spectrophotometry and electrochemical detection. Ammonium molybdate spectrophotometry is a widely adopted phosphate determination method, and has the defects of accurate and stable detection result, complex operation, long time consumption, requirement of special equipment and trained testers, requirement of carcinogenic chemical reagents during detection and the like.
An electrochemical sensor is a sensing device that can receive an external physical signal (e.g., optical or electrical) and convert it into a signal that can be transmitted, measured, or controlled. The use of electrochemical detection of phosphate includes two major categories: enzyme bioelectrochemical sensors and enzyme-free electrochemical sensors. Although the electrode for preparing the biological enzyme electrode has good selectivity on phosphate radical, the electrode preparation process consumes long time, the enzyme is poor in stability as a bioactive substance, the service life of the sensor is greatly influenced, the enzyme is expensive, the detection range is narrow, and the like, so that the development of the enzyme bioelectrochemical sensor is limited.
In the process of environmental investigation and monitoring, problems of monitoring data lag, inaccurate data and the like caused by self limitation of a spectrophotometry method and an enzyme bioelectrochemical sensor cause that environmental protection departments cannot accurately acquire environmental parameters in real time and make decisions in time before environmental pollution expansion and ecological crisis outbreak are difficult. Therefore, there is a strong need for a method that is sensitive, reliable, simple to operate, and capable of rapidly detecting phosphate concentration.
An Ion-Selective Electrode (ISE) is an enzyme-free electrochemical sensor, also called an ionic Electrode, which is an electrochemical sensor for measuring Ion activity or concentration in a solution by using a membrane potential, and the principle is that when the prepared Ion-Selective Electrode is contacted with a solution to be measured, a membrane potential related to the concentration of a specific Ion to be measured is generated on a phase interface between an Electrode sensitive membrane and the solution, the potential and the logarithm of the given Ion activity in the solution form a linear relationship, and the concentration of the corresponding Ion is calculated by combining an nernst equation. The construction of the ion selective electrode is mainly divided into two parts: ion selective membranes and internal conduction systems. The ion selective membrane is the most critical component of the ion selective electrode, determines the characteristics of the electrode, converts specific activity of ions to be detected in a solution into a signal of a potential, the membrane potential changes along with the change of the activity of the ions to be detected, and then the membrane potential transmits the signal to an internal conduction system. The function of the internal conduction system is to extract the membrane potential and transmit the signal. There are two general categories that can be distinguished by the configuration of the selective membrane: liquid film electrodes and solid film electrodes. The solid membrane electrode is an electrode taking a solid material as a sensitive membrane, and has the advantages of simple preparation, long storage time, wide detection range, low detection limit, capability of quickly detecting the concentration of specific ions anytime and anywhere, and the like, so that the solid membrane electrode is concerned by researchers in recent years.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a preparation method and application of a solid membrane ion selective electrode for quickly and accurately detecting phosphate in water, and overcomes the defects of complex operation, expensive preparation and long detection time consumption in the conventional spectrophotometric detection method of phosphate in water, and the problems of narrow detection range, high cost and the like of an enzyme electrochemical sensor.
In order to solve the above problems, the present invention proposes the following technical solutions:
the preparation method of the cobalt/pyrrole/mesoporous carbon-based solid film phosphate ion selective electrode is characterized by comprising the following steps of:
and 5, immersing the prepared electrode in a phosphate radical sample solution to activate until the potential is stable, and then detecting phosphate radical.
Preferably, the pyrrole monomer is selected from distilled pyrrole monomers.
It should be noted that the electrochemical workstation used was CHI 660E, and the three-electrode system used included: working electrode (glassy carbon electrode), auxiliary electrode (platinum wire), reference electrode (calomel electrode).
The further technical proposal is that the electrolyte is selected from at least one of potassium chloride and sodium sulfate.
The technical scheme is that in the step 1, pyrrole monomers need to be dissolved under the condition of avoiding light.
The further technical proposal is that the cobalt source is selected from cobalt chloride hexahydrate.
The method further adopts the technical scheme that the specific operation in the step 3 is to polish the glassy carbon electrode by using alumina powder with the grain diameter of 0.2-0.4 mm and 0.03-0.08 mm in sequence, clean the glassy carbon electrode and dry the glassy carbon electrode at the temperature of 40-55 ℃.
