CN112697859B - Electrochemical sensing analysis method for nitrophenol by environmental hormone - Google Patents
Electrochemical sensing analysis method for nitrophenol by environmental hormone Download PDFInfo
- Publication number
- CN112697859B CN112697859B CN202011457692.4A CN202011457692A CN112697859B CN 112697859 B CN112697859 B CN 112697859B CN 202011457692 A CN202011457692 A CN 202011457692A CN 112697859 B CN112697859 B CN 112697859B
- Authority
- CN
- China
- Prior art keywords
- concentration
- environmental hormone
- dispersion liquid
- liquid
- electrochemical sensing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Electrochemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Investigating Or Analysing Biological Materials (AREA)
Abstract
The invention discloses an electrochemical sensing analysis method of environmental hormone 4-NP, which is implemented by mixing WO 2.9 /g‑C 3 N 4 Ultrasonically dispersing the stepped heterojunction in deionized water to obtain a dispersion liquid, wherein the concentration of the obtained dispersion liquid is 0.0002-0.01 g/mL; adding 1-10 mu L of WO on a clean and impurity-free bare glassy carbon electrode 2.9 /g‑C 3 N 4 Modifying the dispersion liquid, and then baking for 3-10 min under an infrared lamp to obtain a modified electrode; placing the modified electrode in liquid to be tested for DPV test; if an obvious oxidation peak appears in the range of 0.8-1.2V, the liquid to be detected is qualitatively detected according to the oxidation peak. When the concentration is in the range of 0.4-100 mu mol/L, the oxidation peak current value and the concentration have good linear relation, the detection limit is 0.13 mu mol/L, and the method has good stability and reproducibility and can be applied to the detection of the environmental hormone 4-NP in an actual water sample.
Description
Technical Field
The invention belongs to the technical field of electrochemical sensing, and particularly relates to an electrochemical sensing analysis method of environmental hormone p-nitrophenol.
Background
The environmental hormone refers to chemical substances which externally interfere the internal secretion of organisms, and the chemical substances are similar to hormones and are combined with hormone receptors in human bodies to influence the original hormone amount in the organisms, so that normal hormone imbalance is caused, the metabolic balance in the organisms is interfered, and the normal physiological function of the organisms is further influenced. Among them, the phenol environmental hormone has the highest attention, and as industrialization develops and environmental pollution increases, the phenol environmental hormone has increasing residue in the environment, has mutagenic, cytotoxic and phytotoxic effects, and is considered as a main priority pollutant in industrial wastewater. According to statistics, p-nitrophenol (4-NP) is one of the most harmful and toxic phenol environmental hormones, and is widely applied to production of pesticides, herbicides, synthetic dyes and the like at present, and the 4-NP which is inhaled or ingested by a human body and remains the environmental hormone causes headache, sleepiness, nausea and cyanosis, and finally causes serious harm to the health of the human body and the environment. The current method for detecting residual environmental hormone 4-NP in the environment mainly uses analytical instruments such as a liquid chromatograph-mass spectrometer, an inductively coupled plasma mass spectrometer and the like which have strong specialization and high testing cost. Therefore, it is urgently needed to develop a rapid, sensitive and real-time analysis method for detecting the environmental hormone 4-NP.
g-C 3 N 4 Has the advantages of high hardness, low density, high chemical stability, strong wear resistance, good biocompatibility, no toxicity, rich source of synthesized precursor, easy functionalization of the surface and the like, and g-C 3 N 4 Has a similar structure of graphene, can form pi-pi stacking interaction with aromatic environmental hormone molecules, and can accelerate environmental hormone analytes to be in g-C 3 N 4 And (4) enriching the surface. But the application of the material in the fields of photoelectrocatalysis and the like is limited due to the defects of wider band gap, serious carrier recombination, lack of surface active sites, thicker lamella, smaller specific surface area and the like.
Disclosure of Invention
The invention aims to provide an electrochemical sensing analysis method for efficiently detecting environmental hormone 4-NP, which has the advantages of low manufacturing cost, simple operation, high efficiency and sensitivity, and can be successfully applied to the detection of 4-NP in an actual water sample.
