CN115201310A - Method for detecting trace disinfection byproducts in water body - Google Patents
Method for detecting trace disinfection byproducts in water body Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000004659 sterilization and disinfection Methods 0.000 title claims abstract description 17
- 239000006227 byproduct Substances 0.000 title claims abstract description 13
- 238000001514 detection method Methods 0.000 claims abstract description 51
- PXSGFTWBZNPNIC-UHFFFAOYSA-N 618-80-4 Chemical compound OC1=C(Cl)C=C([N+]([O-])=O)C=C1Cl PXSGFTWBZNPNIC-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000002131 composite material Substances 0.000 claims abstract description 33
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 24
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- 239000011258 core-shell material Substances 0.000 claims abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 114
- 239000000243 solution Substances 0.000 claims description 36
- 239000010970 precious metal Substances 0.000 claims description 29
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 24
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 24
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 21
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- 150000003839 salts Chemical class 0.000 claims description 8
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- 239000006185 dispersion Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000000835 electrochemical detection Methods 0.000 claims description 4
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- 230000015572 biosynthetic process Effects 0.000 claims description 2
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- 239000000463 material Substances 0.000 abstract description 8
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- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract description 2
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- 230000000694 effects Effects 0.000 description 9
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- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical class OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 8
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- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- 239000008399 tap water Substances 0.000 description 4
- 235000020679 tap water Nutrition 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- OFAPWTOOMSVMIU-UHFFFAOYSA-N 2,4-dichloro-5-nitrophenol Chemical compound OC1=CC([N+]([O-])=O)=C(Cl)C=C1Cl OFAPWTOOMSVMIU-UHFFFAOYSA-N 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
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- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 2
- NWSIFTLPLKCTSX-UHFFFAOYSA-N 4-chloro-2-nitrophenol Chemical compound OC1=CC=C(Cl)C=C1[N+]([O-])=O NWSIFTLPLKCTSX-UHFFFAOYSA-N 0.000 description 2
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 2
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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
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
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Abstract
The invention discloses a method for detecting trace disinfection byproducts in a water body, which combines noble metal and a core-shell structure metal organic framework material ZIF-8@ ZIF-67 to prepare a noble metal doped ZIF-8@ ZIF-67 composite material. The electrochemical sensor is constructed by the glassy carbon electrode modified by the noble metal doped ZIF-8@ ZIF-67 composite material to detect 2,6-dichloro-4-nitrophenol, so that the reaction rate of reducing nitro in 2,6-dichloro-4-nitrophenol to hydroxylamine can be improved, the catalytic performance of the hydroxylamine is greatly improved, and a wider linear range and a lower detection limit are obtained by means of the rich pores of the noble metal doped ZIF-8@ ZIF-67 composite material, the synergistic effect among core shells and the excellent catalytic performance of noble metal nanoparticles.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a method for detecting trace disinfection byproducts in a water body.
Background
The water body disinfection can prevent the transmission and the prevalence of water-mediated infectious diseases, however, in the disinfection process, the disinfectant can generate a series of disinfection byproducts through chemical reaction with different types of organic matters. The disinfection by-products are substances generated by chemical reaction of disinfection agents with organic substances and inorganic ions in water in the disinfection process, and the disinfection by-products generally have triple effects (carcinogenesis, teratogenesis and mutagenesis), especially halogenated nitrophenol disinfection by-products attract extensive attention due to relatively high toxicity. Therefore, the method is particularly important for quantitative detection of the halogenated nitrophenol in the water body.
At present, methods for detecting halogenated nitrophenols include gas chromatography, gas chromatography-mass spectrometry, high performance liquid chromatography and the like. However, the above methods all have certain disadvantages, such as: the equipment has high cost, complex operation and maintenance, complex operation, long analysis time, large error, difficult real-time monitoring and the like. Therefore, it is highly desirable to develop a simple, efficient, fast, and low-cost method for detecting trace amounts of halogenated nitrophenols in water in real time. Electrochemical analysis techniques are a class of methods that use the electrochemical properties of a solution to convert the concentration of a substance being measured into an electrical signal for detection. The method has the advantages of simple operation, low cost, high sensitivity, high analysis speed and the like. Therefore, applications in the fields of foods, pharmaceuticals and cosmetics are becoming widespread.
ZIF-8@ ZIF-67 has abundant pore structures, and the core and shell ZIF-8 and ZIF-67 have similar topological structures and larger specific surface areas, so that the adsorbent is stronger. The ZIF-8 and the ZIF-67 have a certain synergistic effect, and can play a certain role in catalyzing an object to be tested while the nanoparticles are well dispersed. Noble metal nanoparticles, such as Ag, pd, au, etc., are receiving much attention due to their excellent properties and high efficiency heterogeneous catalytic activity applications.