The further technical scheme is that in the step 4, the deposition current is 0.0005A.
The further technical scheme is that in the step 4, the deposition time is 100-600 s.
The further technical scheme is that in the step 5, the electrode activation time is 30-40 min; the concentration of the phosphate radical sample solution is 10-4mol/L and pH 4.0.
The invention also provides a solid film phosphate radical ion selective electrode prepared by the preparation method of the cobalt/pyrrole/mesoporous carbon-based solid film phosphate radical ion selective electrode.
The invention also provides a solid membrane phosphate radical ion selective electrode prepared by the preparation method of the cobalt/pyrrole/mesoporous carbon-based solid membrane phosphate radical ion selective electrode, or an application of the solid membrane phosphate radical ion selective electrode in the field of water quality detection.
Compared with the prior art, the invention can achieve the following technical effects:
the invention adopts a one-step electrodeposition method to deposit cobalt/pyrrole/mesoporous carbon on the surface of the glassy carbon electrode to prepare the phosphate solid film ion selective electrode, the preparation method is simple, the raw materials are conventional, the preparation conditions are easy to control, and the prepared electrode has wide phosphate detection range, high response speed and good stability and reproducibility. The prepared phosphate solid membrane ion selective electrode has wide application prospect in the field of phosphate water quality detection.
Drawings
FIG. 1 is a graph showing the response characteristics of the solid membrane ion-selective electrode prepared in example 2 of the present invention to phosphate detection.
Fig. 2 is a response characteristic curve of solid membrane ion selective electrodes prepared from cobalt and pyrrole in different proportions in examples 1-3 of the present invention for phosphate detection.
FIG. 3 is a graph showing the response characteristics of solid film ion-selective electrodes prepared at different deposition times in examples 2, 4-8 of the present invention to phosphate detection.
FIG. 4 shows a solid membrane ion-selective electrode 10 prepared in example 9 of the present invention-4And (3) continuously detecting the potential and time response curve diagram of 1800s at mol/L.
Fig. 5 is a graph showing the response characteristics of the 10-support solid film ion-selective electrode prepared in example 10 of the present invention to phosphate detection.
Detailed Description
The technical solutions in the embodiments will be described clearly and completely with reference to the accompanying drawings in the embodiments of the present invention, wherein like reference numerals represent like elements in the drawings. It is apparent that the embodiments to be described below are only a part of the embodiments of the present invention, and not all of them. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It will be understood that the terms "comprises" and/or "comprising," when used in this specification and the appended claims, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
It is also to be understood that the terminology used in the description of the embodiments of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of embodiments of the invention. As used in the description of embodiments of the present invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
Example 1
1) 0.9212g of cobalt chloride hexahydrate are dissolved in 20ml of deionized water, followed by addition of 0.135ml of distilled pyrrole monomer and stirring at 300r/min for 1 hour with exclusion of light.
2) 0.28408g of potassium chloride and 0.1491g of sodium sulfate are added into the solution to be used as electrolyte, 10mg of mesoporous carbon is added, and stirring is continued for 1 hour until the mixture is uniformly mixed, so that the deposition solution is prepared.
3) The glassy carbon electrode was polished and cleaned sequentially on 0.3mm, 0.05mm alumina powder and then dried in an oven at 50 ℃ for use.
4) Using the electrochemical workstation CHI 660E, a three-electrode system was used comprising: working electrode (glassy carbon electrode), auxiliary electrode (platinum wire), reference electrode (calomel electrode). The adopted deposition current is 0.0005A, the deposition time is 200s, and cobalt/pyrrole/mesoporous carbon is deposited on the surface of the glassy carbon electrode in one step to prepare the phosphate solid film ion selective electrode.
5) Immersing the prepared electrode in 10-4Activating until the potential is stable in the phosphate solution of mol/L, and then detecting the phosphate. Record 10 in turn-6～10-1The potential values of the solid membrane ion selective electrode prepared in the standard solution of phosphate in mol/L relative to the reference electrode are shown in FIG. 2, and this example corresponds to the potential values of Co: py 2:1 curve, the detection range of the electrode for phosphate is 10-1～10-4mol/L, slope-28.8 mV/dec.