In order to achieve the purpose, the technical scheme is as follows:
the electrochemical sensing analysis method of the environmental hormone 4-NP comprises the following steps:
mixing WO 2.9 /g-C 3 N 4 Ultrasonically dispersing the stepped heterojunction in deionized water to obtain a dispersion liquid, wherein the concentration of the obtained dispersion liquid is 0.0002-0.01 g/mL;
adding 1-10 mu L of WO on a clean and impurity-free bare glassy carbon electrode 2.9 /g-C 3 N 4 Modifying the dispersion liquid, and then baking for 3-10 min under an infrared lamp to obtain a modified electrode;
placing the modified electrode in liquid to be tested to carry out Differential Pulse Voltammetry (DPV) test;
if an obvious oxidation peak appears in the range of 0.8-1.2V, the liquid to be detected is concluded to contain the environmental hormone 4-NP; thereby carrying out qualitative detection on the liquid to be detected.
According to the scheme, the method further comprises the following steps:
preparing a 4-NP solution sample with a known concentration of 0.04-100 mu mol/L, respectively carrying out differential pulse voltammetry on the 4-NP solution sample with the known concentration by using a modified electrode, and calculating a linear equation according to the oxidation peak current and the corresponding 4-NP concentration: i is p =0.0491c +0.0908; c is the concentration of 4-NP,. Mu.mol/L, I p μ a for oxidation peak current; the concentration of 4-NP in the liquid to be detected is quantitatively detected according to the method.
According to the above scheme, said WO 2.9 /g-C 3 N 4 The step-type heterojunction is prepared by adopting the following method:
heating melamine in a muffle furnace at a speed of 3-12 ℃/min to 500-600 ℃, keeping the temperature for 3-10h, and cooling to obtain light yellow g-C 3 N 4 A block body;
the obtained g-C 3 N 4 Placing the block in a high pressure reaction kettle with polytetrafluoroethylene lining, adding deionized water, mixing to obtain dispersion, and subjecting to g-C treatment with cell wall breaking ultrasonic instrument 3 N 4 Carrying out ultrasonic treatment on the dispersion liquid of the block; diluting the supernatant, placing in an ultrasonic cleaning machine, continuously performing ultrasonic treatment, and standing to obtain thin layer g-C 3 N 4 A dispersion liquid;
formulation of WCl 6 Transferring the absolute ethyl alcohol solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing and heating to 150-200 ℃ for 10-15 hours; naturally cooling, washing the substrate with absolute ethyl alcohol for 3-5 times, and vacuum drying at 50-80 ℃ to obtain WO 2.9 ；
Mixing WO 2.9 With a thin layer g-C 3 N 4 Mixing the dispersion liquid in a penicillin bottle, and putting the mixture into an ultrasonic cleaner for ultrasonic treatment for 20-80 min at 80-140W to obtain WO 2.9 /g-C 3 N 4 A step-type heterojunction.
According to the scheme, a cell wall breaking ultrasonic instrument is used for measuring the g-C 3 N 4 The power of ultrasonic treatment of the block body is 800-1500W, the start/stop time ratio is 10.
According to the scheme, the concentration of the diluted supernatant is 0.00001-0.0003 g/mL, and the continuous ultrasonic treatment power is 80-140W, and the treatment time is 1-4 h.
According to the scheme, WCl 6 The concentration of the solution in the absolute ethyl alcohol is 1 to 10g/L.
According to the above scheme, WO 2.9 And g-C 3 N 4 The mass ratio of (1) is (0.006-0.3).
The invention has the beneficial effects that:
the invention prepares WO with enhanced current signal on the surface of a glassy carbon electrode 2.9 /g-C 3 N 4 A step-type heterojunction material, and develops an electrochemical sensing analysis method for efficiently detecting environmental hormones.
The present invention utilizes WO 2.9 Nanoparticles and g-C 3 N 4 Electrostatic self-assembly of nano-sheet and preparation of WO 2.9 /g-C 3 N 4 The oxygen vacancy mediated stepped heterojunction has simple synthesis and low cost. Due to WO 2.9 And g-C 3 N 4 Recombination to form an oxygen vacancy mediated stepped heterojunction, WO 2.9 Due to the introduction of oxygen vacancies in the nanoparticles, excitons can be effectively dissociated into free charge carriers, thereby improving the electrocatalytic activity related to the carriers. Meanwhile, the stepped heterojunction can inhibit the recombination of useful electrons and holes on a heterointerface, so that the electrocatalysis rate of the surface of the modified electrode is improved.
