CN117825472B - Nitrate ion detection method of all-solid-state nitrate ion selective electrode based on cobalt-tungsten bimetallic selenide - Google Patents
Nitrate ion detection method of all-solid-state nitrate ion selective electrode based on cobalt-tungsten bimetallic selenide Download PDFInfo
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 title claims abstract description 88
- JPNWDVUTVSTKMV-UHFFFAOYSA-N cobalt tungsten Chemical compound [Co].[W] JPNWDVUTVSTKMV-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 150000003346 selenoethers Chemical class 0.000 title claims abstract description 60
- 238000001514 detection method Methods 0.000 title claims abstract description 24
- 150000002500 ions Chemical class 0.000 claims abstract description 38
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- -1 nitrate ions Chemical class 0.000 claims abstract description 19
- 230000004044 response Effects 0.000 claims abstract description 10
- 229910021607 Silver chloride Inorganic materials 0.000 claims abstract description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims abstract description 5
- 238000005259 measurement Methods 0.000 claims abstract description 4
- 230000003213 activating effect Effects 0.000 claims abstract description 3
- 230000026683 transduction Effects 0.000 claims description 30
- 238000010361 transduction Methods 0.000 claims description 30
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 239000006185 dispersion Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 13
- 238000012360 testing method Methods 0.000 claims description 12
- 229920006254 polymer film Polymers 0.000 claims description 11
- 235000010333 potassium nitrate Nutrition 0.000 claims description 10
- 239000004323 potassium nitrate Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 7
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 239000007810 chemical reaction solvent Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000012937 correction Methods 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 229920005597 polymer membrane Polymers 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical group [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical group [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- RCCTXJDEWUVEST-UHFFFAOYSA-N tetrakis(4-chlorophenyl)azanium borate Chemical compound B([O-])([O-])[O-].ClC1=CC=C(C=C1)[N+](C1=CC=C(C=C1)Cl)(C1=CC=C(C=C1)Cl)C1=CC=C(C=C1)Cl.ClC1=CC=C(C=C1)[N+](C1=CC=C(C=C1)Cl)(C1=CC=C(C=C1)Cl)C1=CC=C(C=C1)Cl.ClC1=CC=C(C=C1)[N+](C1=CC=C(C=C1)Cl)(C1=CC=C(C=C1)Cl)C1=CC=C(C=C1)Cl RCCTXJDEWUVEST-UHFFFAOYSA-N 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000011896 sensitive detection Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 9
- 239000000523 sample Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004769 chrono-potentiometry Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- CFPFMAGBHTVLCZ-UHFFFAOYSA-N (4-chlorophenoxy)boronic acid Chemical compound OB(O)OC1=CC=C(Cl)C=C1 CFPFMAGBHTVLCZ-UHFFFAOYSA-N 0.000 description 1
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical group CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910003266 NiCo Inorganic materials 0.000 description 1
- ORJNTPGYBORNOD-UHFFFAOYSA-N [W]=[Se].[Co] Chemical compound [W]=[Se].[Co] ORJNTPGYBORNOD-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000000050 nutritive effect Effects 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000006176 redox buffer Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- UOBBAWATEUXIQF-UHFFFAOYSA-N tetradodecylazanium Chemical compound CCCCCCCCCCCC[N+](CCCCCCCCCCCC)(CCCCCCCCCCCC)CCCCCCCCCCCC UOBBAWATEUXIQF-UHFFFAOYSA-N 0.000 description 1
- FHCPAXDKURNIOZ-UHFFFAOYSA-N tetrathiafulvalene Chemical compound S1C=CSC1=C1SC=CS1 FHCPAXDKURNIOZ-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
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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
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- General Health & Medical Sciences (AREA)
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Abstract
The invention discloses a nitrate ion detection method of an all-solid-state nitrate ion selective electrode based on cobalt-tungsten bimetallic selenide, which comprises the steps of firstly preparing nano structured cobalt-tungsten bimetallic selenide, then preparing the all-solid-state ion selective electrode, and finally using the all-solid-state nitrate ion selective electrode for detecting nitrate in a water body, wherein the detection step comprises the steps of (a) activating the all-solid-state ion selective electrode; (b) And carrying out potential response measurement on the electrode by adopting an electrochemical workstation, using an Ag/AgCl electrode as a reference electrode, and using the all-solid-state nitrate ion selective electrode as an indication electrode to detect the nitrate concentration in the water body. The invention can realize the rapid and sensitive detection of nitrate ions in the environmental water body sample.