Based on the method, the invention provides an electrochemical analysis method for detecting one of halogenated nitrophenol disinfection byproducts in water, more specifically 2,6-dichloro-4-nitrophenol, by using an electrode modified by a noble metal doped ZIF-8@ ZIF-67 composite material to construct an electrochemical sensor.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for detecting trace disinfection byproducts in a water body.
A method for detecting trace disinfection byproducts in a water body comprises the following steps:
s1, synthesis of a precious metal doped ZIF-8@ ZIF-67 composite material:
a1, preparing ZIF-8: respectively dissolving zinc nitrate hexahydrate and 2-methylimidazole in a methanol solution, mixing and stirring the methanol solution of the zinc nitrate hexahydrate and the methanol solution of the 2-methylimidazole, separating out a white product, purifying the obtained white product, and drying to obtain ZIF-8;
a2, preparing ZIF-8@ ZIF-67: respectively dissolving cobalt chloride hexahydrate and 2-methylimidazole in a methanol solution, and then mixing and stirring the methanol solution of the cobalt chloride hexahydrate and the methanol solution of the 2-methylimidazole to obtain a precursor solution; dissolving ZIF-8 in a methanol solution, performing ultrasonic treatment until the ZIF-8 is completely dispersed, adding a precursor solution into the methanol solution of ZIF-8, stirring, precipitating a purple product, purifying the obtained purple product, and performing vacuum drying to obtain a core-shell material ZIF-8@ ZIF-67;
a3, preparing a precious metal doped ZIF-8@ ZIF-67 composite material: ultrasonically dispersing the ZIF-8@ ZIF-67 prepared in the step A2 in an n-hexane solvent, adding a noble metal soluble salt solution while stirring, continuously stirring, standing, precipitating a precipitate, and drying; adding NaBH into the dried precipitate 4 The obtained product is stirred to react, centrifugally collected, purified and dried in vacuum to obtain the precious metal doped ZIF-8@ ZIF-67A composite material;
s2, preparing the noble metal doped ZIF-8@ ZIF-67 composite material modified electrode: pretreating the glassy carbon electrode, then dropwise coating the surface of the pretreated glassy carbon electrode with a dispersion liquid of the precious metal doped ZIF-8@ ZIF-67 composite material, and drying to obtain the precious metal doped ZIF-8@ ZIF-67 composite material modified electrode;
s3, electrochemical detection: a noble metal doped ZIF-8@ ZIF-67 composite material modified electrode is used as a working electrode, a platinum sheet is used as a counter electrode, saturated silver chloride is used as a reference electrode to form a three-electrode system, and the content of 2,6-dichloro-4-nitrophenol in a water body is detected by adopting a differential pulse voltammetry method.
Preferably, in the precious metal doped ZIF-8@ ZIF-67 composite material, the mass percentage of the precious metal elements is 2 to 3wt%.
Preferably, the soluble salt of the noble metal is selected from any one of soluble salts of Au, ag and Pd.
Preferably, the soluble salt of the noble metal is AgNO 3 。
Preferably, in the step A1, the volumes of the methanol for dissolving the 2-methylimidazole and the zinc nitrate hexahydrate are the same, wherein the molar ratio of the zinc nitrate hexahydrate, the 2-methylimidazole and the methanol (the total amount of the methanol for dissolving the 2-methylimidazole and the zinc nitrate hexahydrate is 1:3~5:100 to 140, and the vacuum drying temperature is 55 to 65 ℃, and the drying time is 10 to 15h.
Preferably, in the step A2, the volumes of the methanol in which the 2-methylimidazole, the cobalt chloride hexahydrate and the ZIF-8 are dissolved are the same, wherein the mass ratio of the ZIF-8, the 2-methylimidazole, the cobalt chloride hexahydrate and the methanol (which refers to the total amount of the methanol in which the 2-methylimidazole, the cobalt chloride hexahydrate and the ZIF-8 are dissolved) is 1:10 to 15:2~4:2000, the vacuum drying temperature is 55 to 65 ℃, and the drying time is 10 to 15h.
Preferably, in the step A3, ZIF-8@ ZIF-67, soluble salt of noble metal and NaBH 4 And n-hexane in a mass ratio of 1:1~2:15 to 20:900.
preferably, in step S2, the step of pretreating the glassy carbon electrode comprises: grinding a bare glass carbon electrode by using 0.05 mu m, 0.1 mu m and 0.3 mu m aluminum powder in sequence, then carrying out ultrasonic treatment in ethanol and ultrapure water for 15 to 30min respectively, and then placing in a drying box for drying at 55 to 65 ℃ for 1 to 3h.