When the concentration of the environmental hormone 4-NP is in the range of 0.4-100 mu mol/L, the oxidation peak current value and the concentration on the modified electrode have good linear relation, and the detection limit is 0.13 mu mol/basedL；WO 2.9 /g-C 3 N 4 The modified electrode has good stability and reproducibility when detecting the environmental hormone 4-NP; in addition, the sensing analysis method is also successfully applied to the detection of the environmental hormone 4-NP in an actual water sample.
Drawings
FIG. 1: differential pulse voltammogram of the environmental hormone 4-NP at different modified electrodes.
Detailed Description
The following examples further illustrate the technical solutions of the present invention, but should not be construed as limiting the scope of the present invention.
Example 1:
WO 2.9 /g-C 3 N 4 preparing a step-type heterojunction:
weighing 2-10 g of melamine, adding the melamine into a ceramic crucible, heating and stirring the mixture evenly, putting the mixture into a muffle furnace for heating at the heating rate of 3-12 ℃/min and the heating temperature of 500-600 ℃, keeping the temperature for 3-10h, and cooling the mixture to obtain the yellowish g-C 3 N 4 And (3) powder. Then g-C is added 3 N 4 Placing the cell in a cell wall breaking instrument for ultrasonic treatment, wherein the ultrasonic power is 800-1500W, and the ultrasonic treatment is started: the stop time ratio is 10. Taking 2-10 mL of supernatant fluid, diluting to 0.5-1.5L, carrying out ultrasonic treatment with the power of 80-140W for 1-4 h, standing overnight to obtain a thin layer g-C 3 N 4 A dispersion liquid; 0.05 to 0.20g of WCl 6 Putting the mixture into 20-50 mL of absolute ethyl alcohol, performing ultrasonic treatment to completely dissolve the mixture, wherein the ultrasonic power is 80-140W, the ultrasonic time is 3-10 min, then transferring the solution into a stainless steel high-pressure reaction kettle with a capacity of 50-100 mL and a polytetrafluoroethylene lining, sealing and heating the reaction kettle to 150-200 ℃ for 10-15 h, after the reaction is finished, naturally cooling the reaction kettle to room temperature, thoroughly washing the substrate with absolute ethyl alcohol for 3-5 times, and drying the substrate in a vacuum drying oven at 50-80 ℃ to obtain WO 2.9 (ii) a Weighing 0.001-0.05 g of WO 2.9 Placing the mixture into a penicillin bottle, and then adding 5-10 ml of thin layer g-C 3 N 4 Dispersing liquid, namely putting a penicillin bottle in an ultrasonic cleaner for ultrasonic treatment, wherein the ultrasonic power is 80-140W, and the ultrasonic treatment time is 20-80 min, so as to prepare WO 2.9 /g-C 3 N 4 A step-type heterojunction.
Preparing a modified electrode:
mixing WO 2.9 /g-C 3 N 4 Adding the step-type heterojunction powder into deionized water, and uniformly dispersing by ultrasonic, wherein the ultrasonic power is 80-140W, and the ultrasonic time is 5-30 min. Simultaneously using 0.02-1 mu mAl for the glassy carbon electrode 2 O 3 Polishing the polishing powder to a mirror surface, and cleaning the mirror surface by using deionized water. Transferring 1-10 mu LWO 2.9 /g-C 3 N 4 The dispersion liquid is dripped on the surface of a glassy carbon electrode, and after the glassy carbon electrode is baked for 3 to 10min under an infrared lamp, a layer of blue film is observed on the surface of the electrode, namely the WO is obtained 2.9 /g-C 3 N 4 And modifying the electrode.
Will modify the good WO 2.9 /g-C 3 N 4 Electrode and g-C 3 N 4 Electrode, WO 2.9 Electrode, WO 3 /g-C 3 N 4 Electrode, WO 3 And respectively carrying out DPV scanning on the electrode and the bare electrode in a solution to be detected containing the environmental hormone 4-NP. As can be seen from FIG. 1, WO 2.9 /g-C 3 N 4 The current of the environmental hormone 4-NP measured by the modified electrode is obviously higher than that of other electrodes. Conditions such as buffer solution, pH value and the like are optimized to maximize the oxidation peak current of the environmental hormone 4-NP.