Description
Technical Field
The invention relates to application of an ion selective electrode in the field of water detection, in particular to a nitrate ion detection method based on the ion selective electrode.
Background
The electrochemical sensor has the advantages of small volume, simple operation, uneasy influence of solution turbidity and the like, and can meet the requirements of real-time and dynamic monitoring, thus receiving more and more attention. The polymer film all-solid-state ion selective electrode is an important electrochemical sensor, and can realize direct potential detection of various ions in environmental water based on a Nernst equation. The solid ion-electron transduction layer is an important component of the all-solid ion selective electrode, is positioned between the ion selective membrane and the conductive substrate, has the function of ion-electron transduction, and can provide stable phase interface potential, thereby ensuring high stability and reproducibility of the all-solid ion selective electrode. Therefore, the key to the improvement of stability and reproducibility of all-solid-state ion-selective electrodes is the introduction of solid-state transduction layers with good performance (high specific capacitance).
Currently, porous carbon materials and noble metal nanomaterials with large specific surface areas and high hydrophobicity have been used as solid state transduction layers for all solid state ion selective electrodes. The transduction material has large double-layer capacitance and can provide good potential stability for all-solid-state ion selective electrodes. However, such electric double layer transduction materials still face a significant challenge in improving the reproducibility of the E o value (initial potential) of all-solid-state ion-selective electrodes. The Bu hlmann group of problems (Anal. Chem.2014, 86, 7111-7118.) adds redox-buffered electron pairs to ion-selective membranes to improve reproducibility of the all-solid ion-selective electrode E o. However, the redox buffer electron pairs used in this method tend to leak from the ion selective membrane into the sample solution, resulting in a drift in the value of electrode E o. To solve this problem Kozma et al (electrochem. Commun., 2021, 123, 106903) propose that carbon materials modified with redox-active groups are used as solid transduction layers to ensure good reproducibility of the E o values of the electrodes; however, the preparation of the transduction material is complicated and time-consuming.
Studies have shown that ion-electron transduction layers with redox activity have great potential in improving reproducibility of the electrode E o values. Conductive polymers are a typical redox type transduction material, and mainly comprise polypyrrole, polyaniline, polythiophene and the like. Since the conductive polymer has a wide electrode potential, it may exhibit a sustained oxidation-reduction potential as a solid state transduction layer, thereby shifting the E o value of the electrode. To solve this problem Vanamo et al (anal. Chem. 2014, 86, 10540-10545.) have used a short circuit to improve the reproducibility of the E o value of the conductive polymer-based all-solid ion-selective electrode. However, the short-circuit method is time-consuming to operate and the potential of the electrode may drift over time.
In recent years, new redox materials have been developed to improve the reproducibility of the E o values of electrodes, mainly including NiCo 2S4, co (II) and Co (III) complexes, tetrathiafulvalene, tetra (4-chlorophenyl) borate doped gold nanoclusters, ag@AgCl/1-tetradecyl-3-methylimidazole chloride and metal-organic frameworks. Various cation selective electrodes are constructed by using these materials as solid state transduction layers, but there are few reports on the construction of anion selective electrodes.