Example 2
1) 0.9212g of cobalt chloride hexahydrate are dissolved in 20ml of deionized water, followed by addition of 0.27ml of distilled pyrrole monomer and stirring at 300r/min for 1 hour with exclusion of light.
2) 0.28408g of potassium chloride and 0.1491g of sodium sulfate were added to the solution as an electrolyte, 10mg of mesoporous carbon was added, and stirring was continued for 1 hour to prepare a deposition solution.
3) The glassy carbon electrode was polished and cleaned sequentially on 0.3mm, 0.05mm alumina powder and then dried in an oven at 50 ℃ for use.
4) Using the electrochemical workstation CHI 660E, a three-electrode system was used comprising: working electrode (glassy carbon electrode), auxiliary electrode (platinum wire), reference electrode (calomel electrode). The adopted deposition current is 0.0005A, the deposition time is 200s, and cobalt/pyrrole/mesoporous carbon is deposited on the surface of the glassy carbon electrode in one step to prepare the phosphate solid film ion selective electrode.
5) Immersing the prepared electrode in 10-4The solution of phosphate in mol/L is activated until the potential is stable, and then the solution is used for detecting phosphate. Record 10 in turn-6～10-1The potential values of the solid membrane ion selective electrode prepared in the phosphate standard solution of mol/L relative to the reference electrode are shown in FIG. 1, FIG. 2 and FIG. 3. In fig. 2, the present embodiment corresponds to Co: curve Py 1: 1; in fig. 3, the present embodiment corresponds to a curve labeled 200 s.
The detection range of the electrode prepared in this example for phosphate was 10-5～10-1mol/L, slope of-29.6 mV/dec, correlation coefficient R20.9912. Coefficient of correlation R2The value is very high, which shows that the prepared phosphate radical solid membrane ion selective electrode is 10-5-10-1Good linearity in mol/L phosphate solutionTherefore, the prepared ion selective electrode has good performance.
According to the definition of the response time in the nernst response: response time refers to the time required for the working electrode to reach 95% of steady state from instability. The results of the calculations show that the electrode prepared in this example is at 10-1The longest response time in mol/L phosphate standard solution is 6.4 s. The response time in the rest solutions is lower than 6.4s, which shows that the prepared electrode has fast response speed to phosphate radical.
Example 3
1) 0.9212g of cobalt chloride hexahydrate are dissolved in 20ml of deionized water, followed by addition of 0.54ml of distilled pyrrole monomer and stirring at 300r/min for 1 hour with exclusion of light.
2) 0.28408g of potassium chloride and 0.1491g of sodium sulfate were added to the solution as an electrolyte, 10mg of mesoporous carbon was added, and stirring was continued for 1 hour to prepare a deposition solution.
3) The glassy carbon electrode was polished and cleaned sequentially on 0.3mm, 0.05mm alumina powder and then dried in an oven at 50 ℃ for use.
4) Using the electrochemical workstation CHI 660E, a three-electrode system was used comprising: working electrode (glassy carbon electrode), auxiliary electrode (platinum wire), reference electrode (calomel electrode). The adopted deposition current is 0.0005A, the deposition time is 200s, and cobalt/pyrrole/mesoporous carbon is deposited on the surface of the glassy carbon electrode in one step to prepare the phosphate solid film ion selective electrode.
5) Immersing the prepared electrode in 10-4Activating until the potential is stable in the phosphate solution of mol/L, and then detecting the phosphate. Sequentially record 10-6～10-1The potential values of the solid membrane ion selective electrode prepared in the standard solution of phosphate in mol/L relative to the reference electrode are shown in FIG. 2, and this example corresponds to the potential values of Co: py is 1:2 curve. The detection range of the electrode for phosphate is 10-1～10-4mol/L, slope 27.1 mV/dec.
Example 4
1) 0.9212g of cobalt chloride hexahydrate are dissolved in 20ml of deionized water, followed by addition of 0.27ml of distilled pyrrole monomer and stirring at 300r/min for 1 hour with exclusion of light.
2) 0.28408g of potassium chloride and 0.1491g of sodium sulfate were added to the solution as an electrolyte, 10mg of mesoporous carbon was added, and stirring was continued for 1 hour to prepare a deposition solution.
