CN113125535A - Novel polyurethane foam electrode for ultra-sensitive detection of Hg2+ - Google Patents
Novel polyurethane foam electrode for ultra-sensitive detection of Hg2+ Download PDFInfo
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- CN113125535A CN113125535A CN202110253020.XA CN202110253020A CN113125535A CN 113125535 A CN113125535 A CN 113125535A CN 202110253020 A CN202110253020 A CN 202110253020A CN 113125535 A CN113125535 A CN 113125535A
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- 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
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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
- G01N27/3335—Ion-selective electrodes or membranes the membrane containing at least one organic component
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Abstract
The invention discloses a novel polyurethane foam electrode for ultra-sensitive detection of Hg2+, which is characterized in that by means of a photoelectric reaction system, 3D polyurethane foam is used as a substrate to load a semiconductor material to form a heterojunction which is a photoelectric signal enhancement module, so that rapid detection of Hg2+ in a solution is realized, and compared with analytical methods for detecting Hg2+, the method comprises an atomic absorption spectrometry, an inductive coupling plasma spectrometry, a surface enhanced Raman scattering method, fluorescence detection and a colorimetric method, the detection method has the advantages of simple sample pretreatment, less time consumption and accurate and reliable detection results.
Description
Technical Field
The invention relates to the technical field of photoelectric detection, in particular to a novel polyurethane foam electrode for ultra-sensitively detecting Hg2+。
Background
Under the irradiation of light, the light is absorbed by metal or semiconductor electrode materials or reactants in a solution near the electrode, so that energy accumulation is caused or electrode reaction is promoted to occur, and the energy is converted into electric energy and chemical energy, such as photoelectron emission; photoelectric conversion of the photoelectrochemical cell; electrochemiluminescence, and the like. The development of photoelectric synthesis is wide, and the origin of life is probably generated by natural photoelectric synthesis. The photoelectrochemistry principle can enrich rare metals and noble metals, record and store information, and erase information at any time by a simple method, which are necessary means for developing science and technology. Effective purification of industrial waste water is an urgent need to solve the problem of ever decreasing water resources. In recent years, semiconductor photocatalytic technology has shown great potential as an environmentally friendly, sustainable wastewater treatment technology in the field of wastewater treatment.
The compounding of components with large differences in physical and chemical properties on a nanoscale to achieve the multifunction of materials is a hot spot field of nano synthesis. The components in the nano composite material system can generate strong mutual coupling effect, not only can enhance the respective intrinsic characteristics of the material, but also can show a plurality of novel physicochemical characteristics, thereby breaking through the limitation of the material performance of a single component, and having wide application in the fields of novel functional material research and development, energy conversion and storage, environmental protection and pollution treatment, biological medicine and the like. With the rapid development of synthesis technology and characterization means, people can control the synthesis of the nano composite material on the atom and molecule level, observe the interface structure of different components of the composite material, reveal the coupling principle among different components of the composite material, and regulate and control the physicochemical property of the composite material.
Heavy metal ions, particularly mercury ions, can be metabolized by excretion, hair, and the like. If a large amount of the drug is accumulated in a human body, serious diseases such as pneumonia, enteritis, bronchitis and the like are caused. And is the only metal present in a liquid state at normal temperature and pressure. Mercury is slightly soluble in water and increases in solubility in the presence of air. Mercury is ubiquitous in nature, and animals and plants generally contain trace mercury, so that the food contains trace mercury, and the mercury can be accumulated in organisms and can be easily absorbed by skin, respiratory tract and digestive tract. Prolonged exposure to high mercury environments can lead to brain damage and death. Despite the high boiling point of mercury, saturated mercury vapor reaches several times the toxic dose at room temperature.