Nitrate is an important type of nutritive salt in the water environment, and is not only the basis of ocean primary productivity and food chains, but also a factor causing eutrophication of water. Therefore, detecting the concentration of nitrate ions in the water environment is of great importance for monitoring the health of the water environment. At present, the detection method of the water sample is to carry out complicated separation and enrichment on the water sample, and realize sample detection through large-scale equipment. Although the method has high analysis precision and accurate quantification, the method still has the problems of expensive equipment, complex operation process, long detection time consumption, difficulty in realizing on-site rapid detection and the like. Therefore, it is necessary to develop a portable technology capable of performing rapid analysis and detection on site to realize real-time and dynamic detection of nitrate concentration in a water environment.
Disclosure of Invention
The invention aims to solve the technical problem of providing a nitrate ion detection method of an all-solid-state nitrate ion selective electrode based on cobalt-tungsten bimetallic selenide, which realizes rapid and sensitive detection of nitrate ions in an environmental water body sample, and the all-solid-state nitrate ion selective electrode has higher stability and reproducibility.
The invention adopts the following technical scheme:
The nitrate ion detection method of the all-solid-state nitrate ion selective electrode based on cobalt-tungsten bimetallic selenide comprises the following steps of:
(1) Preparation of nanostructured cobalt-tungsten bimetallic selenide
(A) Dissolving a cobalt source, a tungsten source and urea in a certain molar ratio in a reaction solvent, and reacting to obtain a cobalt-tungsten bimetallic intermediate;
(b) Dispersing cobalt-tungsten bimetallic intermediate and selenium powder in a reaction solvent to obtain a dispersion liquid; continuing to react to obtain nano structured cobalt-tungsten bimetallic selenide;
(2) Preparation of all solid ion-selective electrode
Firstly, preparing a nitrate ion selective polymer film, and then coating the prepared nitrate ion selective polymer film on a glassy carbon electrode loaded with the nano structured cobalt-tungsten bimetallic selenide to obtain an all-solid-state ion selective electrode;
(3) The all-solid-state nitrate ion selective electrode is used for detecting nitrate in water body
(A) Activating the all-solid-state ion selective electrode;
(b) And carrying out potential response measurement on the electrode by adopting an electrochemical workstation, using an Ag/AgCl electrode as a reference electrode, and using the all-solid-state nitrate ion selective electrode as an indication electrode to detect the nitrate concentration in the water body.
Preferably, the specific steps of step (a) of step (3) are as follows:
prior to testing, the all-solid nitrate ion selective electrode was activated in 10 -3 M aqueous potassium nitrate for at least 8 hours.
Preferably, the specific steps of step (b) of step (3) are as follows:
Firstly testing open circuit potentials of an all-solid-state nitrate ion selective electrode at a plurality of nitrate concentrations, recording potential-time curves of the open circuit potentials, correcting the concentrations of potassium nitrate aqueous solutions with different concentrations into activities, and drawing correction curves; and finally, calculating according to the Nernst equation to obtain the concentration of nitrate ions.
Preferably, the cobalt source is cobalt chloride, cobalt nitrate or cobalt acetate; the tungsten source is tungstate; the molar ratio of the cobalt source to the tungsten source to the urea to the selenium powder is (0.01-0.1): (0.01-0.1): (0.1-1): (0.02-0.2).
Preferably, the reaction solvent is one or more of ethanol, ultrapure water and hydrazine hydrate in any proportion.
Preferably, the temperature of the reaction is 120-180 ℃ and the reaction time is 6-12 h.
Preferably, the nitrate ion selective polymer membrane is prepared according to the following steps: and (3) weighing nitrate ion carrier, tetra (4-chlorophenyl) ammonium borate, polyvinyl chloride and dioctyl sebacate, dissolving in tetrahydrofuran, and uniformly stirring to obtain the nitrate ion selective polymer membrane.
