CN113125545A - Water quality detection instrument and detection method - Google Patents
Water quality detection instrument and detection method Download PDFInfo
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- CN113125545A CN113125545A CN202110430740.9A CN202110430740A CN113125545A CN 113125545 A CN113125545 A CN 113125545A CN 202110430740 A CN202110430740 A CN 202110430740A CN 113125545 A CN113125545 A CN 113125545A
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Abstract
The invention relates to a water heavy metal detection instrument, which is prepared by the following method: (1) dissolving nickel salt, cobalt salt and sodium citrate in a glycerol solution, and carrying out microwave solvothermal reaction to obtain the flower-shaped NiCo formed by nanosheets2O4(ii) a (2) Adding zinc salt into glycerol, completely dissolving with ultrasound, continuously adding ammonium fluoride, and adding the flower-shaped NiCo prepared in the step (1)2O4Adding the mixture into a high-temperature reaction kettle, and carrying out hydrothermal reaction to obtain the candied gourd-shaped ZnO2Loaded on flower-like NiCo2O4Between the two-dimensional nano sheets; (3) the prepared composite material suspension is dripped on the surface of a glassy carbon electrode and is used as a working electrode to form a three-electrode system with a reference electrode and a counter electrode to form an electrochemical sensor, the instrument can be used for synchronously detecting cadmium and lead ions, has high response speed, high sensitivity and good stability, and can be used for quickly detecting heavy metal ions in water.
Description
Technical Field
The invention relates to a water quality heavy metal ion detection instrument and a detection method, in particular to an electrochemical sensor for detecting lead and cadmium ions in water with high sensitivity and a detection method, and belongs to the technical field of water quality monitoring.
Background
With the rapid development of society, the environmental pollution problem seems to be more and more prominent, and the heavy metal pollution problem in water is more and more prominent. The mining and smelting of heavy metals and heavy metal-containing ores, and the production process of heavy metal-containing building materials, living goods and chemical raw chemicals can generate wastewater containing heavy metal elements, thereby causing serious pollution to the environment. Heavy metals enter the human body along with the transfer of food chains, which damages human health. Therefore, the development of a convenient, efficient, rapid and practical analysis method for heavy metal pollution, especially a method for detecting heavy metal elements such as lead and cadmium, is the current research focus.
The existing heavy metal ion detection method comprises an absorption spectrum and emission spectrum method, a biochemical analysis method, a mass spectrometry method and a high performance liquid chromatography of an atomic spectrum technology, and although the detection methods have the advantages, the required equipment is expensive, the operation cost is high, the detection time is long, and the like, so that the actual demand of rapid and in-situ detection of heavy metals is difficult to meet. The electrochemical detection method is used for determining by utilizing the fact that the change of the heavy metal ions in the chemical cell such as resistance, current, potential, electric quantity and the like has a certain relation with the concentration of a substance to be detected, has high sensitivity, low detection limit, low instrument and equipment cost and small occupied area, and overcomes the defects of expensive detection instruments, complex detection steps, high detection cost and the like of the traditional heavy metal detection method.
Disclosure of Invention
The invention relates to a water quality heavy metal ion detection instrument and a detection method, in particular to an electrochemical sensor for detecting lead and cadmium ions in water with high sensitivity and a specific detection method.
A water quality heavy metal detection instrument is prepared by the following method:
(1) dissolving nickel salt, cobalt salt and sodium citrate in glycerol solution, fully stirring and dissolving, transferring to a microwave reaction kettle, carrying out microwave solvothermal reaction for 5-12h at the temperature of 180 ℃ and 200 ℃ to obtain flower-shaped NiCo formed by nanosheets2O4；
(2) Adding zinc salt into glycerol, completely dissolving with ultrasound, adding ammonium fluoride, stirring for 30min, and mixing with flower-like NiCo formed by nanosheets2O4Adding into a high-temperature reaction kettle, heating to 180-200 ℃, and then preserving heat for 3-5 hours to obtain the sugarcoated haw-shaped ZnO2Loaded on flower-like NiCo2O4Between the two-dimensional nano sheets;
(3) dispersing the prepared composite material in N, N-dimethylformamide, ultrasonically mixing uniformly, taking a suspension to be dripped on the surface of a glassy carbon electrode, drying the glassy carbon electrode dripped with the suspension on the surface at room temperature, taking the glassy carbon electrode as a working electrode, and forming a three-electrode system with a reference electrode and a counter electrode to form the electrochemical sensor.
