CN115096972B - Electrochemical sensor for simultaneously detecting multiple endocrine disruptors and preparation method - Google Patents
Electrochemical sensor for simultaneously detecting multiple endocrine disruptors and preparation method Download PDFInfo
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- 239000000598 endocrine disruptor Substances 0.000 title claims abstract description 20
- 231100000049 endocrine disruptor Toxicity 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000001514 detection method Methods 0.000 claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- 239000004744 fabric Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 9
- 150000003624 transition metals Chemical class 0.000 claims abstract description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 150
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 148
- 239000000243 solution Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
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- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
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- 239000004202 carbamide Substances 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
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- 239000011259 mixed solution Substances 0.000 claims description 8
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- 239000012535 impurity Substances 0.000 claims description 6
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 5
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
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- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 claims description 2
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3277—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction being a redox reaction, e.g. detection by cyclic voltammetry
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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
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
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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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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
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Abstract
The invention discloses an electrochemical sensor for simultaneously detecting various endocrine disruptors and a preparation method thereof, which are characterized in that the electrochemical sensor is prepared by taking a self-supporting electrode of ternary transition metal NiCoFe-LDHs loaded on hydrophilic Carbon Cloth (CC) as a working electrode, placing the self-supporting electrode in a three-electrode system, and connecting the self-supporting electrode with an electrochemical workstation to form the electrochemical sensor for detecting various endocrine disruptors. The NiCoFe-LDHs/CC self-supporting electrode obtained by the in-situ growth method has large specific surface area, rich active sites and good conductivity, can be used for detecting the content of toxic endocrine disruptors in the environment as an accurate, simple, fast and economical electrochemical sensor, has higher sensitivity, wider linear range and lower detection limit, and can realize in-situ detection.
Description
Technical Field
The invention relates to the technical field of electrochemical detection of pollutants, in particular to an electrochemical sensor for simultaneously detecting multiple pollutants and a preparation method thereof.
Background
With the wide production and application of high polymer materials and fine chemical products, many chemical raw materials are continuously released into the environment, so that the health of human beings and other organisms is endangered and the ecological environment is destroyed, and therefore, the detection of harmful substances has become a focus of attention in the environmental field. Environmental Endocrine Disruptors (EDCs) are exogenous chemical substances that are released into the environment as a result of the production and life of humans and have estrogenic properties that affect normal hormone levels in humans and animals. For example, catechol (CA) and Hydroquinone (HQ) belong to EDCs, the estrogen effect can be caused by low dosage, and the source of the Catechol (CA) and the Hydroquinone (HQ) is wide, and the catechol and the hydroquinone are important raw materials in industries of industry such as industry, agriculture, medicine, leather, cosmetics and the like, and the catechol and the hydroquinone have the characteristics of high toxicity and difficult degradation and belong to persistent toxic and harmful substances. When the HQ intake of the human body is more than 1g, fatigue, headache, liver and kidney function damage, respiratory failure and further death phenomena are generated. In addition, when a human body directly touches CA, skin eczema is caused, and CA enters the human body to be combined with cells, so that the cells die, and the nervous system is poisoned and disordered. While HQ and CA are dihydroxybenzene isomers, similar in chemical nature, and can exist in the same environment at the same time and interfere with each other. Therefore, it is important to develop an effective environmental endocrine disruptor detection technique.
Currently, commonly used methods for detecting environmental endocrine disruptors include High Performance Liquid Chromatography (HPLC), gas chromatography-mass spectrometry (GC-MS), liquid chromatography-mass spectrometry (LC-MS), enzyme-linked immunosorbent assay (ELISA), colorimetry, electrochemistry and the like. And various chromatographic methods, mass spectrometry and ELISA instruments have high cost, complicated pretreatment and low accuracy of the colorimetric method, so that the application is limited. In the electrochemical method, if the traditional glassy carbon electrode or the traditional gold electrode is used, the key problems of high oxidation overpotential, poor selectivity, serious oxidation-reduction peak overlapping and the like affecting the measurement still exist in the process of detecting the environmental endocrine disruptors. It is therefore highly desirable to find electrode materials with good catalytic properties and good electrical conductivity to solve these problems.