Further preferably, the preparation steps of the glassy carbon electrode are as follows:
Firstly, dispersing the prepared nano structured cobalt-tungsten bimetallic selenide in absolute ethyl alcohol, and carrying out ultrasonic treatment to form uniform dispersion; then, dripping the dispersion liquid on the surface of a glassy carbon electrode, and baking the dispersion liquid under an infrared lamp to obtain a uniform and compact transduction layer; and finally, dripping the prepared nitrate ion selective polymer film on the surface of the glassy carbon electrode, and putting the glassy carbon electrode into a constant temperature and humidity box for drying to obtain the glassy carbon electrode loaded with cobalt-tungsten bimetallic selenide.
Still more preferably, the dropping volume of the nitrate ion-selective polymer film dropped on the surface of the glassy carbon electrode is 8 to 12. Mu.L.
Compared with the prior art, the invention has the following beneficial effects:
the nano structured cobalt-tungsten bimetallic selenide is synthesized by adopting a solvothermal method, and the transduction of ions and electrons is effectively realized by utilizing the good conductivity and high redox characteristic of the bimetallic selenide. Then, dispersing the prepared cobalt-tungsten bimetallic selenide in ethanol solution, dripping the cobalt-tungsten bimetallic selenide on a glassy carbon electrode, and finally dripping an ion selective membrane to obtain the all-solid-state ion selective electrode. Based on the large redox capacitance of cobalt-tungsten bimetallic selenide, the electrode can construct an all-solid-state ion selective electrode with high stability and reproducibility. In addition, the constructed potential type all-solid-state ion selective electrode can be used for detecting nitrate in a water body environment sample.
The invention also has the following characteristics:
According to the invention, the bimetal selenide is used as the all-solid-state ion selective electrode of the ion-electron transduction material, so that the capacitance of the electrode can be effectively increased, and the stability of the electrode can be greatly improved.
The second, the invention uses the bimetallic selenide as the ion-electron transduction material of the all-solid ion selective electrode, which has better oxidation-reduction characteristic, the characteristic improves the reproducibility of the electrode, and provides a technical foundation for developing the all-solid ion selective electrode without correction.
Thirdly, the invention constructs the all-solid-state nitrate ion selective electrode, which is successfully used for detecting nitrate ions in water environmental samples (lake water, sea water, tap water, drinking water and the like), has the characteristics of rapidness and sensitivity, and has certain universality.
Drawings
Fig. 1 is a schematic diagram of a preparation flow of a tri-solid state nitrate ion selective electrode according to an embodiment of the present invention.
Fig. 2 is a scanning electron microscope image (a) of a cobalt-tungsten bimetallic intermediate and a scanning electron microscope image (B) of a cobalt-tungsten bimetallic selenide according to a fourth embodiment of the present invention.
Fig. 3 is an X-ray diffraction pattern of a cobalt-tungsten bi-metal intermediate and cobalt-tungsten bi-metal selenide provided in embodiment five of the invention.
Fig. 4 shows cyclic voltammograms (a) and corresponding integrated areas (B) of glassy carbon electrodes with different volumes of cobalt-tungsten bi-metal selenide dispersion drop wise provided in example six of the present invention.
Fig. 5 is a timing potential curve (a) and a corresponding capacitance change chart (B) of a glassy carbon electrode to which cobalt-tungsten bi-metal selenide dispersion liquid of different volumes is added dropwise according to the sixth embodiment of the present invention.
Fig. 6 is a timing potential comparison chart of all solid-state nitrate ion selective electrodes prepared by dropping a transduction layer and not dropping a transduction layer according to a seventh embodiment of the present invention.
FIG. 7 is a graph showing the electrochemical impedance of an all-solid nitrate ion-selective electrode prepared by dropping a transduction layer and not dropping a transduction layer according to an embodiment eight of the present invention.
Fig. 8 is a real-time potential change response chart (a) and a calibration graph (B) of an all-solid-state nitrate ion-selective electrode according to a ninth embodiment of the present invention.
Detailed Description
The following description of the embodiments of the present invention is further provided in connection with the accompanying examples, and it should be noted that the embodiments described herein are for the purpose of illustrating and explaining the present invention, and are not intended to limit the scope of the present invention.