Preferably, the molar ratio of the nickel salt to the cobalt salt to the sodium citrate is 1: 2: (0.1-0.8);
preferably, the nickel salt is nickel nitrate or nickel acetate;
preferably, the cobalt salt is cobalt nitrate or cobalt acetate;
a method for detecting heavy metals in water comprises the following steps: placing a working electrode of the electrochemical detection instrument prepared in the method in a solution to be detected, connecting the working electrode into an electrolytic cell of a three-electrode system for electrochemical detection, enriching heavy metal ions on the surface of a glassy carbon electrode by using a differential pulse anodic stripping voltammetry, then dissolving out the heavy metal ions, establishing a linear regression equation according to the concentration of the heavy metal ions and the change of stripping current, and further calculating the content of lead and cadmium metal ions in water.
The technical effects are as follows:
the invention uses ZnO2/NiCo2O4The composite material is used as a modified electrode and is made of sugarcoated haw-shaped ZnO2Loaded on flower-like NiCo2O4A unique three-dimensional structure is ingeniously designed between the two-dimensional nanosheets for the first time, the three-dimensional special structure is favorable for improving the specific surface area of the material, the full exposure of active sites is ensured, heavy metal cations can be well adsorbed, the heavy metal ions are easy to deposit, cadmium and lead ions can be synchronously detected, the response speed is high, the sensitivity is high, the stability is good, and the possibility of on-site and on-line quick detection of the heavy metal ions in water is realized.
Drawings
Fig. 1 is an SEM image of the composite material of the present application.
Detailed Description
Example 1
(1) Dissolving 2mmol of nickel nitrate, 4mmol of cobalt nitrate and 0.5mmol of sodium citrate in 80ml of glycerol solution, fully stirring and dissolving, transferring into a microwave reaction kettle, and carrying out microwave solvothermal reaction for 5 hours at the temperature of 200 ℃ to obtain flower-shaped NiCo formed by nanosheets2O4；
(2) Adding 2mmol of zinc nitrate into 30ml of glycerol, performing ultrasonic complete dissolution, continuously adding 2mmol of ammonium fluoride, stirring for 30min, and adding the flower-shaped NiCo formed by the nanosheets prepared in the step (1)2O4Adding into a high-temperature reaction kettle, heating to 200 ℃, and preserving heat for 5 hours to obtain ZnO2Loaded on flower-like NiCo2O4Between the two-dimensional nano sheets;
(3) dispersing 5mg of the prepared composite material in 5ml of N, N-dimethylformamide, ultrasonically mixing uniformly, dripping 5 microliters of suspension on the surface of a glassy carbon electrode, drying the glassy carbon electrode dripped with the suspension on the surface at room temperature, taking the glassy carbon electrode as a working electrode, and forming a three-electrode system with a reference electrode and a counter electrode to form the electrochemical sensor.
Example 2
(1) Dissolving 3mmol of nickel nitrate, 6mmol of cobalt nitrate and 0.8mmol of sodium citrate in 100ml of glycerol solution, fully stirring and dissolving, transferring to a microwave reaction kettle, and carrying out microwave solvothermal reaction for 5 hours at 190 ℃ to obtain flower-shaped NiCo formed by nanosheets2O4；
(2) Adding 2mmol of zinc nitrate into 30ml of glycerol, performing ultrasonic complete dissolution, continuously adding 1mmol of ammonium fluoride, stirring for 30min, and adding the flower-shaped NiCo formed by the nanosheets prepared in the step (1)2O4Adding into a high-temperature reaction kettle, heating to 200 deg.C, and maintaining for 3 hr to obtain sugarcoated haw-shaped ZnO2Loaded on flower-like NiCo2O4Between the two-dimensional nano sheets;
(3) dispersing 5mg of the prepared composite material in 5ml of N, N-dimethylformamide, ultrasonically mixing uniformly, dripping 5 microliters of suspension on the surface of a glassy carbon electrode, drying the glassy carbon electrode dripped with the suspension on the surface at room temperature, taking the glassy carbon electrode as a working electrode, and forming a three-electrode system with a reference electrode and a counter electrode to form the electrochemical sensor.
And (3) testing the performance of the electrochemical sensor:
lead and cadmium ion solutions with different concentrations are respectively added into an acetate buffer solution with the pH value of 4.5, and the electrochemical sensor prepared in example 1 is combined with a differential pulse stripping voltammetry to measure the lead and cadmium ions, and test results show that the modified electrode has good linear relation (R2 is 0.9963 and 0.9910 respectively) to the lead and cadmium ions, the linear ranges are 26.0pM-319.0pM and 50.0pM-283.6pM respectively, and the detection limits are low (7.4 pM and 7.9pM respectively), so that the sensing electrode can efficiently detect the lead and cadmium ions in water.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (5)
1. A water quality heavy metal detection instrument is prepared by the following method:
(1) dissolving nickel salt, cobalt salt and sodium citrate in glycerol solution, fully stirring and dissolving, transferring to a microwave reaction kettle, carrying out microwave solvothermal reaction for 5-12h at the temperature of 180 ℃ and 200 ℃ to obtain flower-shaped NiCo consisting of two-dimensional nano sheets2O4；
(2) Adding zinc salt into glycerol, completely dissolving with ultrasound, continuously adding ammonium fluoride, stirring, and forming flower-like NiCo from the nanosheets2O4Adding into a high-temperature reaction kettle, heating to 180-200 ℃, and then preserving heat for 3-5 hours to obtain the sugarcoated haw-shaped ZnO2Loaded on flower-like NiCo2O4Between the two-dimensional nano sheets;
(3) dispersing the prepared composite material in N, N-dimethylformamide, ultrasonically mixing uniformly, taking a suspension to be dripped on the surface of a glassy carbon electrode, drying the glassy carbon electrode dripped with the suspension on the surface at room temperature, taking the glassy carbon electrode as a working electrode, and forming a three-electrode system with a reference electrode and a counter electrode to form an electrochemical detection instrument.
2. The water quality heavy metal detecting instrument according to claim 1, wherein the molar ratio of the nickel salt to the cobalt salt to the sodium citrate is 1: 2: (0.1-0.8).
3. The water quality heavy metal detecting instrument according to claim 1, wherein the nickel salt is nickel nitrate or nickel acetate.
4. The water quality heavy metal detecting instrument according to claim 1, wherein the cobalt salt is cobalt nitrate or cobalt acetate.
5. A method for detecting heavy metal in water quality is characterized in that a working electrode of a water quality heavy metal detector prepared in the method in claim 1 is placed in a solution to be detected, the solution is connected into an electrolytic cell of a three-electrode system for electrochemical detection, heavy metal ions are pre-enriched on the surface of a glassy carbon electrode by utilizing a differential pulse anodic stripping voltammetry, then the heavy metal ions are dissolved out, a linear regression equation is established according to the concentration of the heavy metal ions and the change of stripping current, and the content of lead and cadmium metal ions in water is calculated.
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| CN202110430740.9A CN113125545A (en) | 2021-04-21 | 2021-04-21 | Water quality detection instrument and detection method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114720531A (en) * | 2022-04-07 | 2022-07-08 | 费县鸿腾环保科技中心 | Water quality detection method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114720531A (en) * | 2022-04-07 | 2022-07-08 | 费县鸿腾环保科技中心 | Water quality detection method |
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