Example 2
Preparing a sample of environmental hormone 4-NP at a known concentration of 0.04-100. Mu.M, and mixing WO 2.9 /g-C 3 N 4 The modified electrode is subjected to DPV scanning in the environmental hormone 4-NP, and a linear equation is calculated according to the oxidation peak current and the corresponding concentration of the environmental hormone 4-NP: i is p ＝0.0491c+0.0908(R 2 = 0.9985); c is the concentration of the environmental hormone 4-NP (. Mu.mol/L), I p The oxidation peak current (. Mu.A). According to the equation, the unknown concentration of the environmental hormone 4-NP can be quantitatively detected.
Example 3
Referring to example 1, preparation of WO 2.9 /g-C 3 N 4 A modified electrode, which is put into sodium acetate-acetic acid buffer solution with pH value of 3-7 containing the substance to be detected for DPV scanning and is measuredMeasuring the current intensity corresponding to the electrocatalytic oxidation peak of the environmental hormone 4-NP, and determining the content of the environmental hormone 4-NP. The optimum pH was 5, with the peak current being the greatest. Analyzing the electron proton transfer quantity according to the relation between pH and voltage, and performing linear regression analysis on the pH value and the voltage to obtain E pa (V)＝-0.06019pH+1.376(R 2 = 0.993), according to the formula d Epc /d pH =0.059m/n, where m is the number of protons and n is the number of electrons, giving dE pc /d pH =0.06019, close to 0.059, so m/n =1 can be obtained, i.e. in WO 2.9 /g-C 3 N 4 On the electrode, the number of transferred electrons in the 4-NP electrocatalytic oxidation process is equal to the number of protons.
Example 4
WO 2.9 /g-C 3 N 4 Preparation of modified electrode referring to example 1, the modified electrode was placed in a phosphate buffer system containing the analyte to be measured, DPV scanning was performed, and the content of the environmental hormone 4-NP in the water sample was obtained by measuring the current intensity corresponding to the electrocatalytic oxidation peak of the environmental hormone 4-NP according to the linear equation in example 2.
Example 5
The method is applied to a water sample in an actual environment, the taken water sample is filtered to be clear, and the environmental hormone 4-NP is detected. Under the optimal condition, a differential pulse voltammetry test is carried out, the concentration of 4-NP is calculated by adopting a standard addition method, the recovery rate is between 98.8 and 108.8 percent and the Relative Standard Deviation (RSD) is within 4.8 percent according to the linear equation of the oxidation peak current magnitude and the corresponding concentration of the environmental hormone 4-NP obtained in the example 2.
Example 6
Adding pyrocatechol, hydroquinone and Ca in an amount which is 10 to 200 times of that of the environmental hormone 4-NP solution with a proper concentration 2+ 、Cu 2+ And 20-300 times of glucose and Na 2+ 、Mg 2+ 、K + 、Cl - 、CO 3- And (3) carrying out interference test on the plasma, and finding that the substances do not interfere with the detection of the environmental hormone 4-NP, which shows that the electrochemical sensing analysis method has good interference resistance.