Example one example of the preparation of nanostructured cobalt tungsten bi-metal selenide as an ion electron transduction layer material for an all solid state ion selective electrode.
Weighing 2.9107 g cobalt nitrate, 3.2985 g sodium tungstate and 6.006 g urea, and dissolving in ultrapure water and ethanol according to a volume ratio of 1:1, carrying out ultrasonic treatment in the mixed solution of 80 mL until the mixed solution is completely dissolved; then, the solution is transferred to a polytetrafluoroethylene reaction kettle together, and the reaction is carried out at 150 ℃ for 12 h; after the reaction is finished, naturally cooling the reaction kettle to room temperature, and centrifugally cleaning the reaction kettle for five times by using water and ethanol to obtain a cobalt-tungsten bimetallic intermediate in a precipitate form. Then dispersing the cobalt-tungsten bimetallic intermediate and 1.5792 g selenium powder in hydrazine hydrate and ethanol according to a volume ratio of 1:1, and continuing to react at 150 ℃ in the 50mL mixed solution of the catalyst, wherein the reaction is carried out for 12 h; and after the reaction is finished, naturally cooling the reaction kettle to room temperature, centrifugally cleaning the reaction kettle for five times by using water and ethanol, and finally drying the reaction kettle in a vacuum drying oven at 60 ℃ for 12 h to obtain the product of the nanostructured cobalt-tungsten bimetallic selenide.
Example two, preparation of nitrate ion-selective polymer membrane.
1.00 Wt% of nitrate ion carrier, 1.00% by weight of ETH500 [ tetra (4-chlorophenyl) borate ] tetradodecyl ammonium ], 32.70% wt% of PVC (polyvinyl chloride) and 65.30 wt% of DOS (dioctyl sebacate) are weighed, the total amount of solute is 100 mg, and the solution is dissolved in 1.5 mL of tetrahydrofuran and stirred uniformly to obtain the nitrate ion selective polymer membrane. Stored in a desiccator.
Example three, preparation example of cobalt-tungsten bimetallic selenide loaded glassy carbon electrode.
The nanostructured cobalt tungsten bi-metal selenide 40 mg prepared in example one was dispersed in 1mL absolute ethanol solution and sonicated 1 h to form a uniform dispersion. And then, dripping the dispersion liquid on the surface of the glassy carbon electrode, and baking the dispersion liquid under an infrared lamp to obtain the uniform and compact transduction layer. And finally, dripping the nitrate ion-selective polymer film prepared in the second embodiment on the surface of the glassy carbon electrode, and putting the glassy carbon electrode into a constant temperature and humidity box for drying overnight to obtain the glassy carbon electrode loaded with cobalt-tungsten bimetallic selenide.
Fig. 1 shows a schematic flow chart of the preparation of the all-solid-state nitrate ion-selective electrode of the present embodiment.
Example IV, cobalt-tungsten double-metal selenide appearance characterization example.
And (3) observing the cobalt-tungsten bimetallic intermediate and the nano structured cobalt-tungsten bimetallic selenide prepared in the first embodiment under a scanning electron microscope, and obtaining a scanning electron microscope picture shown in fig. 2.
As can be seen from fig. 2a, the cobalt-tungsten bimetallic intermediate synthesized by solvothermal method exhibits a smooth micro-morphology of microparticles. After selenization, the morphology of the material is that of microparticles composed of wrinkled nano-sheets (B in fig. 2), and the nanostructure can increase the specific surface area of the transduction layer material, so that the stability of the electrode can be improved.
Fifth, cobalt-tungsten bi-metal selenide phase characterization example.
And (3) carrying out phase analysis on the cobalt-tungsten bimetallic intermediate and the nano structured cobalt-tungsten bimetallic selenide prepared in the first embodiment by adopting an X-ray powder diffractometer to obtain an X-ray diffraction pattern shown in figure 3.