Disclosure of Invention
The invention provides a novel polyurethane foam electrode for ultra-sensitive detection of Hg2+The method does not need complex and tedious large-scale equipment support and can be easily realized in most laboratories. The specific preparation scheme is as follows:
(1) preparation of Ni (OH)2/PU electrode: cutting commercial polyurethane foam into 1.0 cm multiplied by 1.0 cm sheets, washing the sponge with deionized water for several times, then drying at 60-70 ℃ for 0.5-1.5H, dissolving 2.5-3.5 g NiCl 26H 2O and 0.3-0.4 g NH4Cl in 40-60 mL distilled water to obtain a green solution, adding 5-7 mL ammonia water to change the solution from light green to dark blue, then putting white clean PU sponge sheets into a 10 mL autoclave, immersing in the dark blue solution, sealing the autoclave and heating at 80-100 ℃ for 11-13H to obtain green from white sponge, and finally taking out the green sponge and drying at 40-60 ℃ for 7-9H to obtain a Ni (OH)2/PU (NPU) electrode;
(2) rGO modified foam electrode: extruding and immersing the foam into a high-concentration graphene oxide suspension for soaking for 0.5-1.5h, then drying in an oven at 50-60 ℃ for 0.5-1.5h to obtain a sample, namely 3DGO/NPU, immersing in a boiling AA solution with the concentration of 0.15-0.3M for 40-50 min, cleaning with deionized water (DIW) and ethanol, and drying the reduced sample at room temperature to obtain the sample labeled as 3 DrGO/NPU;
(3) dissolving 0.37-0.39 mmol of zinc nitrate containing 0.37-0.39 mmol of TAA in 60-80 mL of ethanol, stirring for 25-35 min, transferring the mixture into an autoclave (with the capacity of 100 mL) lined with polytetrafluoroethylene, heating to 160-180 ℃, heating for 2-4h, cooling the precipitate to room temperature, purifying by high-speed centrifugation, washing with ethanol and water for 3-5 times in sequence, preparing the precipitate into 8-10 mg/mL, dripping the precipitate onto a foam electrode for 5-10 times, and drying at 50-70 ℃;
(4) placing the modified electrode with a certain Hg concentration2+In PBS (pH =7.4), left at room temperature for 5-7 min to complete the modification of the Hg on the electrode surface2+The electrochemical workstation needs to be calibrated for at least about 20 min to reach proper measurement conditions for photocurrent testing, and then the modified electrodes are usedDecorated electrode various concentrations of Hg were detected in PBS (pH =7.4) containing 0.15M triethanolamine2+The photocurrent response was recorded, noting that the PBS solution was degassed with nitrogen for several minutes before the measurement experiment was performed, and then maintained under a nitrogen atmosphere throughout the experiment.
The invention has the beneficial effects that:
(1) the method has the advantages of low experimental cost, simple and efficient operation and safe and easily controlled reaction conditions;
(2) compared with the prior photoelectrode, the polyurethane foam electrode system has good stability, and the 3D pore structure and the self-contained mass of nitrogen atoms can play a role in accumulating mercury ions, so that the signal enhancing performance is outstanding.
(3) Based on the metal semiconductor compound, the self-supported material forms a heterojunction, which is beneficial to the separation of electrons and holes, so that the photocurrent density is higher and the signal enhancement is more beneficial.
Example 1 (detection of Hg in solution)2+）
(1) Preparation of Ni (OH)2/PU electrode: cutting commercial polyurethane foam into 1.0 cm × 1.0 cm pieces, washing the sponge with deionized water several times, drying at 50 ℃ for 1H, dissolving 2.97 g NiCl 26H 2O and 0.33 g NH4Cl in 50 mL distilled water to obtain a green solution, adding 6 mL ammonia water to change the solution from light green to dark blue, placing the white cleaned PU sponge piece into a 10 mL autoclave, immersing in the dark blue solution, sealing the autoclave and heating at 90 ℃ for 12H to obtain green from the white sponge, and finally taking out the green sponge and drying at 50 ℃ for 8H to obtain a Ni (OH)2/PU (NPU) electrode;
(2) rGO modified foam electrode: extruding and immersing the foam into a high-concentration graphene oxide suspension for 1 h, drying in an oven at 55 ℃ for 1 h to obtain a sample named as 3DGO/NPU, immersing in a boiling AA solution with the concentration of 0.2M for 45 min, cleaning with deionized water (DIW) and ethanol, and drying the reduced sample at room temperature and marked as 3 DrGO/NPU;
(3) dissolving 0.38 mmol of zinc nitrate and thioacetamide containing 0.38 mmol in 70 mL of ethanol, stirring for 30 min, transferring the mixture into an autoclave (the volume is 100 mL) lined with polytetrafluoroethylene, heating to 180 ℃ for 3 h, cooling the precipitate to room temperature, purifying by high-speed centrifugation, washing with ethanol and water for 3 times in sequence, preparing the precipitate into 8 mg/mL, dripping the precipitate on a foam electrode for 10 times, and drying at 60 ℃;
(4) placing the modified electrode with a certain Hg concentration2+In PBS (pH =7.4) at room temperature for 5.0 min to complete the interaction of Hg2+ on the surface of the modified electrode with the electrode, the electrochemical workstation needs to calibrate for at least about 20 min to reach the appropriate measurement conditions for photocurrent testing, and then the modified electrode is used to detect different concentrations of Hg in PBS (pH =7.4) containing 0.15M triethanolamine2+The photocurrent response was recorded, noting that the PBS solution was degassed with nitrogen for several minutes before the measurement experiment was performed, and then maintained under a nitrogen atmosphere throughout the experiment.
Claims (1)
1. The invention relates to a novel polyurethane foam electrode for ultra-sensitive detection of Hg2+The method is characterized by comprising the following steps:
(1) preparation of Ni (OH)2/PU electrode: cutting commercial polyurethane foam into 1.0 cm × 1.0 cm pieces, washing the sponge with deionized water several times, drying at 50 ℃ for 1H, dissolving 2.97 g NiCl 26H 2O and 0.33 g NH4Cl in 50 mL distilled water to obtain a green solution, adding 6 mL ammonia water to change the solution from light green to dark blue, placing the white cleaned PU sponge piece into a 10 mL autoclave, immersing in the dark blue solution, sealing the autoclave and heating at 90 ℃ for 12H to obtain green from the white sponge, and finally taking out the green sponge and drying at 50 ℃ for 8H to obtain a Ni (OH)2/PU (NPU) electrode;
(2) rGO modified foam electrode: extruding and immersing the foam into a high-concentration graphene oxide suspension for 1 h, drying in an oven at 55 ℃ for 1 h to obtain a sample named as 3DGO/NPU, immersing in a boiling AA solution with the concentration of 0.2M for 45 min, cleaning with deionized water (DIW) and ethanol, and drying the reduced sample at room temperature and marked as 3 DrGO/NPU;
(3) dissolving 0.38 mmol of zinc nitrate and thioacetamide containing 0.38 mmol in 70 mL of ethanol, stirring for 30 min, transferring the mixture into an autoclave (the volume is 100 mL) lined with polytetrafluoroethylene, heating to 180 ℃ for 3 h, cooling the precipitate to room temperature, purifying by high-speed centrifugation, washing with ethanol and water for 3 times in sequence, preparing the precipitate into 8 mg/mL, dripping the precipitate on a foam electrode for 10 times, and drying at 60 ℃;
(4) the modified electrode is placed in PBS (pH =7.4) containing a certain concentration of Hg2+, and is placed at room temperature for 5.0 min to finish the modification of Hg on the surface of the electrode2+Interaction with the electrode, the electrochemical workstation required calibration for at least about 20 min to reach appropriate measurement conditions for photocurrent testing, followed by detection of various concentrations of Hg in PBS (pH =7.4) containing 0.15M triethanolamine using the modified electrode2+The photocurrent response was recorded, noting that the PBS solution was degassed with nitrogen for several minutes before the measurement experiment was performed, and then maintained under a nitrogen atmosphere throughout the experiment.
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| CN202110253020.XA CN113125535A (en) | 2021-03-09 | 2021-03-09 | Novel polyurethane foam electrode for ultra-sensitive detection of Hg2+ |
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| CN202110253020.XA CN113125535A (en) | 2021-03-09 | 2021-03-09 | Novel polyurethane foam electrode for ultra-sensitive detection of Hg2+ |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103308577A (en) * | 2013-06-27 | 2013-09-18 | 江南大学 | Photoelectrochemical measurement of mercury ions |
| CN103983672A (en) * | 2014-05-21 | 2014-08-13 | 河南师范大学 | Preparation method of graphene-sulfide quantum dot composite material |
| CN106353377A (en) * | 2016-09-21 | 2017-01-25 | 太原理工大学 | Method for preparing nanometer composite material ZnO-CdS-GO and method for constructing sensors from same and detecting mercury ions |
| US20180011054A1 (en) * | 2015-01-21 | 2018-01-11 | Sysmex Corporation | Metal ion detection method, test substance detection method |
-
2021
- 2021-03-09 CN CN202110253020.XA patent/CN113125535A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103308577A (en) * | 2013-06-27 | 2013-09-18 | 江南大学 | Photoelectrochemical measurement of mercury ions |
| CN103983672A (en) * | 2014-05-21 | 2014-08-13 | 河南师范大学 | Preparation method of graphene-sulfide quantum dot composite material |
| US20180011054A1 (en) * | 2015-01-21 | 2018-01-11 | Sysmex Corporation | Metal ion detection method, test substance detection method |
| CN106353377A (en) * | 2016-09-21 | 2017-01-25 | 太原理工大学 | Method for preparing nanometer composite material ZnO-CdS-GO and method for constructing sensors from same and detecting mercury ions |
Non-Patent Citations (5)
| Title |
|---|
| DAWEI HUANG ET AL.: "A highly sensitive protocol for the determination of Hg2+ in environmental water using time-gated mode", 《TALANTA》 * |
| LIXIANG ZHANG ET AL.: "Synergetic Ag2S and ZnS quantum dots as the sensitizer and recognition probe: A visible light-driven photoelectrochemical sensor for the "signal-on" analysis of mercury (II)", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
| SHIXIGUO ET AL.: "A facile and sensitive electrochemical sensor for non-enzymatic glucose detection based on three-dimensional flexible polyurethane sponge decorated with nickel hydroxide", 《ANALYTICA CHIMICA ACTA》 * |
| 张旭艳: "石墨烯—硫化物量子复合材料的制备及在光电化学传感中的应用", 《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》 * |
| 胡新军 等: "ZnS/还原氧化石墨烯复合材料的制备及光催化性能", 《复合材料学报》 * |
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