Preferably, in the step S2, in the dispersion of the precious metal doped ZIF-8@ ZIF-67 composite, the mass-to-volume ratio of the precious metal doped ZIF-8@ ZIF-67 composite to ultrapure water is 1 to 2.2mg:1mL, and the dropping amount of the noble metal doped ZIF-8@ ZIF-67 composite material is 4~7 muL.
Preferably, the water sample needs to be pretreated before detection, and the method comprises the following specific steps: taking a water sample to be detected, filtering and removing impurities by using a filter membrane, and adjusting the pH value of the water sample to be detected to be 5.8 to 6.2.
The invention has the following beneficial effects:
(1) Based on the characteristics of a core-shell structure metal organic framework material ZIF-8@ ZIF-67, precious metal and 2,6-dichloro-4-nitrophenol, the invention combines the precious metal (Ag, pd or Au) with the core-shell structure metal organic framework material ZIF-8@ ZIF-67 for the first time, takes ZIF-8@ ZIF-67 as a carrier of the precious metal, adopts a double-solvent method to uniformly load precious metal nano particles in pores of a core-shell material metal organic framework, and prepares the precious metal doped ZIF-8@ ZIF-67 composite material, wherein in the composite material, the ZIF-8@ ZIF-67 as a carrier material has a larger specific surface area and a rich pore structure, so that the precious metal nano particles can be well dispersed to prevent the precious metal nano particles from being agglomerated, the precious metal doped ZIF-8@ ZIF-67 composite material also has a stronger adsorption effect on 2,6-dichloro-4-nitrophenol in a water body, and meanwhile, the synergistic effect of the precious metal nano particles also has a certain promotion effect on the catalytic action of the core-shell structure. Experiments prove that the precious metal doped ZIF-8@ ZIF-67 composite material prepared by the invention has excellent electrochemical catalysis effect on 2,6-dichloro-4-nitrophenol;
the invention takes the glassy carbon electrode modified by the noble metal doped ZIF-8@ ZIF-67 composite material as a working electrode to construct an electrochemical sensor, and an electrochemical analysis method is adopted to detect 2,6-dichloro-4-nitrophenol. Under the optimal test condition, the result is obtained by adopting differential pulse voltammetry detection: the current intensity of the detection limit reduction peak and the concentration of 2,6-dichloro-4-nitrophenol are 0.24 mu mol.L -1 ~288μmol·L -1 Exhibits a good linear relationship with a minimum detection Limit (LOD) of 2 nmol.L -1 Namely, the invention depends on rich pores and the synergistic effect among core shells of the precious metal doped ZIF-8@ ZIF-67 composite material and the excellent catalytic performance of precious metal nano particles, can greatly improve the reaction rate of reducing the nitro in 2,6-dichloro-4-nitrophenol into hydroxylamine, greatly improves the catalytic performance of 2,6-dichloro-4-nitrophenol, and finally obtains a wider linear range and a lower detection limit. In addition, the invention also carries out an anti-interference capability test, and the result shows that the Ag/ZIF-8@ ZIF-67 modified electrode shows higher selectivity for detecting 2,6-dichloro-4-nitrophenol.
(2) The detection method has the characteristics of wide detection linear range, low detection limit, strong anti-interference capability, simple operation, high efficiency, rapidness, low cost, strong portability and the like, and effectively solves the technical problems of high equipment manufacturing cost, inconvenience in carrying, complex operation, long analysis time, high analysis cost and the like of the traditional detection method. The detection method can be combined with a monitoring platform (an electrochemical workstation or a portable electrochemical workstation) to realize real-time monitoring of 2,6-dichloro-4-nitrophenol, so the detection method has strong practical value.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is an SEM picture of Ag/ZIF-8@ ZIF-67;
FIG. 2 is a graph of cyclic voltammograms measured on different electrodes for a phosphate buffer solution (0.2M, pH = 6) containing 20mg/L of 2,6-dichloro-4-nitrophenol;
FIG. 3 is a graph showing the signal response of electrodes modified by differential pulse voltammetry with different amounts of Ag/ZIF-8@ ZIF-67 drop to a phosphate buffer solution (0.2M, pH = 6) containing 20 mg/L2,6-dichloro-4-nitrophenol;
FIG. 4 is a signal response curve diagram of detection of 20 mg/L2,6-dichloro-4-nitrophenol in phosphate buffer solutions of different pH values using an Ag/ZIF-8@ ZIF-67 modified electrode as a working electrode by differential pulse voltammetry;
FIG. 5 is a differential pulse voltammetry graph of an electrochemical sensor constructed with Ag/ZIF-8@ ZIF-67 modified electrodes for detecting 2,6-dichloro-4-nitrophenol with different concentration gradients;
FIG. 6 is a fitting curve graph of signal response of an electrochemical sensor constructed by Ag/ZIF-8@ ZIF-67 modified electrode to 2,6-dichloro-4-nitrophenol with different concentrations under a detection peak and a standard sample concentration;
FIG. 7 is a graph showing the anti-interference test results of Ag/ZIF-8@ ZIF-67 modified electrode;
FIG. 8 is a graph showing the results of repeated five measurements of the current signal response generated using 5 Ag/ZIF-8@ ZIF-67 modified electrodes;
FIG. 9 is a graph showing the reproducibility of the current signal response measured on the first day and 7 days after the electrode was modified with Ag/ZIF-8@ ZIF-67.