As can be seen from fig. 3, the synthesized cobalt-tungsten bimetallic intermediate is CoWO 4, and the end product after selenization is bimetallic cobalt-tungsten selenide (CoWSe 2).
Example six, cobalt-tungsten double metal selenide drop amount selection example of glassy carbon electrode.
Based on the glassy carbon electrode loaded with cobalt-tungsten bimetallic selenide obtained in the third embodiment, the dropping volume of the material of the transduction layer is optimized through an electric cyclic voltammetry, and specifically comprises the following steps: the electrodes were tested in 10 -1 M KCl electrolyte solution using a three electrode system for cyclic voltammetry. The parameters are as follows: the potential window is-0.8-0.65V and the scan rate is 100 mV s -1. The cyclic voltammogram and corresponding integrated area map shown in fig. 4 were obtained.
As can be seen from fig. 4a and fig. 4B, the glassy carbon electrode with a drop volume of 10 μl of cobalt-tungsten bi-metal selenide has a greater current response, indicating an optimal drop volume of 10 μl.
Based on the glassy carbon electrode loaded with cobalt-tungsten bimetallic selenide obtained in the third embodiment, the loading capacity of the material of the transduction layer is further optimized by a chronopotentiometry, and the glassy carbon electrode is specifically as follows: the applied current was 100 nA and the applied time was +60 s. The chronopotentiometric curve shown in fig. 5 and the corresponding capacitance change diagram are obtained.
As can be seen in fig. 5a and 5B, the glassy carbon electrode of cobalt-tungsten bi-metal selenide with a drop volume of 10 μl exhibited a smaller potential drift, and the drop volume of 10 μl exhibited the largest capacitance value, indicating the optimal drop volume of 10 μl, calculated according to the formula Δe/Δt=i/C (Δe/Δt is potential drift, I is applied current, and C is capacitance). The results are consistent with cyclic voltammetric test results.
Example seven, stability test example of all solid state nitrate ion selective electrode based on cobalt tungsten bi-metal selenide.
Based on the cobalt-tungsten bimetallic selenide-based all-solid nitrate ion-selective electrode (GC/CoWSe 2/NO3 - -ISM) obtained in example three, its short term stability was characterized by chronopotentiometry and compared with the performance of a wire-coated nitrate ion-selective electrode (GC/NO 3 - -ISM), in particular: prior to testing, the all solid state nitrate ion selective electrode was activated in 10 -3 M aqueous potassium nitrate for 10h. Then, the cobalt-tungsten bimetallic selenide-based all-solid-state ion selective electrode in the third embodiment and the comparative electrode (GC/NO 3 - -ISM) arranged above were subjected to a chronopotentiometric test by using a three-electrode system in 10 -3 M potassium nitrate solution with nitrate ions as a model. The parameters are as follows: applying a current: +1 nA for 60 s each. A timing potential contrast diagram shown in fig. 6 was obtained.
As can be seen from fig. 6, the introduction of the cobalt-tungsten bi-metal selenide of the transduction layer significantly reduces the potential drift of the all-solid-state ion selective electrode, and significantly improves the stability of the electrode.
Example eight, ion-electron diffusion rate experimental example for an all-solid nitrate ion selective electrode based on cobalt-tungsten bi-metal selenide.
Based on the cobalt-tungsten bimetallic selenide-based all-solid-state nitrate ion-selective electrode (GC/CoWSe 2/NO3 - -ISM) obtained in the third embodiment, the ion-electron transduction characteristic of the electrode is characterized by an electrochemical impedance method, and the performance of the electrode is compared with that of a wire-coated nitrate ion-selective electrode (GC/NO 3 - -ISM), specifically: the activated electrode is subjected to electrochemical impedance test in 10 -3 M potassium nitrate solution by adopting a three-electrode system. The parameters are as follows: the frequency range is: 0.01-10 5 H with amplitude of 100 mV. A comparison of electrochemical impedance is obtained as shown in fig. 7.
As can be seen from fig. 7, the introduction of the transduction layer reduces the contact resistance (the contact resistance between the membrane and the conductive matrix interface) and increases the ion-electron diffusion rate between the interfaces, as compared to an electrode without the transduction layer material.
Example nine, an example of an all-solid state nitrate ion selective electrode based on cobalt-tungsten bimetallic selenide applied to nitrate ion detection.
Based on the cobalt-tungsten bimetallic selenide-based all-solid-state ion selective electrode obtained in the third embodiment, the activated electrode (the all-solid-state nitrate ion selective electrode is activated in 10 -3 M potassium nitrate aqueous solution for 10 h) is used for detecting nitrate ions in the solution, and specifically: and carrying out potential response measurement on the electrode by adopting an electrochemical workstation, taking an Ag/AgCl electrode as a reference electrode, and taking the prepared all-solid nitrate ion selective electrode as an indication electrode. The electrodes were tested for open circuit potential in nitrate ion solutions of different concentrations against a water background and corresponding potential versus time curves and correction (log of activity versus potential) curves were plotted, see fig. 8.
As can be seen from the graph a in fig. 8, the all-solid-state ion-selective electrode based on cobalt-tungsten bi-metal selenide has a faster potential response speed and better potential stability. Firstly, testing the open-circuit potential of an all-solid-state nitrate ion selective electrode at the nitrate concentration of 10 -1M、 10-2M、10-3 M、10-4M、 10-5M、 10-6M、10-7 M and 10 -8 M, recording the potential-time curve of the open-circuit potential, correcting the concentration of potassium nitrate aqueous solutions with different concentrations into activity, and drawing a correction curve; and finally, calculating according to the Nernst equation to obtain the concentration of nitrate ions. As can be seen from the curve B in FIG. 8, the electrode exhibits a linear performance Style response in an aqueous solution having a potassium nitrate concentration of 10 -1- 10-8mol L-1, a response slope of 59.7.+ -. 1.4 mV/dec, a Nernst response linear range of 10 -1- 10-5mol L-1, and a detection limit of 3.2 ×10-6mol L-1. The result shows that the detection limit of the electrode meets the detection of nitrate ions in an actual sample.
Embodiment ten, detection verification example of nitrate ions in water environment.
The cobalt-tungsten bimetallic selenide-based all-solid-state ion selective electrode obtained based on the embodiment is used for detecting nitrate ions in a water body environment. The method comprises the following steps: the concentration of nitrate ions in lake water, sea water, tap water and drinking water is directly tested by taking the constructed all-solid-state nitrate ion selective electrode as an indicating electrode and Ag/AgCl as a reference electrode, and compared with the test result of the traditional method (ICP-MS). The results show that the test results of the nitrate ion selective electrode constructed by the invention are consistent with the test results of ICO-MS.
The cobalt nitrate is cobalt nitrate hexahydrate, and the sodium tungstate is sodium tungstate dihydrate. The reagents used in the embodiment of the invention are all commercially available except the reagents providing the preparation method, wherein tungstate, cobalt salt, urea and selenium powder are all analytically pure.
Claims (9)
1. The nitrate ion detection method of the all-solid-state nitrate ion selective electrode based on cobalt-tungsten bimetallic selenide is characterized by comprising the following steps of:
(1) Preparation of nanostructured cobalt-tungsten bimetallic selenide
(A) Dissolving a cobalt source, a tungsten source and urea in a certain molar ratio in a reaction solvent, and reacting to obtain a cobalt-tungsten bimetallic intermediate;
(b) Dispersing cobalt-tungsten bimetallic intermediate and selenium powder in a reaction solvent to obtain a dispersion liquid; continuing to react to obtain nano structured cobalt-tungsten bimetallic selenide;
(2) Preparation of all solid ion-selective electrode
Firstly, preparing a nitrate ion selective polymer film, and then coating the prepared nitrate ion selective polymer film on a glassy carbon electrode loaded with the nano structured cobalt-tungsten bimetallic selenide to obtain an all-solid-state ion selective electrode;
(3) The all-solid-state nitrate ion selective electrode is used for detecting nitrate in water body
(A) Activating the all-solid-state ion selective electrode;
(b) And carrying out potential response measurement on the electrode by adopting an electrochemical workstation, using an Ag/AgCl electrode as a reference electrode, and using the all-solid-state nitrate ion selective electrode as an indication electrode to detect the nitrate concentration in the water body.
2. The method for detecting nitrate ions of an all-solid-state nitrate ion-selective electrode based on cobalt-tungsten double metal selenide according to claim 1, wherein the specific steps of (a) of the step (3) are as follows: prior to testing, the all-solid nitrate ion selective electrode was activated in 10 -3 M aqueous potassium nitrate for at least 8 hours.
3. The method for detecting nitrate ions of an all-solid-state nitrate ion-selective electrode based on cobalt-tungsten double metal selenide according to claim 1, wherein the specific steps of (b) of the step (3) are as follows: firstly testing open circuit potentials of an all-solid-state nitrate ion selective electrode at a plurality of nitrate concentrations, recording potential-time curves of the open circuit potentials, correcting the concentrations of potassium nitrate aqueous solutions with different concentrations into activities, and drawing correction curves; and finally, calculating according to the Nernst equation to obtain the concentration of nitrate ions.
4. The nitrate ion detection method of an all-solid-state nitrate ion selective electrode based on cobalt-tungsten bimetallic selenide according to claim 1,2 or 3, wherein the cobalt source is cobalt chloride, cobalt nitrate or cobalt acetate; the tungsten source is tungstate; the molar ratio of the cobalt source to the tungsten source to the urea to the selenium powder is (0.01-0.1): (0.01-0.1): (0.1-1): (0.02-0.2).
5. The nitrate ion detection method of an all-solid-state nitrate ion selective electrode based on cobalt-tungsten bimetallic selenide according to claim 1,2 or 3, wherein the reaction solvent is one or more of ethanol, ultrapure water and hydrazine hydrate in any proportion.
6. The method for detecting nitrate ions of all-solid-state nitrate ion selective electrode based on cobalt-tungsten bi-metal selenide according to claim 1,2 or 3, wherein the reaction temperature is 120-180 ℃ and the reaction time is 6-12 h.
7. The nitrate ion detection method of an all solid state nitrate ion selective electrode based on cobalt tungsten bi-metal selenide according to claim 1 or 2 or 3, wherein the nitrate ion selective polymer film is prepared according to the steps of: and (3) weighing nitrate ion carrier, tetra (4-chlorophenyl) ammonium borate, polyvinyl chloride and dioctyl sebacate, dissolving in tetrahydrofuran, and uniformly stirring to obtain the nitrate ion selective polymer membrane.
8. The method for detecting nitrate ions of an all-solid-state nitrate ion selective electrode based on cobalt-tungsten bimetallic selenide according to claim 7, wherein the preparation steps of the glassy carbon electrode are as follows:
Firstly, dispersing the prepared nano structured cobalt-tungsten bimetallic selenide in absolute ethyl alcohol, and carrying out ultrasonic treatment to form uniform dispersion; then, dripping the dispersion liquid on the surface of a glassy carbon electrode, and baking the dispersion liquid under an infrared lamp to obtain a uniform and compact transduction layer; and finally, dripping the prepared nitrate ion selective polymer film on the surface of the glassy carbon electrode, and putting the glassy carbon electrode into a constant temperature and humidity box for drying to obtain the glassy carbon electrode loaded with cobalt-tungsten bimetallic selenide.
9. The method for detecting nitrate ions of the all-solid-state nitrate ion selective electrode based on cobalt-tungsten bimetallic selenide according to claim 8, wherein the dropping volume of the nitrate ion selective polymer film which is dropped on the surface of the glassy carbon electrode is 8-12 mu L.
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