The hydrotalcite (LDHs) material is used as an anion or hydrotalcite-like clay, and has the characteristics of low synthesis cost, environmental friendliness, simple synthesis, strong redox activity, strong adsorptivity, easiness in chemical modification and the like. In terms of electrochemistry, besides being used for preparing oxygen evolution, hydrogen evolution and supercapacitor materials, the LDHs material is also developed into different types of electrochemical sensors or biosensors for detecting hydrogen peroxide, glucose, glyphosate, dopamine and the like, and is considered as an electrode material with wide prospects. However, few reports of the use of existing LDHs materials for simultaneous detection of multiple endocrine disruptors and related research have focused on bimetallic hydrotalcite, which results in sensing performance limited by low specific surface area and low conductivity. Compared with binary LDHs, the ternary transition metal-based LDHs has higher conductivity, better electrocatalytic performance and the like, and has become one of the most competitive electrocatalytic materials. The ternary metal LDHs is synthesized by doping divalent metal or trivalent metal with similar ionic radius on the basis of the original binary LDHs, and the electronic structure of the original dual metal LDHs can be changed to a required direction by utilizing the synergistic effect between the main metal and the doped metal. However, the conductivity of the ternary transition metal-based LDHs materials prepared after the incorporation of divalent metals is still difficult to be greatly improved, which limits further improvement of the electrochemical properties thereof.
In electrochemical detection, the traditional glassy carbon electrode or gold electrode often has the defects of low sensitivity, poor repeatability, easy falling of materials after loading and the like, which greatly limits the detection performance of the modified electrode, and the self-supporting carbon cloth electrode has a unique porous network structure and can provide higher conductivity. In addition, the electrode with the three-dimensional porous network structure can provide the advantages of accelerating the electron transmission of the electrode surface, increasing the electrochemical active surface area, promoting the electrolyte permeation and the like. Accordingly, carbon cloths have begun to receive increasing attention as substrates supporting different nanostructure materials for use in electrocatalytic and electrochemical analysis.
Disclosure of Invention
The invention aims to prepare an electrochemical sensor material which is sensitive in detection and can simultaneously measure more than two pollutants (such as Catechol (CA) and Hydroquinone (HQ)) and a preparation method thereof. The prepared material has high sensitivity, low detection limit and simple and economic preparation method.
In order to solve the technical problems, the invention adopts the following technical scheme:
preparing a three-electrode system taking a modified hydrophilic carbon cloth electrode as a working electrode, wherein the surface of the modified hydrophilic carbon cloth electrode is loaded with ternary transition metal NiCoFe-LDHs, and the electrode system is connected with an electrochemical workstation to form an electrochemical sensor for detecting various endocrine disruptors. Wherein the working electrode preparation step:
(1) Pretreating hydrophilic Carbon Cloth (CC), removing surface impurities, and drying.
(2) Dissolving soluble nickel salt, soluble cobalt salt and soluble ferric salt in deionized water, and then NH 4 F was added to the above metal salt solution and designated as solution A. Urea was dissolved in deionized water and noted as solution B. Solution B was slowly poured into solution a and stirred to form a homogeneous solution.
(3) And (3) transferring the mixed solution in the step (2) into a high-pressure reaction kettle, immersing the hydrophilic carbon cloth in the step (1) into the mixed solution for hydrothermal reaction, and repeatedly washing and drying to obtain the ternary transition metal-based catalytic electrode, which is named as NiCoFe-LDHs/CC.
According to the invention, the three-dimensional electroactive material is directly grown on the carbon cloth substrate by a simple hydrothermal method, so that the problems of low conductivity, easy agglomeration and the like of the LDHs can be solved, an adhesive is not needed, the contact resistance is reduced, the acceleration of electron transfer of the electrode is facilitated, and the electrochemical performance of the sensing electrode is remarkably improved.
In the preparation route, the specific process conditions of each step are as follows:
(one) in the step (1):
and (3) preprocessing the hydrophilic carbon cloth, cutting the carbon cloth into blocks, washing with acetone, ethanol and deionized water, and drying the hydrophilic carbon cloth with surface impurities removed in an oven.
Preferably, in the step (1), acetone, ethanol and deionized water are used for ultrasonic washing for 5-40 min respectively, and the temperature of drying the hydrophilic carbon cloth after removing the surface impurities in an oven is 30-100 ℃.
Further preferably, in the step (1), acetone, ethanol and deionized water are used for ultrasonic washing for 10-30 min respectively, and the temperature of drying the hydrophilic carbon cloth after removing the surface impurities in an oven is 40-80 ℃.
Under the preferable condition, the pretreated hydrophilic carbon cloth has the highest peak current, good conductivity and better electron transfer efficiency.
(II) in the step (2):
the soluble nickel salt may be nickel chloride, nickel nitrate, nickel sulfate, nickel acetate, etc., the soluble cobalt salt may be cobalt nitrate, cobalt chloride, cobalt bromide, etc., and the soluble iron salt may be ferric chloride, ferric sulfate, ferric bromide, ferric nitrate, etc.
The invention constructs ternary metal with similar ionic radius, which is beneficial to improving the oxidation-reduction capability of the modified electrode, and greatly improves the defects of poor conductivity, easy agglomeration and the like of the layered double hydroxide due to the in-situ growth on the surface of the carbon cloth.
Preferably, the soluble nickel salt is Ni (NO 3 ) 2 The soluble cobalt salt is Co (NO 3 ) 2 The soluble ferric salt is Fe (NO) 3 ) 3 ，Ni 2+ ∶Co 2+ ∶Fe 3+ =1 to 5:1 to 3:1=2, ni (NO 2 ) 2 、Co(NO 3 ) 2 、Fe(NO 3 ) 3 Dissolving in 20-50 mL deionized water, adding 3-25 mmol NH 4 F, designated solution A. Further preferably, ni 2+ ∶Co 2+ ∶Fe 3+ =1-3:1-2:1-2, dissolved in 30-45 mL deionized water, added with 5-15 mmol NH 4 F, designated solution A.
Preferably, 5 to 40mmol of urea is dissolved in 20 to 50ml of deionized water; it is further preferred that 10 to 30mmol of urea is dissolved in 20 to 40ml of deionized water, designated as solution B.
Preferably, solution B is slowly poured into solution A and stirred for 5-20 min to form a homogeneous solution.
(III) in the step (3):
preferably, the mixed solution in step (2) is transferred to a polytetrafluoroethylene-lined autoclave.
According to the invention, three-dimensional electroactive materials are directly grown on a carbon cloth substrate by a simple hydrothermal method, the preparation of the NiCoFe-LDHs/CC is mainly controlled by the time and the temperature of hydrothermal reaction, preferably, the hydrothermal temperature is 50-200 ℃, and the reaction time is 5-20 h; further preferably, the hydrothermal temperature is 100 to 150 ℃ and the reaction time is 8 to 13 hours.
Preferably, the ternary transition metal catalytic electrode after the hydrothermal reaction is repeatedly washed by distilled water and ethanol and dried in an oven at 30-80 ℃ for several hours; it is further preferable that the washing is repeated with distilled water and ethanol, and the washing is dried in an oven at 40 to 70℃for several hours.
The obtained NiCoFe-LDHs/CC combines the advantages of the NiCoFe-LDHs and carbon cloth, and has the advantages of large specific surface area, rich active sites, good conductivity and the like.
According to the invention, the NiCoFe-LDHs is loaded on hydrophilic carbon cloth (NiCoFe-LDHs/CC) by an in-situ growth method, so that a self-supporting electrode capable of being used for simultaneously detecting more than two pollutants is obtained.
Compared with the prior art, the invention has the beneficial effects that:
(1) Through the synergistic effect between the ternary transition metal LDHs and the carbon cloth, the problems of low conductivity, easy agglomeration and the like of the LDHs can be solved, an adhesive is not needed, and the contact resistance is reduced.
(2) The catalytic electrode prepared by the invention has higher sensitivity, wider linear range and lower detection limit (as low as 0.1 mu M).
(3) The self-supporting unbonded electrode provided by the invention can be used as an efficient and economical electrochemical sensor for measuring the content of toxic pollutants in tap water and lake water, and has feasibility in practical application.
(4) The electrochemical sensor can accurately, simply, conveniently and rapidly detect various environmental endocrine disruptors, and can realize in-situ detection.
Drawings
FIG. 1 is a scanning electron microscope image of (a) CC and (b-d) NiCoFe-LDHs/CC.
FIG. 2-a is a cyclic voltammogram of CC, niFe-LDHs/CC, coFe-LDHs/CC and NiCoFe-LDHs/CC in 0.1M PBS (pH=7) containing 200. Mu.M HQ and CA (scan rate 50mV s) -1 )；
FIG. 2-b is a cyclic voltammogram of NiCoFe-LDHs/CC in 200. Mu.M HQ, 200. Mu.M CA and 0.1M PBS (pH=7) containing 200. Mu.M HQ and CA (scan rate 50mV s) -1 )；
FIG. 2-c is a graph of differential pulses of CC, niFe-LDHs/CC, coFe-LDHs/CC and NiCoFe-LDHs/CC in 0.1M PBS (pH=7) containing 50. Mu.M HQ and CA.
FIG. 3-a is a graph showing the differential pulse profile after continuous addition of different concentrations of HQ (5-200. Mu.M) to 0.1M PBS (pH=7) containing 50. Mu.M CA: linear relation of oxidation peak current and HQ concentration;
FIG. 3-b is a graph showing the differential pulse profile after continuous addition of CA (5-200. Mu.M) at various concentrations in 0.1M PBS (pH=7) containing 50. Mu.M HQ, as shown in the inset: linear relation of oxidation peak current and CA concentration;
FIG. 3-c is a graph showing the differential pulse profile after continuous addition of the same concentrations of HQ and CA (5-200. Mu.M) in 0.1M PBS (pH=7), inset: linear relationship of oxidation peak current to HQ and CA concentrations;
FIG. 4-a is a cyclic voltammogram of NiCoFe-LDHs/CC at different sweep rates in 0.1M PBS (pH=7) containing 200. Mu.M HQ and CA;
FIG. 4-b is a linear relationship of peak oxide currents of HQ and CA to the square root of scan rate;
FIG. 5-a is a graph showing the anti-interference performance of NiCoFe-LDHs/CC electrodes when mixed solution containing 50. Mu.M HQ and CA is detected;
FIG. 5-b is a stability study of NiCoFe-LDHs/CC electrodes after 10 days with initial cyclic voltammograms (scan rate 50mV s -1 )；
Detailed Description
The invention will be described in further detail with reference to the accompanying drawings and specific examples.
Example 1
The preparation method of the NiCoFe-LDHs/CC comprises the following steps:
(1) The following pretreatment was performed on the hydrophilic Carbon Cloth (CC): firstly, cutting the carbon cloth into blocks, and then washing the blocks with acetone, ethanol and deionized water. Subsequently, the hydrophilic carbon cloth with the surface impurities removed is dried in an oven.
In the embodiment, the carbon cloth detergent and the washing mode are respectively ultrasonic washing for 15min by using acetone, ethanol and deionized water. The oven drying temperature was 60 ℃.
(2) Accurate weighingSoluble nickel salts, soluble cobalt salts, soluble iron salts are dissolved in deionized water, followed by NH 4 F was added to the above metal salt solution and designated as solution A. Urea was dissolved in deionized water and noted as solution B. Solution B was slowly poured into solution a and stirred for 15min to form a homogeneous solution.
The soluble nickel salt used in this example was Ni (NO 3 ) 2 ·6H 2 O, the soluble cobalt salt is Co (NO 3 ) 2 ·6H 2 O, the soluble ferric salt is Fe (NO 3 ) 3 ·9H 2 O, the proportion of which is Ni 2+ ∶Co 2+ ∶Fe 3+ ＝2∶1∶1。
In this example, the parameters are solution a:35mL deionized water, 8mmolNH 4 F, performing the process; solution B:35mL deionized water, 20mmol urea.
(3) And (3) transferring the mixed solution in the step (2) into a high-pressure reaction kettle, immersing the hydrophilic carbon cloth pretreated in the step (1) into the mixed solution for hydrothermal reaction, repeatedly washing and drying for several hours to obtain a product, and marking as NiCoFe-LDHs/CC.
The autoclave in this example is a polytetrafluoroethylene-lined autoclave, the hydrothermal reaction is carried out by a hydrothermal method at 120 ℃ for 10 hours, the flushing mode is repeated flushing with distilled water and ethanol, and the drying mode is oven drying at 60 ℃ for several hours.
Comparative example 1
For comparison, niFe-LDHs/CC was prepared in the same manner.
The procedure of example 1 was repeated except that in step (2), the soluble salts added to solution A were Ni (NO 3 ) 2 、Fe(NO 3 ) 3 And (3) preparing the NiFe-LDHs/CC electrode under the same other test conditions.
Comparative example 2
For comparison, coFe-LDHs/CC was prepared in the same manner.
The procedure of example 1 was repeated except that in step (2), the soluble salts added to solution A were Co (NO 3 ) 2 、Fe(NO 3 ) 3 And (3) preparing the CoFe-LDHs/CC electrode under the same other test conditions.
FIG. 1 is a scanning electron microscope image of (a) CC and (b-d) NiCoFe-LDHs/CC. As can be seen from the graph, the pure carbon cloth surface is smooth, and the NiCoFe-LDHs/CC surface grows dense nanowires, the average diameter of which is 80nm, and the average length of which is 1.2 mu m. The nanowires are wound together, so that the electric activity area is increased, and the sensing performance and sensitivity are improved.
FIG. 2-a is a cyclic voltammogram of a different modified electrode in a 0.1M PBS (pH=7) solution containing 200. Mu.M HQ and CA. From the graph, on pure carbon cloth, the electrochemical response of HQ and CA was weak and the peak division position of the oxidation peak was not obvious. Compared with pure carbon cloth, the redox peak currents of NiFe-LDHs/CC and CoFe-LDHs/CC are obviously increased, which is mainly attributed to the good catalytic performance of the layered double hydroxide on HQ and CA. Compared with the above three electrodes, the electrode is doped with two divalent metals (Ni 2+ And Co 2+ ) The NiCoFe-LDHs/CC prepared later has the largest cyclic voltammetry current response value to 200 mu M HQ and CA, which is probably due to the fact that divalent metals with similar ionic radius are doped on the basis of the original binary layered double hydroxide to be beneficial to improving the redox capacity of the modified electrode, and meanwhile, the defects of poor conductivity, easy agglomeration and the like of the layered double hydroxide are greatly improved due to the fact that the NiCoFe-LDHs/CC grows on the surface of carbon cloth in situ. FIG. 2-b shows cyclic voltammograms of NiCoFe-LDHs/CC electrodes in the presence of HQ (200. Mu.M) or CA (200. Mu.M) and a mixture of HQ (200. Mu.M) or CA (200. Mu.M) simultaneously. It can be seen that a distinct redox peak appears when both HQ and CA are added alone or simultaneously. In addition, HQ and CA have little interaction in the course of detection.
Differential pulse voltammetry was used to examine the catalytic ability of different modified electrodes to HQ and CA. FIG. 2-c is a graph of differential pulses of different modified electrodes in 0.1M PBS (pH=7) solution containing 50. Mu.M HQ and CA. As shown, the differential pulse voltammograms present peak oxidation currents at 0.08V and 0.18V, corresponding to the two contaminants, respectively. Compared with other three materials, the current response value of the NiCoFe-LDHs/CC to 50 mu M HQ and CA is maximum, which shows that the constructed NiCoFe-LDHs/CC can detect HQ and CA at the same time and has higher current response to HQ and CA.
Example 2
The example is the application of NiCoFe-LDHs/CC electrode in HQ and CA detection.
This example is based on the NiCoFe-LDHs/CC prepared in example 1, and specifically comprises the following steps:
the concentration of one target detection object in the electrolyte is fixed, the concentration of the other target detection object is changed, the detection performance of the NiCoFe-LDHs/CC modified electrode pair HQ and CA is researched by adopting a differential pulse voltammetry, and the linear range and the detection limit of the detection of the HQ and CA at the same time are determined.
It can be seen from FIG. 3-a that when the concentration of CA is fixed at 50. Mu.M, the concentration of HQ varies between 5. Mu.M and 200. Mu.M, the peak current of oxidation of HQ gradually increases as the concentration increases, while the peak current of oxidation of CA remains almost unchanged. The limit of detection (LOD) was 0.15 μm (S/n=3). At lower HQ concentrations in solution, the electrode surface has enough reactive sites and therefore the current increases faster. When the HQ concentration is higher, the reactive sites on the electrode surface decrease, resulting in a slow increase in current. From the above, it is explained that the presence of a small amount of CA hardly affects the detection of HQ. It can be seen from FIG. 3-b that at a fixed HQ content of 50. Mu.M, the CA concentration was increased from 5. Mu.M to 200. Mu.M, and the oxidation peak current of CA gradually increased as the concentration increased, while the oxidation peak current of HQ remained almost unchanged. The limit of detection (LOD) was 0.11 μm (S/n=3).
In addition, to further investigate the performance of the NiCoFe-LDHs/CC modified electrode to detect both HQ and CA simultaneously, the peak current response of oxidation at increasing both HQ and CA target analyte concentrations was also tested. HQ and CA have good linear relationship between the target concentration and peak current in the concentration range of 5-200. Mu.M (FIG. 3-c).
Example 3
In the embodiment, the detection performance of the NiCoFe-LDHs/CC modified electrode pair HQ and CA under different scanning rates is studied by changing the scanning rate and adopting a drawing cyclic voltammogram.
FIG. 4-a is a cyclic voltammogram of the square root of NiCoFe-LDHs/CC electrodes for different scan rates (20 mV/s-100 mV/s) in the presence of HQ (200. Mu.M) and CA (200. Mu.M). As shown, the redox peak current gradually increases with increasing scan rate, and the redox peak potential shifts outward, indicating that HQ and CA electron transport at the modified electrode surface is reversible. FIG. 4-b is a graph of oxidation peak current versus square root of scan rate. From the figure, the electrode reaction of HQ and CA on the modified electrode surface is a diffusion control process.
Example 4
This example is a study of stability, selectivity and reproducibility of NiCoFe-LDHs/CC electrodes.
Selectivity is one of the important parameters of electrochemical sensors for practical sample analysis. To investigate the selectivity of the modified electrodes, the changes in peak current response values for HQ (50 μm) and CA (50 μm) were investigated in the absence or presence of common interfering substances (fig. 5-a). The interferents in the detection process comprise 50 times of NaCl and MgCl 2 、CaCl 2 、CuSO 4 And 10 times glucose, ascorbic acid, resorcinol and phenol. The experimental result shows that the influence of inorganic and organic interferents on the oxidation peak current values of HQ and CA is less than 5%, and the NiCoFe-LDHs/CC modified electrode has good selectivity on HQ and CA.
Reproducibility and stability are also important indicators for evaluating electrochemical sensors. The reproducibility was evaluated by continuously scanning the NiCoFe-LDHs/CC modified electrode five times by differential pulse voltammetry, and the relative standard deviation of the oxidation peak current values was 1.3% (HQ) and 0.8% (CA) respectively, as obtained from the experimental data. In addition, five identical modified electrodes were prepared by the same preparation method, and HQ and CA at the same concentration were detected with relative standard deviations of 3.4% and 3.66%, respectively. It can be seen from fig. 5-b that after 10 days of storage of the modified electrode at room temperature, a reduction in HQ of about 7.3% and a reduction in CA of about 4.9% can be obtained by comparing the change in peak current of the sensor. Therefore, the NiCoFe-LDHs/CC modified electrode pair HQ and CA show good reproducibility and stability in simultaneous detection.
Example 5
The procedure of steps (1) (2) (3) and example 2 of example 1 were repeated except that during the preparation of the NiCoFe-LDHs/CC electrode, in step (1), acetone, ethanol and deionized water were used to ultrasonically wash each for 25min, and the oven drying temperature was 70 ℃.
The detection performance of the NiCoFe-LDHs/CC electrode prepared under the conditions of this example on HQ and CA was inferior to that of the NiCoFe-LDHs/CC electrode prepared under the conditions of example 1. The linear range of Hydroquinone (HQ) and Catechol (CA) was 10-150. Mu.M, and the detection Limit (LOD) was 0.30. Mu.M and 0.20. Mu.M, respectively.
Example 6
The procedure of steps (1) (2) (3) and example 2 of example 1 were repeated except that in the preparation of the NiCoFe-LDHs/CC electrode, in step (2), the soluble nickel salt used was nickel chloride, the soluble cobalt salt was cobalt chloride, the soluble iron salt was ferric chloride, and Ni was 2+ ∶Co 2+ ∶Fe 3+ ＝1∶2∶1。
The detection performance of the NiCoFe-LDHs/CC electrode prepared under the conditions of this example on HQ and CA was inferior to that of the NiCoFe-LDHs/CC electrode prepared under the conditions of example 1. The linear range of Hydroquinone (HQ) and Catechol (CA) was 20-120. Mu.M, and the detection Limit (LOD) was 0.35. Mu.M and 0.25. Mu.M, respectively.
Example 7
The procedure of steps (1) (2) (3) and example 2 were repeated in example 1 except that 20mmol of NH was added in step (2) during the preparation of the NiCoFe-LDHs/CC electrode 4 F。
The detection performance of the NiCoFe-LDHs/CC electrode prepared under the conditions of this example on HQ and CA was inferior to that of the NiCoFe-LDHs/CC electrode prepared under the conditions of example 1. The linear range of Hydroquinone (HQ) and Catechol (CA) was 10-140. Mu.M, and the detection Limit (LOD) was 0.36. Mu.M and 0.24. Mu.M, respectively.
Example 8
The procedure of example 1, steps (1) (2) (3) and example 2 were repeated except that in step (2) 15mmol of urea was dissolved in 40mL of deionized water during the preparation of the NiCoFe-LDHs/CC electrode.
The detection performance of the NiCoFe-LDHs/CC electrode prepared under the conditions of this example on HQ and CA was inferior to that of the NiCoFe-LDHs/CC electrode prepared under the conditions of example 1. The linear range of Hydroquinone (HQ) and Catechol (CA) was 15-150. Mu.M, and the detection Limit (LOD) was 0.34. Mu.M and 0.26. Mu.M, respectively.
Example 9
The procedure of steps (1) (2) (3) and example 2 of example 1 were repeated except that in the preparation of the NiCoFe-LDHs/CC electrode, the hydrothermal reaction condition was maintained at 90℃for 10 hours in step (3).
The detection performance of the NiCoFe-LDHs/CC electrode prepared under the conditions of this example on HQ and CA was inferior to that of the NiCoFe-LDHs/CC electrode prepared under the conditions of example 1. The linear range of Hydroquinone (HQ) and Catechol (CA) was 30-126. Mu.M, and the detection Limit (LOD) was 0.47. Mu.M and 0.32. Mu.M, respectively.
The foregoing detailed description of the preferred embodiments and advantages of the invention will be appreciated that the foregoing description is merely illustrative of the presently preferred embodiments of the invention, and that no changes, additions, substitutions and equivalents of those embodiments are intended to be included within the scope of the invention.
Claims (5)
1. The method for preparing the electrochemical sensor for simultaneously detecting various endocrine disruptors is characterized in that the electrochemical sensor is prepared by taking a self-supporting electrode of ternary transition metal NiCoFe-LDHs loaded on hydrophilic carbon cloth as a working electrode, placing the self-supporting electrode in a three-electrode system, and connecting the self-supporting electrode with an electrochemical workstation to form the electrochemical sensor for detecting various endocrine disruptors; the preparation method of the working electrode of the electrochemical sensor is characterized by comprising the following steps:
(1) Pretreating hydrophilic carbon cloth CC, removing surface impurities, and drying;
(2) Dissolving soluble nickel salt, soluble cobalt salt and soluble ferric salt in deionized water, and then NH 4 F, adding the urea into the metal salt solution, namely a solution A, dissolving urea into deionized water, namely a solution B, slowly pouring the solution B into the solution A, and stirring to form a uniform solution; the saidThe soluble nickel salt is nickel chloride, nickel nitrate, nickel sulfate, and nickel acetate, the soluble cobalt salt is cobalt nitrate, cobalt chloride, and cobalt bromide, and the soluble ferric salt is ferric chloride, ferric sulfate, ferric bromide, and ferric nitrate, wherein Ni 2+ :Co 2+ :Fe 3+ =1~5:1~3:1~2；
(3) Transferring the mixed solution in the step (2) into a high-pressure reaction kettle, immersing the hydrophilic carbon cloth in the step (1) into the mixed solution for hydrothermal reaction, and repeatedly washing and drying to obtain a ternary transition metal-based catalytic electrode, which is marked as NiCoFe-LDHs/CC; the hydrothermal temperature is 50-200 ℃, and the reaction time is 5-20 h.
2. The method for preparing an electrochemical sensor for simultaneously detecting multiple endocrine disruptors according to claim 1, wherein in the step (1), acetone, ethanol and deionized water are used for ultrasonic washing for 5-40 min respectively, and the temperature of drying in an oven is 30-100 ℃.
3. The method for preparing an electrochemical sensor for simultaneously detecting multiple endocrine disruptors according to claim 1, wherein in the step (2), 5-40 mmol of urea is dissolved in 20-50 ml of deionized water.
4. An electrochemical sensor for simultaneously detecting multiple endocrine disruptors prepared by the method according to any one of claims 1 to 3, wherein Ni 2+ ，Co 2+ ，Fe 3+ A layered double hydroxide surface is introduced.
5. Use of the electrochemical sensor according to claim 4 for simultaneous detection of catechol, hydroquinone endocrine disruptors.
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