Detailed Description
In the following description, for purposes of explanation and not limitation, specific details are set forth, such as particular system structures, techniques, etc. in order to provide a thorough understanding of the embodiments of the invention. It will be apparent, however, to one skilled in the art that the present invention may be practiced in other embodiments that depart from these specific details. In other instances, detailed descriptions of well-known systems, devices, circuits, and methods are omitted so as not to obscure the description of the present invention with unnecessary detail.
Example 1
The embodiment of the invention provides a method for detecting trace disinfection byproducts in a water body, which comprises the following steps:
s1, preparing an Ag-doped ZIF-8@ ZIF-67 composite material (hereinafter abbreviated as Ag/ZIF-8@ ZIF-67):
a1, preparing ZIF-8: respectively dissolving 5.95g of zinc nitrate hexahydrate and 6.29g of 2-methylimidazole in 50mL of methanol solution, mixing and stirring the two solutions for 24 hours, then mixing the methanol solution of cobalt chloride hexahydrate and the methanol solution of 2-methylimidazole, stirring for 24 hours, separating out a white product, centrifugally separating the white product, washing with methanol for three times, and performing vacuum drying at 60 ℃ for 12 hours to obtain ZIF-8;
a2, ZIF-8@ ZIF-67 preparation: respectively dissolving 177mg of cobalt chloride hexahydrate and 895mg of 2-methylimidazole in 10mL of methanol solution, and then mixing and stirring the methanol solution of the cobalt chloride hexahydrate and the methanol solution of the 2-methylimidazole for 2 hours to obtain a precursor solution; dissolving 80mg of ZIF-8 prepared in the step A1 in 10mL of methanol, performing ultrasonic treatment for 30min until the ZIF-8 is completely dispersed, dropwise adding a precursor solution into the methanol solution of the ZIF-8, stirring for 24h, separating out a purple product, performing centrifugal separation and collection on the product, washing the product with methanol for three times, and performing vacuum drying at 60 ℃ for 12h to obtain a core-shell structure metal-organic framework material ZIF-8@ ZIF-67;
meanwhile, ZIF-67 is prepared, and the specific steps are as follows: respectively dissolving 177mg of cobalt chloride hexahydrate and 895mg of 2-methylimidazole in 10mL of methanol solution, stirring for 24 hours, separating out a white product, centrifugally separating the white product, washing for three times by using methanol, and drying for 12 hours in vacuum at the temperature of 60 ℃ to obtain ZIF-67;
a3, ag/ZIF-8@ ZIF-67 preparation: dispersing 500mg of the core-shell structure metal organic framework material ZIF-8@ ZIF-67 prepared in the step A2 in 40mL of n-hexane solvent, performing ultrasonic treatment for 20min, and adding 1mL of the solvent containing 47.2mg of Ag (NO) while stirring 3 Stirring for 3 hr, standing, removing supernatant, and vacuum drying at 60 deg.C for 12 hr to obtain Ag + ZIF-8@ ZIF-67; weighing 100mg Ag + Adding 5mL of 30mg NaBH in ZIF-8@ ZIF-67 4 Stirring the methanol solution for 30min, centrifuging, collecting, washing with methanol and ultrapure water respectively for three times, and vacuum drying at 60 deg.C for 12 hr to obtain Ag/ZIF-8@ ZIF-67;
s2, preparing an Ag/ZIF-8@ ZIF-67 modified electrode (abbreviated as Ag/ZIF-8@ ZIF-67/GCE):
(1) Sequentially polishing a bare Glassy Carbon Electrode (GCE) by using aluminum powder with the particle size of 0.05 mu m, 0.1 mu m and 0.3 mu m, then respectively carrying out ultrasonic treatment on the polished electrode in ethanol and ultrapure water for 20min, and then placing the polished electrode in a drying oven to dry for 1h at the temperature of 60 ℃; (2) Weighing 2mg of Ag/ZIF-8@ ZIF-67, dissolving in 1mL of ultrapure water, carrying out ultrasonic treatment for 10min, dropwise adding 7 mu L of Ag/ZIF-8@ ZIF-67 dispersion liquid onto the surface of the dried glassy carbon electrode, and standing and drying at room temperature for 3h to obtain Ag/ZIF-8@ ZIF-67/GCE.