3) The glassy carbon electrode was polished and cleaned sequentially on 0.3mm, 0.05mm alumina powder and then dried in an oven at 50 ℃ for use.
4) Using the electrochemical workstation CHI 660E, a three-electrode system was used comprising: working electrode (glassy carbon electrode), auxiliary electrode (platinum wire), reference electrode (calomel electrode). The adopted deposition current is 0.0005A, the deposition time is 100s, and cobalt/pyrrole/mesoporous carbon is deposited on the surface of the glassy carbon electrode in one step to prepare the phosphate solid film ion selective electrode.
5) Immersing the prepared electrode in 10-4Activating until the potential is stable in the phosphate solution of mol/L, and then detecting the phosphate. Record 10 in turn-6～10-1The potential value of the solid membrane ion selective electrode prepared in the standard solution of the phosphate of mol/L relative to the reference electrode is shown in FIG. 3, and the detection range of the electrode for the phosphate is 10-1～10-4mol/L。
Example 5
1) 0.9212g of cobalt chloride hexahydrate are dissolved in 20ml of deionized water, followed by addition of 0.27ml of distilled pyrrole monomer and stirring at 300r/min for 1 hour with exclusion of light.
2) 0.28408g of potassium chloride and 0.1491g of sodium sulfate are added into the solution as electrolyte, 10mg of mesoporous carbon is added, and stirring is continued for 1 hour to prepare a sediment solution.
3) The glassy carbon electrode was polished and cleaned sequentially on 0.3mm, 0.05mm alumina powder and then dried in an oven at 50 ℃ for use.
4) Using the electrochemical workstation CHI 660E, a three-electrode system was used comprising: working electrode (glassy carbon electrode), auxiliary electrode (platinum wire), reference electrode (calomel electrode). The adopted deposition current is 0.0005A, the deposition time is 300s, and cobalt/pyrrole/mesoporous carbon is deposited on the surface of the glassy carbon electrode in one step to prepare the phosphate solid film ion selective electrode.
5) Immersing the prepared electrode in 10-4Activating until the potential is stable in the phosphate solution of mol/L, and then detecting the phosphate. Record 10 in turn-6～10-1The potential value of the solid membrane ion selective electrode prepared in the standard solution of the phosphate of mol/L relative to the reference electrode is shown in FIG. 3, and the detection range of the electrode for the phosphate is 10-1～10-5mol/L, slope 25 mV/dec.
Example 6
1) 0.9212g of cobalt chloride hexahydrate are dissolved in 20ml of deionized water, followed by addition of 0.27ml of distilled pyrrole monomer and stirring at 300r/min for 1 hour with exclusion of light.
2) 0.28408g of potassium chloride and 0.1491g of sodium sulfate were added to the solution as an electrolyte, 10mg of mesoporous carbon was added, and stirring was continued for 1 hour to prepare a deposition solution.
3) The glassy carbon electrode was polished and cleaned sequentially on 0.3mm, 0.05mm alumina powder and then dried in an oven at 50 ℃ for use.
4) Using the electrochemical workstation CHI 660E, a three-electrode system was used comprising: working electrode (glassy carbon electrode), auxiliary electrode (platinum wire), reference electrode (calomel electrode). The adopted deposition current is 0.0005A, the deposition time is 400s, and cobalt/pyrrole/mesoporous carbon is deposited on the surface of the glassy carbon electrode in one step to prepare the phosphate solid film ion selective electrode.
5) Immersing the prepared electrode in 10-4Activating until the potential is stable in the phosphate solution of mol/L, and then detecting the phosphate. Record 10 in turn-6～10-1The potential value of the solid membrane ion selective electrode prepared in the standard solution of the phosphate of mol/L relative to the reference electrode is shown in FIG. 3, and the detection range of the electrode for the phosphate is 10-1～10-4mol/L。
Example 7
1) 0.9212g of cobalt chloride hexahydrate are dissolved in 20ml of deionized water, followed by addition of 0.27ml of distilled pyrrole monomer and stirring at 300r/min for 1 hour with exclusion of light.
2) 0.28408g of potassium chloride and 0.1491g of sodium sulfate were added to the solution as an electrolyte, 10mg of mesoporous carbon was added, and stirring was continued for 1 hour to prepare a deposition solution.
3) The glassy carbon electrode was polished and cleaned sequentially on 0.3mm, 0.05mm alumina powder and then dried in an oven at 50 ℃ for use.
4) Using the electrochemical workstation CHI 660E, a three-electrode system was used comprising: working electrode (glassy carbon electrode), auxiliary electrode (platinum wire), reference electrode (calomel electrode). The adopted deposition current is 0.0005A, the deposition time is 500s, and cobalt/pyrrole/mesoporous carbon is deposited on the surface of the glassy carbon electrode in one step to prepare the phosphate solid film ion selective electrode.
5) Immersing the prepared electrode in 10-4Activating until the potential is stable in the phosphate solution of mol/L, and then detecting the phosphate. Record 10 in turn-6～10-1The potential value of the solid membrane ion selective electrode prepared in the standard solution of the phosphate of mol/L relative to the reference electrode is shown in FIG. 3, and the detection range of the electrode for the phosphate is 10-1～10-4mol/L。
Example 8
1) 0.9212g of cobalt chloride hexahydrate are dissolved in 20ml of deionized water, followed by addition of 0.27ml of distilled pyrrole monomer and stirring at 300r/min for 1 hour with exclusion of light.
2) 0.28408g of potassium chloride and 0.1491g of sodium sulfate were added to the solution as an electrolyte, 10mg of mesoporous carbon was added, and stirring was continued for 1 hour to prepare a deposition solution.
3) The glassy carbon electrode was polished and cleaned sequentially on 0.3mm, 0.05mm alumina powder and then dried in an oven at 50 ℃ for use.
4) Using the electrochemical workstation CHI 660E, a three-electrode system was used comprising: working electrode (glassy carbon electrode), auxiliary electrode (platinum wire), reference electrode (calomel electrode). The adopted deposition current is 0.0005A, the deposition time is 600s, and cobalt/pyrrole/mesoporous carbon is deposited on the surface of the glassy carbon electrode in one step to prepare the phosphate solid film ion selective electrode.
5) Immersing the obtained electrodeAt 10-4Activating until the potential is stable in the phosphate solution of mol/L, and then detecting the phosphate. Record 10 in turn-6～10-1The potential value of the solid membrane ion selective electrode prepared in the standard solution of the phosphate of mol/L relative to the reference electrode is shown in FIG. 3, and the detection range of the electrode for the phosphate is 10-1～10-4mol/L。
Example 9
1) 0.9212g of cobalt chloride hexahydrate are dissolved in 20ml of deionized water, followed by addition of 0.27ml of distilled pyrrole monomer and stirring at 300r/min for 1 hour with exclusion of light.
2) 0.28408g of potassium chloride and 0.1491g of sodium sulfate were added to the solution as an electrolyte, 10mg of mesoporous carbon was added, and stirring was continued for 1 hour to prepare a deposition solution.
3) The glassy carbon electrode was polished and cleaned sequentially on 0.3mm, 0.05mm alumina powder and then dried in an oven at 50 ℃ for use.
4) Using the electrochemical workstation CHI 660E, a three-electrode system was used comprising: working electrode (glassy carbon electrode), auxiliary electrode (platinum wire), reference electrode (calomel electrode). The adopted deposition current is 0.0005A, the deposition time is 200s, and cobalt/pyrrole/mesoporous carbon is deposited on the surface of the glassy carbon electrode in one step to prepare the phosphate solid film ion selective electrode.
5) Immersing the prepared electrode in 10-4Activating until the potential is stable in the phosphate solution of mol/L, and then detecting the phosphate. To further explore the stability of the prepared solid film ion selective electrodes, the prepared electrodes were recorded at 10- 4The potential response value of the phosphate solution of mol/L for 1800s is continuously detected, the result is shown in figure 4, after the potential is stabilized, the prepared phosphate solid membrane ion selective electrode is 10 to 10-4The response value of the phosphate solution is stabilized at about-0.466V, and the deviation between the maximum value and the minimum value is not more than 1mV, so that the prepared phosphate solid membrane ion selective electrode has good stability.
Example 10
1) 0.9212g of cobalt chloride hexahydrate are dissolved in 20ml of deionized water, followed by addition of 0.27ml of distilled pyrrole monomer and stirring at 300r/min for 1 hour with exclusion of light.
2) 0.28408g of potassium chloride and 0.1491g of sodium sulfate are added into the solution as electrolyte, 10mg of mesoporous carbon is added, and stirring is continued for 1 hour to prepare a sediment solution.
3) The glassy carbon electrode was polished and cleaned sequentially on 0.3mm, 0.05mm alumina powder and then dried in an oven at 50 ℃ for use.
4) Using the electrochemical workstation CHI 660E, a three-electrode system was used comprising: working electrode (glassy carbon electrode), auxiliary electrode (platinum wire), reference electrode (calomel electrode). The adopted deposition current is 0.0005A, the deposition time is 200s, and cobalt/pyrrole/mesoporous carbon is deposited on the surface of the glassy carbon electrode in one step to prepare the phosphate solid film ion selective electrode.
5) Preparing 10 electrodes simultaneously, and soaking the prepared electrodes in 10-4Activating until the potential is stable in the phosphate solution of mol/L, and then detecting the phosphate. Sequentially record 10-5～10-1The potential values of the solid membrane ion selective electrode prepared in the phosphate standard solution of mol/L relative to the reference electrode are shown in FIG. 5.
The detection range of the simultaneously prepared 10 electrodes for the phosphate is 10-1～10-5mol/L, the results are shown in Table 1, the relative standard deviation values are all lower than 1%, and the prepared electrode has good reproducibility.
TABLE 1 Standard deviation and relative Standard deviation of reproducibility test of phosphate solid film ion-Selective electrode
In the above embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
While the invention has been described with reference to specific embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (3)
1. The preparation method of the cobalt/pyrrole/mesoporous carbon-based solid film phosphate ion selective electrode is characterized by comprising the following steps of:
step 1, dissolving a cobalt source and a pyrrole monomer in deionized water, wherein the concentration of cobalt in the solution is 0.1-0.3 mol/L, and the concentration of pyrrole is 0.1-0.4 mol/L;
step 2, adding electrolyte and mesoporous carbon into the solution obtained in the step 1, and uniformly mixing to obtain a deposition solution, wherein the concentration of the electrolyte in the deposition solution is 0.1-0.4 mol/L, and the concentration of the mesoporous carbon is 0.3-0.8 g/L;
step 3, polishing and cleaning the glassy carbon electrode on alumina powder, and drying for later use;
step 4, depositing cobalt/pyrrole/mesoporous carbon on the surface of the glassy carbon electrode by using a three-electrode system and adopting a constant current method to prepare a phosphate solid film ion selective electrode;
step 5, soaking the prepared electrode in a phosphate solution to activate the electrode until the potential is stable, and then detecting phosphate;
the electrolyte is selected from at least one of potassium chloride and sodium sulfate;
in the step 1, pyrrole monomers need to be dissolved under the condition of keeping out of the sun;
the cobalt source is selected from cobalt chloride hexahydrate;
in the step 4, the deposition current is 0.0005A;
in the step 4, the deposition time is 100-600 s;
the specific operation of the step 3 is that the glassy carbon electrode is sequentially polished by alumina powder with the grain diameter of 0.2-0.4 mm and 0.03-0.08 mm, and is dried at 40-55 ℃ after being cleaned;
in the step 5, the electrode activation time is 30-40 min; the concentration of the phosphate solution was 10-4mol/L and pH 4.0.
2. A solid membrane phosphate ion selective electrode, characterized by being prepared by the method of claim 1 based on cobalt/pyrrole/mesoporous carbon.
3. The solid membrane phosphate ion selective electrode prepared by the preparation method of the cobalt/pyrrole/mesoporous carbon-based solid membrane phosphate ion selective electrode according to claim 1 or the solid membrane phosphate ion selective electrode according to claim 2, for use in the field of water quality detection.
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| MY159121A (en) * | 2010-12-03 | 2016-12-15 | Mimos Berhad | Phosphate sensor |
| CN104198562A (en) * | 2014-08-29 | 2014-12-10 | 中国科学院烟台海岸带研究所 | Conducting layer material and method for preparing solid contact type ion selective electrode by use of conducting layer material |
| CN106198663B (en) * | 2015-05-05 | 2018-11-02 | 中国科学院烟台海岸带研究所 | A kind of solid contact polymer film cadmium ion electrodes selective and its application |
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