Claims (6)
1. The electrochemical sensing analysis method of the environmental hormone 4-NP is characterized by comprising the following steps:
mixing WO 2.9 /g-C 3 N 4 Ultrasonically dispersing the stepped heterojunction in deionized water to obtain a dispersion liquid, wherein the concentration of the obtained dispersion liquid is 0.0002-0.01 g/mL;
adding 1-10 mu L of WO on a clean and impurity-free bare glassy carbon electrode 2.9 /g-C 3 N 4 Modifying the dispersion liquid, and then baking for 3-10 min under an infrared lamp to obtain a modified electrode;
placing the modified electrode in liquid to be tested to carry out differential pulse voltammetry test;
if an obvious oxidation peak appears in the range of 0.8-1.2V, the liquid to be detected is concluded to contain the environmental hormone 4-NP; carrying out qualitative detection on the liquid to be detected;
said WO 2.9 /g-C 3 N 4 The step-type heterojunction is prepared by adopting the following method:
(1) Heating melamine in a muffle furnace at a speed of 3-12 ℃/min to 500-600 ℃, keeping the temperature for 3-10h, and cooling to obtain light yellow g-C 3 N 4 A block body;
(2) The obtained g-C 3 N 4 Placing the block in a high pressure reaction kettle with polytetrafluoroethylene lining, adding deionized water, mixing to obtain dispersion, and subjecting to g-C treatment with cell wall breaking ultrasonic instrument 3 N 4 Carrying out ultrasonic treatment on the dispersion liquid of the block; diluting the supernatant, placing in an ultrasonic cleaning machine, continuously performing ultrasonic treatment, and standing to obtain thin layer g-C 3 N 4 A dispersion liquid;
(3) Formulation of WCl 6 Transferring the absolute ethyl alcohol solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing and heating to 150-200 ℃ for 10-15 hours; naturally cooling, washing the substrate with absolute ethyl alcohol for 3-5 times, and vacuum drying at 50-80 ℃ to obtain WO 2.9 ；
(4) Mixing WO 2.9 With a thin layer g-C 3 N 4 Mixing the dispersion liquid in a penicillin bottle, and putting the penicillin bottle into an ultrasonic cleaner for ultrasonic treatment of 80-140W for 20-80 min to obtain WO 2.9 /g-C 3 N 4 A step-type heterojunction.
2. The method for electrochemical sensing analysis of environmental hormone 4-NP as claimed in claim 1, further comprising the steps of:
preparing a 4-NP solution sample with a known concentration of 0.04-100 mu mol/L, respectively carrying out differential pulse voltammetry on the 4-NP solution sample with the known concentration by using a modified electrode, and calculating a linear equation according to the oxidation peak current and the corresponding 4-NP concentration: i is p =0.0491c +0.0908; c is the concentration of 4-NP,. Mu.mol/L, I p μ a for oxidation peak current; the concentration of 4-NP in the liquid to be detected is quantitatively detected according to the method.
3. The method for electrochemical sensing analysis of environmental hormone 4-NP as claimed in claim 1, wherein the step (2) is performed by using a cell wall breaking ultrasonic instrument for g-C 3 N 4 The power of ultrasonic treatment of the block body is 800-1500W, the start/stop time ratio is 10.
4. The method for electrochemical sensing analysis of environmental hormone 4-NP as claimed in claim 1, wherein the concentration of diluted supernatant in step (2) is 0.00001-0.0003 g/mL, and the power of continuous ultrasonic treatment is 80-140W for 1-4 h.
5. The method for electrochemical sensing analysis of environmental hormone 4-NP as claimed in claim 1 wherein WCl in step (3) 6 The concentration of the solution in the absolute ethyl alcohol is 1 to 10g/L.
6. The method for electrochemical sensing analysis of environmental hormone 4-NP according to claim 1, wherein WO in the step (4) 2.9 And g-C 3 N 4 The mass ratio of (A) to (B) is 1 (0.006-0.3).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011457692.4A CN112697859B (en) | 2020-12-10 | 2020-12-10 | Electrochemical sensing analysis method for nitrophenol by environmental hormone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011457692.4A CN112697859B (en) | 2020-12-10 | 2020-12-10 | Electrochemical sensing analysis method for nitrophenol by environmental hormone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112697859A CN112697859A (en) | 2021-04-23 |
| CN112697859B true CN112697859B (en) | 2022-11-22 |
Family
ID=75509032
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011457692.4A Active CN112697859B (en) | 2020-12-10 | 2020-12-10 | Electrochemical sensing analysis method for nitrophenol by environmental hormone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112697859B (en) |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110220517A1 (en) * | 2008-01-09 | 2011-09-15 | Toto Ltd. | Method for specifically detecting test substance using photocurrent, sensor unit used therefor, and measuring device |