S3, electrochemical detection: and (2) forming a three-electrode system by using the Ag/ZIF-8@ ZIF-67/GCE prepared in the step S2 as a working electrode, a platinum wire as a counter electrode and a saturated silver chloride electrode as a reference electrode, placing the three-electrode system in an electrolytic cell, connecting the three-electrode system with an electrochemical workstation, and constructing an electrochemical detection device by using a phosphate buffer solution with the pH value of 0.2M & lt =6 & gt as an electrolyte. Scanning by adopting differential pulse voltammetry, wherein the scanning voltage range is as follows: -0.4V to-0.9V, negative scan, scan speed: 0.1V/s, pulse width 200ms, amplitude 50mV, sensitivity 10 -5 (ii) a Under the optimal test condition, the electrochemical response of 2,6-dichloro-4-nitrophenol on Ag/ZIF-8@ ZIF-67/GCE is determined, the electrochemical signal is recorded, a linear fitting curve of the peak current intensity and the concentration of 2,6-dichloro-4-nitrophenol is drawn according to the peak current intensity of the response signal of 2,6-dichloro-4-nitrophenol, and 2,6-dichloro-4-nitrophenol in a water sample is quantitatively analyzed.
1. Characterization of the materials:
as shown in FIG. 1, it is an SEM photograph of Ag/ZIF-8@ ZIF-67. From the results of FIG. 1, it is understood that Ag/ZIF-8@ ZIF-67 has a regular dodecahedron shape, relatively uniform shape and diameter, and an average diameter of about 500nm, and less agglomeration of noble metal nanoparticles Ag, and a small portion of the nanoparticles Ag are distributed on the surface of the ZIF-8@ ZIF-67 support material, and a large portion of the nanoparticles Ag are distributed in the pores of the ZIF-8@ ZIF-67 core-shell metal organic framework as the support material.
2. Cyclic voltammetric characterization of different electrodes
Bare Glassy Carbon Electrode (GCE), ag/ZIF-8 modified electrode, ag/ZIF-67 modified electrode and Ag/ZIF-8@ ZIF-67 modified electrode are used as working electrodes (wherein the preparation of the Ag/ZIF-8 modified electrode and the Ag/ZIF-67 modified electrode refers to the preparation method of the Ag/ZIF-8@ ZIF-67 modified electrode, which is not described herein in detail), detection is carried out in phosphate buffer solution (0.2M, pH = 6) containing 20 mg/L2,6-dichloro-4-nitrophenol, and the cyclic voltammetry curves obtained by different electrode detection are shown in FIG. 2.
From the results in FIG. 2, it can be seen that when 20 mg/L2,6-dichloro-4-nitrophenol is detected by cyclic voltammetry, the response current of the Ag/ZIF-8@ ZIF-67 modified electrode under the detection peak is 1.52 times that of the Ag/ZIF-8 modified electrode, 1.91 times that of the Ag/ZIF-67 modified electrode and 2.24 times that of a bare glassy carbon electrode, which indicates that the Ag/ZIF-8@ ZIF-67 modified electrode has excellent electrocatalytic performance for 2,6-dichloro-4-nitrophenol.
3. The invention optimizes the detection condition.
In order to obtain the largest response peak current with good shape and low background current for detecting 2,6-dichloro-4-nitrophenol by the Ag/ZIF-8@ ZIF-67 modified electrode, the experimental parameters of the dripping amount of Ag/ZIF-8@ ZIF-67, the pH value of a phosphate buffer solution and the like are optimized.
(1) Effect of drop coating amount on Peak Current intensity
A glassy carbon electrode modified with different Ag/ZIF-8@ ZIF-67 dropping amounts (4. Mu.L, 5. Mu.L, 6. Mu.L, 7. Mu.L, 8. Mu.L, 9. Mu.L, 10. Mu.L) by differential pulse voltammetry was used as a working electrode and detected in a phosphate buffer solution (0.2M, pH = 6) containing 20mg/L of 2,6-dichloro-4-nitrophenol, and the effect of the dropping amount on the peak current intensity of 2,6-dichloro-4-nitrophenol signal response was examined, and the detection result is shown in FIG. 3.
From the results of FIG. 3, it is understood that when the dropping amount of Ag/ZIF-8@ ZIF-67 is in the range of 4. Mu.L to 7. Mu.L, the peak current intensity of 2,6-dichloro-4-nitrophenol increases with the increase of the dropping amount, reaches the maximum value when the dropping amount is 7. Mu.L, and then decreases with the increase of the dropping amount. Therefore, the optimal dropping amount of the Ag/ZIF-8@ ZIF-67 modified electrode was selected to be 7. Mu.L.
(2) Effect of buffer solution pH on Peak Current intensity
The differential pulse voltammetry method is adopted, an Ag/ZIF-8@ ZIF-67 modified electrode is used as a working electrode, phosphate buffer solutions with different pH values (pH values of 5, 6, 7, 8 and 9) are used for detecting the 2,6-dichloro-4-nitrophenol with the concentration of 20mg/L, the influence of the pH value of the buffer solution on the peak current intensity is examined, and the detection result is shown in figure 4.
From the results of FIG. 4, it can be seen that in 0.2M phosphate buffer solution, the pH value was in the range of 5~6, the peak current intensity of 2,6-dichloro-4-nitrophenol increased as the pH value increased, reached the maximum at pH 6, and then decreased as the pH value increased. Therefore, the optimal pH of the buffer solution was selected to be 6, i.e., the detection effect of the Ag/ZIF-8@ ZIF-67 modified electrode was the best when the buffer solution was pH = 6.
4. The analytical performance of the Ag/ZIF-8@ ZIF-67 modified electrode.
Under the optimal experimental conditions (namely the pH of the buffer solution is 6, the dropping amount of the Ag/ZIF-8@ ZIF-67 is 7 mu L), an electrochemical sensor constructed by adopting the Ag/ZIF-8@ ZIF-67 modified electrode carries out Differential Pulse Voltammetry (DPV) test on 2,6-dichloro-4-nitrophenol with different concentration gradients (0.24 mu mol/L, 0.48 mu mol/L, 4.8 mu mol/L, 24 mu mol/L, 48 mu mol/L, 96 mu mol/L, 144 mu mol/L, 192 mu mol/L, 240 mu mol/L and 288 mu mol/L), and the test result is shown in figure 5.
From the results in FIG. 5, it is found that the concentration of 2,6-dichloro-4-nitrophenol is 0.24. Mu. Mol. L -1 ~288μmol·L -1 Within the range, good reduction peaks can be observed at about-0.64V, which shows that the signal response of the detection peak of 2,6-dichloro-4-nitrophenol under different concentration gradients has better linear relation.
The peak current intensity of the signal response at different concentration gradients was plotted against the corresponding concentration of 2,6-dichloro-4-nitrophenol (2,6-dichloro-4-nitrophenol purchased from sigma), and the measurements were repeated 3 times to obtain a linear fit curve, as shown in fig. 6.
From the results of fig. 6, it can be seen that the linear fit curve equation is y =0.076 x-2.27 2 = 0.992 (y: current/. Mu.A, x: concentration/. Mu.mol. L) -1 ) It shows that the fitting degree of the fitting curve is better, and the reduction peak current intensity and the concentration are 0.24 mu mol.L -1 ~288μmol·L -1 Exhibits a good linear relationship with a minimum detection Limit (LOD) of 2 nmol.L -1 The results show that the Ag/ZIF-8@ ZIF-67 modified electrode has a wider linear range and a lower detection limit.
5. Selective analysis of electrochemical sensors.
Because various kinds of dryness exist in the water body detection processInterfering substances may influence the detection result, so Mg is selected in the test 2+ 、Cu 2+ 、Ca 2+ Nitrobenzene, nitrophenol, p-nitrophenol, 4-chloro-2-nitrophenol, 2,4-dichloro-5-nitrophenol and humic acid are used as interference substances, and a DPV method is adopted to carry out interference experiment detection on 20 mg/L2,6-dichloro-4-nitrophenol.
Specifically, 20Mg/L of different interfering substances (Mg) were added to a phosphate buffer solution (pH =6,0.2M) 2+ 、Cu 2+ 、Ca 2+ Nitrobenzene, nitrophenol, p-nitrophenol, 4-chloro-2-nitrophenol, 2,4-dichloro-5-nitrophenol, humic acid), an electrochemical sensor constructed with an Ag/ZIF-8@ ZIF-67 modified working electrode using the DPV method was used for detection, and anti-interference results of interference current responses generated by different interfering substances were obtained, as shown in FIG. 7.
As can be seen from the results in FIG. 7, the presence of the above-mentioned interfering substance has no significant effect on 2,6-dichloro-4-nitrophenol, so that the electrochemical sensor constructed by the Ag/ZIF-8@ ZIF-67 modified working electrode of the present invention has high selectivity on 2,6-dichloro-4-nitrophenol, and has high selectivity on the above-mentioned interfering substance, such as metal ions (Mg) 2+ 、Cu 2+ 、Ca 2 ) And 2,6-dichloro-4-nitrophenol isomer (2,4-dichloro-5-nitrophenol).
6. The stability and repeatability of the electrode are modified.
In order to research the stability and repeatability of the constructed Ag/ZIF-8@ ZIF-67 modified electrode, five different Ag/ZIF-8@ ZIF-67 modified electrodes are simultaneously prepared, detection is carried out in 0.2mol/L phosphate buffer solution (pH is 6) containing 20 mg/L2,6-dichloro-4-nitrophenol, each electrode is repeatedly detected for 5 times, and the detection result is shown in figure 8.
From the results in FIG. 8, it can be seen that the average Relative Standard Deviation (RSD) measured with 5 different Ag/ZIF-8@ ZIF-67 modified electrodes was 5.15%, the average Relative Standard Deviation (RSD) measured with the same electrode was 3.47% after 5 repeated detections with the same electrode in the 0.2mol/L phosphate buffer solution (pH 6) containing 20 mg/L2,6-dichloro-4-nitrophenol, and the results show that the different electrodes and repeated detections have less influence on the current response of 2,6-dichloro-4-nitrophenol, indicating that the Ag/ZIF-8@ ZIF-67 modified electrode of the present invention has good stability and repeatability.
7. The reproducibility of the electrode is modified.
In order to study the reproducibility of the constructed Ag/ZIF-8@ ZIF-67 modified electrode, the invention adopts the Ag/ZIF-8@ ZIF-67 modified electrode to carry out detection in a phosphate buffer solution (pH 6,0.2M) containing 20mg/L halogenated nitrophenol, then the electrode is placed at room temperature for 7 days, repeated detection is carried out under the same conditions after 7 days, and the results of the two detections are shown in FIG. 9.
The results in FIG. 9 show that the current response value after being left for 7 days is 95.09% of the current response value of the first day, which indicates that the Ag/ZIF-8@ ZIF-67 modified electrode constructed by the invention has good reproducibility.
8. And (3) detection and analysis of an actual water sample: the electrochemical sensor constructed by the Ag/ZIF-8@ ZIF-67 modified electrode is used for detecting the real water sample.
In order to investigate the practical application performance of the modified electrode, the Ag/ZIF-8@ ZIF-67 modified electrode is used for the determination of 2,6-dichloro-4-nitrophenol in an actual water sample (tap water and swimming pool water) and the standard recovery rate test by adopting a Differential Pulse Voltammetry (DPV) method. The water samples of tap water and swimming pool water are taken from the university of Hunan, and the water samples are filtered by a 0.22 mu M filter membrane to remove solid impurities and flocculation precipitates in the water samples. The pH of the actual water samples was adjusted to 6.0 with 0.2M phosphate buffer solution before assay and the results are shown in table 1 below.
TABLE 1
Remarking: ND means no detection.
The results in Table 1 show that the recovery rate of an actual water sample is 5754-101.64% and RSD is not more than 4.03%, and that an electrochemical sensor constructed by the Ag/ZIF-8@ ZIF-67 modified electrode is feasible for detecting 2,6-dichloro-4-nitrophenol in the actual water sample, so that the Ag/ZIF-8@ ZIF-67 (the dripping amount is 7) prepared by the method is determined to have certain practical application value when being used as a modified electrode material for detecting the content of 2,6-dichloro-4-nitrophenol in tap water and swimming pool water.
In addition, aiming at the detection of 2,6-dichloro-4-nitrophenol in the water body, a portable electrochemical workstation can be adopted for detection: the method is characterized in that the method comprises the steps of dropwise coating the dispersion of Ag/ZIF-8@ ZIF-67 on a working electrode of a printing electrode, and drying, wherein the specific detection process is the same as that of the conventional electrochemical workstation. The portable electrochemical workstation (the size is 8cm multiplied by 4.6cm multiplied by 2 cm) is combined with the printing electrode (the size is 11mm multiplied by 33 mm) of the modified Ag/ZIF-8@ ZIF-67, and a mobile phone is adopted as a data output device, so that the device can be carried about, the portability of the device is greatly improved, and the device can be applied to the fields of field measurement or real-time monitoring of tap water and the like.
The present invention is not limited to the above-described embodiments, and those skilled in the art will be able to make various modifications without creative efforts from the above-described conception, and fall within the scope of the present invention.
Claims (10)
1. A method for detecting trace disinfection byproducts in a water body is characterized by comprising the following steps:
s1, synthesis of a precious metal doped ZIF-8@ ZIF-67 composite material:
a1, preparation of ZIF-8: respectively dissolving zinc nitrate hexahydrate and 2-methylimidazole in a methanol solution, mixing and stirring the methanol solution of the zinc nitrate hexahydrate and the methanol solution of the 2-methylimidazole, separating out a white product, purifying the obtained white product, and drying to obtain ZIF-8;
a2, ZIF-8@ ZIF-67 preparation: respectively dissolving cobalt chloride hexahydrate and 2-methylimidazole in a methanol solution, and then mixing and stirring the methanol solution of cobalt chloride hexahydrate and the methanol solution of 2-methylimidazole to obtain a precursor solution; dissolving ZIF-8 in a methanol solution, performing ultrasonic treatment until the ZIF-8 is completely dispersed, adding a precursor solution into the methanol solution of ZIF-8, stirring, separating out a purple product, purifying the obtained purple product, and performing vacuum drying to obtain a core-shell material ZIF-8@ ZIF-67;
a3, preparing a precious metal doped ZIF-8@ ZIF-67 composite material: ultrasonically dispersing the ZIF-8@ ZIF-67 prepared in the step A2 in an n-hexane solvent, adding a noble metal soluble salt solution while stirring, continuously stirring, standing, precipitating a precipitate, and drying; adding NaBH into the dried precipitate 4 Stirring the mixture to react, centrifugally collecting, purifying and drying in vacuum to obtain the noble metal doped ZIF-8@ ZIF-67 composite material;
s2, preparing the noble metal doped ZIF-8@ ZIF-67 composite material modified electrode: pretreating a glassy carbon electrode, then dropwise coating a dispersion liquid of a precious metal doped ZIF-8@ ZIF-67 composite material on the surface of the pretreated glassy carbon electrode, and drying to obtain a precious metal doped ZIF-8@ ZIF-67 composite material modified electrode;
s3, electrochemical detection: a noble metal doped ZIF-8@ ZIF-67 composite material modified electrode is used as a working electrode, a platinum sheet is used as a counter electrode, saturated silver chloride is used as a reference electrode to form a three-electrode system, and the content of 2,6-dichloro-4-nitrophenol in a water body is detected by adopting a differential pulse voltammetry method.
2. The detection method according to claim 1, wherein in the precious metal doped ZIF-8@ ZIF-67 composite material, the mass percentage of precious metal elements is 2 to 3wt%.
3. The detection method according to claim 2, wherein the soluble salt of a noble metal is selected from any one of soluble salts of Au, ag, pd.
4. The detection method according to claim 3, wherein the soluble salt of a noble metal is AgNO 3 。
5. The detection method according to claim 4, wherein in the step A1, the molar ratio of zinc nitrate hexahydrate, 2-methylimidazole and methanol is 1:3~5:100 to 140, and the vacuum drying temperature is 55 to 65 ℃, and the drying time is 10 to 15h.
6. The detection method according to claim 4, wherein in the step A2, the mass ratio of ZIF-8, 2-methylimidazole, cobalt chloride hexahydrate and methanol is 1:10 to 15:2~4:2000, the vacuum drying temperature is 55 to 65 ℃, and the drying time is 10 to 15h.
7. The detection method according to claim 4, wherein in step A3, ZIF-8@ ZIF-67, soluble salt of noble metal, naBH 4 And n-hexane in a mass ratio of 1:1~2:15 to 20:900.
8. the detection method according to claim 4, wherein in step S2, the pretreatment step of the glassy carbon electrode is as follows: the bare glassy carbon electrode is sequentially polished by aluminum powder of 0.05 mu m, 0.1 mu m and 0.3 mu m, then ultrasonic treatment is carried out for 15 to 30min in ethanol and ultrapure water respectively, and then the bare glassy carbon electrode is placed in a drying box to be dried for 1 to 3h at the temperature of 55 to 65 ℃.
9. The detection method according to claim 4, wherein in step S2, in the dispersion of the precious metal doped ZIF-8@ ZIF-67 composite, the mass-to-volume ratio of the precious metal doped ZIF-8@ ZIF-67 composite to ultrapure water is 1 to 2.2mg:1mL, and the dropping amount of the noble metal doped ZIF-8@ ZIF-67 composite material is 4~7 muL.
10. The detection method according to claim 3, wherein the water sample needs to be pretreated before detection, and the method comprises the following specific steps: taking a water sample to be detected, filtering and removing impurities by using a filter membrane, and adjusting the pH value of the water sample to be detected to be 5.8-6.2.
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