| JP6174790B2 (en) * | 2013-09-19 | 2017-08-02 | カウンスィル オブ サイエンティフィック アンド インダストリアル リサーチＣｏｕｎｃｉｌ Ｏｆ Ｓｃｉｅｎｔｉｆｉｃ ＆ Ｉｎｄｕｓｔｒｉａｌ Ｒｅｓｅａｒｃｈ | Nitrogen-doped porous carbon electrode catalyst and method for producing the same |
| CN105536842B (en) * | 2015-12-14 | 2017-11-10 | 西北师范大学 | A kind of carbonitride/tungsten trioxide nano composite and its preparation method and application |
| WO2019021189A1 (en) * | 2017-07-27 | 2019-01-31 | Sabic Global Technologies B.V. | Methods of producing a nanocomposite heterojunction photocatalyst |
| CN108745397A (en) * | 2018-05-03 | 2018-11-06 | 东南大学 | A kind of transient metal doped carbonitride/WO3Composite photo-catalyst and its preparation method and application |
| CN108525699B (en) * | 2018-05-04 | 2021-01-19 | 淮北师范大学 | Ultra-thin 2D WO3/g-C3N4Z-type heterojunction photocatalyst and preparation method thereof |
-
2020
- 2020-12-10 CN CN202011457692.4A patent/CN112697859B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112697859A (en) | 2021-04-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ensafi et al. | Simultaneous determination of ascorbic acid, epinephrine, and uric acid by differential pulse voltammetry using poly (p-xylenolsulfonephthalein) modified glassy carbon electrode | |
| Wang et al. | Covalent modification of glassy carbon electrode with L-cysteine for the determination of acetaminophen | |
| CN112505116B (en) | Electrochemical luminescence aptamer sensor for specifically detecting kanamycin, and preparation method and application thereof | |
| Ensafi et al. | Simultaneous determination of ascorbic acid, dopamine, and uric acid by differential pulse voltammetry using tiron modified glassy carbon electrode | |
| CN110618177B (en) | Preparation method and application of streptomycin electrochemical-photoelectrochemical dual-method ratiometric aptamer sensor | |
| CN110057882A (en) | A kind of electrochemica biological sensor and its application based on two-dimentional titanium carbon compound | |
| CN109655510B (en) | Construction of myocardial troponin I immunosensor based on flaky copper molybdenum sulfide | |
| CN111208182A (en) | Preparation method of electrochemical sensor for simultaneously detecting lead and cadmium heavy metals in soil | |
| CN106324056B (en) | A method of detecting chloramphenicol using ultrasound stripping porous carbon modified electrode | |
| Liu et al. | Fabrication of a highly sensitive electrochemiluminescence chlorpromazine sensor using a Ru (bpy) 3 2+ incorporated carbon quantum dot–gelatin composite film | |
| CN109187687B (en) | Preparation of conjugated organic microporous material modified electrode and application of modified electrode as peroxynitroso anion electrochemical sensor | |
| CN114524453A (en) | ZIF-8 derived ZnO/g-C3N4Preparation method of (A) and application of (A) in oxytetracycline sensors | |
| CN112697859B (en) | Electrochemical sensing analysis method for nitrophenol by environmental hormone | |
| CN113155917A (en) | Construction method of photo-assisted bipolar self-powered sensor for detecting ochratoxin A or aflatoxin B1 | |
| CN113176313A (en) | Preparation method of photoelectrochemical biosensor for detecting tetracycline | |
| CN111239212A (en) | Ciprofloxacin detection method | |
| CN114720456B (en) | Zinc porphyrin covalent organic framework and application thereof | |
| CN112858407B (en) | Electrochemical sensor for detecting ciprofloxacin and detection method thereof | |
| CN112010359B (en) | NiO/C nano composite electrode material and preparation method and application thereof | |
| Sun et al. | A Rapid and Easy Procedure of Enzyme Biosensor based on Nitrogen-Doped Graphene for Detection of Methyl Parathion in CHM | |
| Zhang et al. | Preparation of Novel Cystine-multiwalled Carbon Nanotubes-graphene Oxide-glassy Carbon Electrode and Electrochemical Detection of Riboflavin and Dopamine. | |
| CN111812174A (en) | Electrochemical immunosensor for detecting LGG (LGG), and preparation and use methods thereof | |
| CN111521658A (en) | Preparation method of high-sensitivity sensor for pesticide detection, product and application thereof | |
| CN111830103A (en) | Preparation and application methods of electrochemical sensor for rapidly detecting hydrogen peroxide | |
| Ensafi et al. | Voltammetric determination of dopamine in the presence of uric acid using a 2-hydroxy-1-(1-hydroxynaphthyl-2-azo)-naphthalin-4-sulfonic acid modified glassy carbon electrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |