CN107271522B - Electrochemical sensor based on multi-stage porous Cu-BTC material and its application in the detection of pesticide glyphosate - Google Patents
Electrochemical sensor based on multi-stage porous Cu-BTC material and its application in the detection of pesticide glyphosate Download PDFInfo
- Publication number
- CN107271522B CN107271522B CN201710690861.0A CN201710690861A CN107271522B CN 107271522 B CN107271522 B CN 107271522B CN 201710690861 A CN201710690861 A CN 201710690861A CN 107271522 B CN107271522 B CN 107271522B
- Authority
- CN
- China
- Prior art keywords
- electrode
- glyphosate
- stage porous
- btc
- electrolytic solution
- 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
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
- G01N27/36—Glass electrodes
-
- 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
Abstract
Electrochemical sensor based on multi-stage porous Cu-BTC material and its application in the detection of pesticide glyphosate, it is related to the technology of preparing of electrochemical sensor material, multi-stage porous Cu-BTC material and perfluorinated sulfonic acid are successively modified in indium tin oxide-coated glass surface, the electrochemical sensor based on multi-stage porous Cu-BTC material is obtained.Using the electrochemical sensor as working electrode, as reference electrode, platinum electrode is used as to electrode saturated calomel electrode, is formed three-electrode system, can accurately be detected to testing liquid glyphosate content.Pass through test, the results showed that the sensitivity that the electrode detects glyphosate significantly improves, and modified electrode preparation is simple, reproducibility and stability are good, the range of linearity is wide, the content of detectable actual sample glyphosate, with simplicity, quickly, the advantages that accuracy is high.
Description
Technical field
The present invention relates to the technologies of preparing of electrochemical sensor material, are also related to the detection skill of electrically inactive pesticide glyphosate
Art field.
Background technique
Organophosphorus insecticide becomes current because having many advantages, such as that residual life is short, degradation is fast, less toxic, efficient and selectivity is strong
One of the most widely used pesticide in China, while being widely applied, organophosphorus pesticide can be rich in the environment such as soil, water
Collect, may there is a problem of that pesticide is exceeded after absorbing this kind of pesticide in plant growing process.Therefore, it is carried out quickly
Efficient detection has important Practical significance.
Glyphosate is a kind of common organophosphorus herbicide, and what as one kind, widely used, non-selective, seedling stage was used has
Machine phosphorus herbicide is widely used in weeding and vegetation control.Due to its high herbicidal and to the hypotoxicity of mammal, glyphosate
It is widely used in crops, woods crop and water plant.However, due to the absorption of soil and the highly dissoluble of water, it is this to be not added
The use of selection increases residual enrichment of the pesticide in soil and water, to endanger health and pollution environment.
In current glyphosate detection method reported in the literature, skill is mostly detected based on mature and stable chromatography
Art mainly includes high performance liquid chromatography (HPLC), gas chromatography (GC) and capillary electrophoresis etc..Although being based on chromatography skill
Detection method high sensitivity, the stability of art are strong, but detection device somewhat expensive, the disadvantages of sample pre-treatments are cumbersome limit
It is widely used.Therefore exploitation rapid and convenient, the detection technique of precise and high efficiency, be modern residue detection developing direction it
One.
Electrochemical sensor because have simple structure, high sensitivity, it is easy to operate, be easy to be miniaturized and convenient for large quantities of gauges
The advantages that mould produces, gathers around in fields such as food, environment measurings and has broad application prospects.As a kind of non-electroactive agriculture
Medicine, glyphosate are difficult to adopt traditional electrochemical method and are detected.By unremitting effort, researchers gradually overcome
Inadaptability of the electrochemistry in glyphosate detection, detection methods for organophosphorus pesticide studies based on electrochemical sensor technology
It quickly grew over the past two years.Glyphosate electrochemical measuring technique is concentrated mainly on electrochemical sensor containing enzyme, molecular engram electrification
Sensor and aptamers electrochemical sensor are learned, the preparation method of sensor is relatively complicated, and higher cost, and detection cycle is long
(with about when 1 hour or more).Therefore, preparing easy glyphosate electrochemical sensor becomes urgent problem to be solved.
Cu-BTC is a kind of common MOFs material, and multi-stage porous Cu-BTC material has micropore MOF material and mesoporous simultaneously
The characteristic feature of material has a wide range of applications in absorption, gas storage and catalysis.
Summary of the invention
Object of the present invention is to propose a kind of purposes that multi-stage porous Cu-BTC material is new, as electrochemical sensor.
The technical scheme is that: multi-stage porous Cu-BTC material and perfluorinated sulfonic acid are successively modified in tin indium oxide conduction glass
Glass surface obtains the electrochemical sensor based on multi-stage porous Cu-BTC material.
Due to using multi-stage porous Cu-BTC material as detection material, the present invention first modifies multi-stage porous Cu-BTC material
Perfluorinated sulfonic acid is then added dropwise in indium tin oxide-coated glass surface, realizes the embedding effect to the electrode surface for being covered with Cu-BTC,
Modified electrode can be preferably protected, keeps multi-stage porous Cu-BTC material not easily to fall off in the detection process.
Tests prove that: using the above-mentioned electrochemical sensor based on multi-stage porous Cu-BTC material as working electrode, saturation
As reference electrode, platinum electrode is used as to electrode calomel electrode, forms three-electrode system, can be to testing liquid glyphosate
Content is accurately detected.Pass through test, the results showed that the sensitivity that the electrode detects glyphosate significantly improves, and the modification
Electrode preparation is simple, reproducibility and stability are good, the range of linearity is wide, can detect the content of actual sample glyphosate, has letter
Just, quickly, the advantages that accuracy is high.
Further, the present invention disperses multi-stage porous Cu-BTC material in ethyl alcohol, and then drop coating is in tin indium oxide conduction
Glass surface, through drying, then drop coating perfluorinated sulfonic acid ethanol solution.Skeleton is easily caused since multi-stage porous Cu-BTC material encounters the water capacity
Collapse, and in ethanol then will not, so the present invention disperses multi-stage porous Cu-BTC material in ethyl alcohol.It, can by operate
To reach good detection effect in the uniform drop coating to electrode of multi-stage porous Cu-BTC material.
The dispersion ratio of the multi-stage porous Cu-BTC material and ethyl alcohol is 5 mg: 1 mL.Under the ratio, multi-stage porous Cu-BTC
Material dissolves more uniform in ethanol, is unlikely to overrich or excessively dilute.
The concentration of the perfluorinated sulfonic acid ethanol solution is 0.1 wt%, this is designed as the system of perfluorinated sulfonic acid ethanol solution standard
Preparation Method facilitates operation.
The present invention another object is that: by the electrochemical sensor based on multi-stage porous Cu-BTC material be applied to pesticide
The quick detection of glyphosate.
Further, it using the electrochemical sensor based on multi-stage porous Cu-BTC material as working electrode, is saturated sweet
As reference electrode, platinum electrode is used as to electrode mercury electrode, forms three-electrode system, at least three kinds of mixed electrolytic solution difference
Cyclic voltammetry scan is carried out, each mixed electrolytic solution is made of phosphate buffer solution and glyphosate standard solution, described each mixed
The phosphate buffer solution content closed in electrolyte is identical, and the glyphosate standard solution content in each middle mixed electrolytic solution is different；-
In 0.6 V and+0.6 V potential range, using the sweep speed of 50 mV/s, the peak point current of each mixed electrolytic solution is obtained respectively；
Obtain the peak point current of mixed electrolytic solution and the linear relationship of glyphosate concentration；
Testing sample solution is being mixed to composition mixed electrolytic solution to be measured with the phosphate buffer solution again, it is described to be measured mixed
The content for closing phosphate buffer solution in electrolyte is identical as the phosphate buffer solution content in above-mentioned each mixed electrolytic solution；
The three-electrode system is placed in mixed electrolytic solution to be measured, in -0.6 V and+0.6 V potential range, is used
The sweep speed of 50 mV/s obtains the peak point current of mixed electrolytic solution to be measured；
By the peak point current of the mixed electrolytic solution and the linear relationship of glyphosate concentration, obtain in testing sample solution
The concentration of glyphosate.
Compared with prior art, the invention has the following advantages:
1, the present invention is for the first time by the modification of multi-stage porous Cu-BTC material on electro-conductive glass.
2, Cu-BTC is applied to detect glyphosate on electrochemical sensor for the first time by the present invention, as a result has superelevation to glyphosate
Sensitivity response, detection be limited to 5.3 × 10-13Mol/L is minimum so far.
3, the present invention increases electrode reaction number of sites by the way that detection performance can be improved using Cu-BTC as detection matrix
Amount enhances adsorption capacity, expands the current-responsive to glyphosate, improves detection sensitivity.
4, Cu-BTC is applied on electrochemical sensor, glyphosate, optimization is detected using Differential Pulse Stripping Voltammetry
Influence of the factors such as enrichment time, accumulating potential, solution ph to dissolution peak current.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of multi-stage porous Cu-BTC material made from the method for the present invention.
Fig. 2 is the transmission electron microscope picture of multi-stage porous Cu-BTC material made from the method for the present invention.
Fig. 3 is cyclic voltammetric comparison diagram of the glyphosate in naked conductive glass electrode and electrochemical sensor of the present invention.
Fig. 4 is that concentration is respectively 0,1.0 × 10-12、5.0×10-12、1.0×10-11、5.0×10-11、1.0×10-10、
5.0×10-10The glyphosate of mol/L and the relational graph of peak current.
Fig. 5 is that concentration is respectively 5.0 × 10-10、1.0×10-9、5.0×10-9、1.0×10-8、5.0×10-8、1.0×
10-7、5.0×10-7、1.0×10-6、5.0×10-6、1.0×10-5The glyphosate of mol/ L and the relational graph of peak current.
Fig. 6 is that electrochemical sensor of the present invention is 1.0 × 10 to concentration-8Parallel determination 10 times peaks of mol/L glyphosate
Current graph.
Fig. 7 is the glyphosate concentration of sample to be tested and the relational graph of peak point current.
Specific embodiment
One, the preparation of multi-stage porous Cu-BTC material:
Take 0.435 g(1.8 mmol of Gerhardite), 0.620 mL(10.8 mmol of acetic acid), 0.50 mL of triethylamine
It mixes, and is stirred at room temperature 1 hour with 12 mL of ethyl alcohol.Then, 0.210 g(1.0 mmol of trimesic acid is added), continue
Stirring 2 hours.Then, mixture is transferred in the stainless steel autoclave containing polytetrafluoroethyllining lining, is reacted at 85 DEG C
12 hours.After reaction, by the way that product is collected by centrifugation, and three times with ethanol washing.Finally, by product dry 12 at 65 DEG C
Hour, obtain multi-stage porous Cu-BTC material.
Fig. 1 is the scanning electron microscope (SEM) photograph of Cu-BTC produced by the present invention, the pattern hole knot of available Cu-BTC from figure
Structure, large specific surface area.
Fig. 2 is the transmission electron microscope picture of Cu-BTC produced by the present invention, and Cong Tuzhong is clear that the structure of Cu-BTC is
Hierarchical porous structure.
Two, the preparation of electrochemical sensor:
It disperses 5 mg multi-stage porous Cu-BTC materials in the centrifuge tube equipped with 1 mL ethyl alcohol, 5 μ L is taken to be uniformly mixed
Cu-BTC dispersant liquid drop is added to clean conductive glass surface, and room temperature is dried, and 5 μ L perfluorinated sulfonic acids (Nafion) are then added dropwise again
Ethanol solution (0.1 wt%) is in the surface for being modified with multi-stage porous Cu-BTC materials conductive glass, to embed Cu-BTC, preferably
Modified electrode is protected, so that Cu-BTC is uniformly fixed on conductive glass surface by the film forming of Nafion.Under room temperature, to electricity
Pole surface solution evaporation is dry to get the electrochemical sensor based on multi-stage porous Cu-BTC material.
Three, Response Mechanism research of the electrochemical sensor to glyphosate based on multi-stage porous Cu-BTC material:
Respectively using the above-mentioned electrochemical sensor of preparation and clean electro-conductive glass as working electrode, to be saturated calomel electricity
Pole forms two groups of three-electrode systems, three-electrode system is respectively placed in pH as reference electrode using platinum electrode as to electrode
Value is in the 5.5, phosphate buffer solution that concentration is 0.1 mol/L, in -0.6 V and+0.6 V potential range, with 50 mV/s
Sweep speed carry out cyclic voltammetry scan, obtain two groups of cyclic voltammetry curves, as shown in Figure 3: making with clean electro-conductive glass
When for working electrode, there is no redox peaks in curve a in Fig. 3；And irreversible oxidation peak is observed in Fig. 3 in curve b.With
Clean electro-conductive glass is compared, and the oxidation current of Cu-BTC modified electrode significantly increases.These results should be attributed to multi-stage porous Cu-
The contribution of BTC material, since multi-stage porous Cu-BTC material has narrow aperture and the significant effective area for increasing electrode, because
This increases the reaction site of electrode, enhancing adsorption capacity and the current-responsive for amplifying Cu-BTC modified electrode.
Again using the above-mentioned electrochemical sensor of preparation as working electrode, using saturated calomel electrode as reference electrode, with platinum
Silk electrode is used as to electrode, forms three-electrode system, the phosphate buffer solution and 1.0 × 10 for being 0.1 mol/L with concentration-8
The mixed electrolytic solution of mol/L glyphosate composition, and mixed electrolytic solution pH value is 5.5, in -0.6 V and+0.6 V potential range
It is interior, cyclic voltammetry scan is carried out with the sweep speed of 50 mV/s, obtains curve c in Fig. 3.As expected, it is handled with glyphosate
Afterwards, the oxidation current of above-mentioned electrochemical sensor significantly reduces, this is because the part on above-mentioned electrochemical sensor surface is more
Grade hole Cu-BTC material is reacted with glyphosate, and oxidation current is caused to reduce.Therefore, inspection of the above-mentioned electrochemical sensor to glyphosate
It surveys and shows very strong response.
It prepares the electrolyte of different glyphosate concentrations: being mixed, matched with phosphate buffer solution and glyphosate standard solution respectively
Following electrolyte sample a, b, c, d, e, f, g are made, phosphate buffer solution content is 0.1 mol/L in each electrolyte sample, and
Glyphosate concentration of standard solution is respectively 0,1.0 × 10-12、5.0×10-12、1.0×10-11、5.0×10-11、1.0×10-10、
5.0×10-10 mol/ L。
Using above-mentioned electrochemical sensor as working electrode, saturated calomel electrode is as reference electrode, platinum electrode conduct
To electrode, in -0.6 V and+0.6 V potential range, with the sweep speed of 50 mV/s under conditions of, respectively to above each
Electrolyte cycles samples voltammetric scan, Response Mechanism of the research work electrode to glyphosate.
The Stripping Voltammetry curve that series of standards strength glyphosate solution is detected under the above same experimental conditions, obtains peak
The relational graph of electric current and glyphosate concentration.As shown in Figure 4.
Fig. 4 is illustrated: being 1.0 × 10 in glyphosate mark content-12L~1.0 × 10 mol/-9In the range of mol/ L, grass
The concentration of sweet phosphine and Stripping Voltammetry peak point current are in a linear relationship, linear equation be the log of Δ I=2.4767 (C)+
34.001。
Similarly, the electrolyte of different glyphosate concentrations is prepared: mixed with phosphate buffer solution and glyphosate standard solution respectively
It closes, prepares following electrolyte sample g, h, i, j, k, l, m, n, o, p, q, phosphate buffer solution content is in each electrolyte sample
0.1 mol/L, and glyphosate standard solution content is respectively 5.0 × 10-10、1.0×10-9、5.0×10-9、1.0×10-8、5.0
×10-8、1.0×10-7、5.0×10-7、1.0×10-6、5.0×10-6、1.0×10-5 mol/L。
Using Cu-BTC modified electrode as working electrode, saturated calomel electrode is as reference electrode, platinum electrode conduct pair
Electrode, in -0.6 V and+0.6 V potential range, with the sweep speed of 50 mV/s under conditions of, respectively to above each electricity
Solve liquid cycles samples voltammetric scan, Response Mechanism of the research work electrode to glyphosate.
The Stripping Voltammetry curve that series of standards strength glyphosate solution is detected under same experimental conditions, obtains peak current
With the relational graph of glyphosate concentration, as shown in Figure 5.
Fig. 5 is illustrated: being 1.0 × 10 in glyphosate mark content-9Mol/L~1.0 × 10-5In the range of mol/L, grass is sweet
The concentration of phosphine and Stripping Voltammetry peak point current are in a linear relationship, and linear equation is the log of Δ I=0.7524 (C)+17.669.
In addition, by test it is also shown that the detection of the sensor is limited to 5.3 × 10-13Mol/L illustrates it to glyphosate
Detection has hypersensitivity.
Respectively using electrochemical sensor made from ten above methods as working electrode, using saturated calomel electrode as reference
Electrode forms ten groups of three-electrode systems using platinum electrode as to electrode, is 5.5 in pH, the phosphorus for being 0.1 mol/L with concentration
Acid buffering solution and 1.0 × 10-8In the mixed electrolytic solution of mol/L glyphosate composition, in -0.6 V and+0.6 V potential range
It is interior, cyclic voltammetry scan is carried out with the sweep speed of 50 mV/s, detects the dissolution peak current of each electrolyte glyphosate respectively
Value, as shown in Figure 6: the relative standard deviation of the dissolution peak current of 10 above-mentioned electrochemical sensors is only 4.1%, is shown above-mentioned
Electrochemical sensor has preferable reproducibility.
As it can be seen that applying the electrochemical sensor produced by the present invention based on multi-stage porous Cu-BTC material in electrochemical sensing
Glyphosate content is detected on device, the electrode substantially increases the sensitivity to glyphosate detection, and modification electricity as the result is shown
Pole preparation is simple, reproducibility and stability are good, the range of linearity is wide, detection limit (5.3 × 10-13Mol/L) minimum, it can be further
Detect the content of actual sample glyphosate.
Five, it applies:
1, the pretreatment of sample:
Soybean sample is prepared by the following method: being weighed 5 g powdered soybean prints, is dissolved in 50 mL distilled water at ultrasound
Manage 20 min.Static 5 min takes 5 mL of supernatant in 10 mL centrifuge tubes, and the glyphosate standard solution of known concentration is added
Into the soybean sample matrix of acquisition.Then it is stored for future use after being filtered again with 0.45 μm of film.
2, the preparation of mixed electrolytic solution:
It takes and mixes 10.0 μ L treated sample solution with phosphate buffer solution, forming pH is 5.5, phosphate buffer solution
Concentration be 0.1 mol/L mixed electrolytic solution.
3, it detects:
Using above-mentioned electrochemical sensor as working electrode, saturated calomel electrode is as reference electrode, platinum electrode conduct
To electrode, in -0.6 V and+0.6 V potential range, with the sweep speed of 50 mV/s under conditions of, to mixed electrolytic solution
Cyclic voltammetry scan is carried out, obtaining peak point current is -6.277 μm, as shown in Figure 7.
4, the calculating of sample solution glyphosate concentration:
According to the relational graph or linear equation of the glyphosate of Fig. 6 and peak current: the log of Δ I=0.7524 (C)+
17.669。
Bring the above peak point current into above formula for -6.277 μm, can calculate and obtain the concentration of glyphosate is 1.01 × 10-6
mol/L。
The above operation about uses 35 minutes when sharing from the pretreatment of sample to the concentration for calculating acquirement glyphosate
The half that other methods are detected.
It is drawn a conclusion by the above experimental result, electrochemical sensor, which is made, in multi-stage porous Cu-BTC material by the present invention has
Excellent performance can be used as a kind of new electrode materials.Therefore, have as efficient sensor in medicine bioengineering, environmentally
Broad application prospect.
Claims (2)
1. application of the electrochemical sensor of multi-stage porous Cu-BTC material in the detection of pesticide glyphosate, the multi-stage porous Cu-BTC
The construction method of material electrochemical sensor is: multi-stage porous Cu-BTC material and perfluorinated sulfonic acid successively being modified and led in tin indium oxide
Electric glass surface；The preparation method of the multi-stage porous Cu-BTC material is: taking 0.435 g of Gerhardite, acetic acid 0.620
ML, 0.50 mL of triethylamine and 12 mL of ethyl alcohol mixing, and be stirred at room temperature 1 hour, then, trimesic acid 0.210 is added
G continues stirring 2 hours, then, mixture is transferred in the stainless steel autoclave containing polytetrafluoroethyllining lining, in 85 DEG C
Lower reaction 12 hours；After reaction, by the way that product is collected by centrifugation, and three times with ethanol washing；Finally, by product at 65 DEG C
It is 12 hours dry, obtain multi-stage porous Cu-BTC material.
2. application according to claim 1, it is characterised in that: passed with the electrochemistry based on multi-stage porous Cu-BTC material
Sensor is as working electrode, and as reference electrode, platinum electrode is used as to electrode saturated calomel electrode, forms three-electrode system,
Cyclic voltammetry scan is carried out respectively at least three kinds of mixed electrolytic solutions, each mixed electrolytic solution is sweet by phosphate buffer solution and grass
Phosphine standard solution forms, and the phosphate buffer solution content in each mixed electrolytic solution is identical, the grass in each middle mixed electrolytic solution
Sweet phosphine standard solution content is different；In -0.6 V and+0.6 V potential range, using the sweep speed of 50 mV/s, take respectively
Obtain the peak point current of each mixed electrolytic solution；Obtain the peak point current of mixed electrolytic solution and the linear relationship of glyphosate concentration；
Testing sample solution is mixed to composition mixed electrolytic solution to be measured, the mixed electrolytic solution to be measured with the phosphate buffer solution
The content of middle phosphate buffer solution is identical as the phosphate buffer solution content in above-mentioned each mixed electrolytic solution；
The three-electrode system is placed in mixed electrolytic solution to be measured, in -0.6 V and+0.6 V potential range, using 50
The sweep speed of mV/s obtains the peak point current of mixed electrolytic solution to be measured；
By the peak point current of the mixed electrolytic solution and the linear relationship of glyphosate concentration, show that testing sample solution medium-height grass is sweet
The concentration of phosphine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710690861.0A CN107271522B (en) | 2017-08-14 | 2017-08-14 | Electrochemical sensor based on multi-stage porous Cu-BTC material and its application in the detection of pesticide glyphosate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710690861.0A CN107271522B (en) | 2017-08-14 | 2017-08-14 | Electrochemical sensor based on multi-stage porous Cu-BTC material and its application in the detection of pesticide glyphosate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107271522A CN107271522A (en) | 2017-10-20 |
| CN107271522B true CN107271522B (en) | 2019-11-01 |
Family
ID=60080326
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710690861.0A Active CN107271522B (en) | 2017-08-14 | 2017-08-14 | Electrochemical sensor based on multi-stage porous Cu-BTC material and its application in the detection of pesticide glyphosate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107271522B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109776811B (en) * | 2017-11-15 | 2021-07-06 | 浙江工商大学 | Preparation and application of glyphosate molecularly imprinted solid phase extraction column |
| CN109883877A (en) * | 2019-03-14 | 2019-06-14 | 飞思仪表（深圳）有限公司 | Quartz crystal microbalance and humidity sensor based on metal-organic framework material |
| CN112798665B (en) * | 2021-01-08 | 2023-02-17 | 江西农业大学 | Preparation method and application of copper-based-organic metal framework electrochemical sensor for measuring zearalenone |
| CN112903781B (en) * | 2021-01-11 | 2022-07-08 | 北京理工大学 | Molecularly imprinted electrochemical sensor of electro-copper-based MOFs sensitive membrane modified electrode and preparation method and detection method thereof |
| CN113607767B (en) * | 2021-08-03 | 2023-11-03 | 广东五研检测技术有限公司 | MOFs composite TiO 2 Preparation method and application of photoactive material electrode |
| CN114324515B (en) * | 2021-12-01 | 2022-09-27 | 江南大学 | Electrochemical sensor for detecting glyphosate based on copper porphyrin metal organic framework modified carbon paper electrode |
| CN114878662B (en) * | 2022-05-20 | 2023-02-28 | 中南大学 | Application of Cu-HHB or Cu-BTC in detection of pyocin |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106568811A (en) * | 2016-11-18 | 2017-04-19 | 桂林电子科技大学 | Cu-BTC/polypyrrole nanowire/graphene nano composited material-based ammonia gas sensor, and preparation method thereof |
-
2017
- 2017-08-14 CN CN201710690861.0A patent/CN107271522B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| Cu-BTC frameworks-based electrochemical sensing platform for rapid and simple determination of Sunset yellow and Tartrazine;Liudi Jia et al.;《Sensors and Actuators B: Chemical》;20161231;第231卷;第2.3节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107271522A (en) | 2017-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107271522B (en) | Electrochemical sensor based on multi-stage porous Cu-BTC material and its application in the detection of pesticide glyphosate | |
| Cao et al. | An electrochemical sensor on the hierarchically porous Cu-BTC MOF platform for glyphosate determination | |
| Tan et al. | Electrochemical sensor based on molecularly imprinted polymer reduced graphene oxide and gold nanoparticles modified electrode for detection of carbofuran | |
| CN101458223B (en) | Preparation of quantitative rapid detecting sensor of microcapsule algae toxin and applications | |
| CN103926294B (en) | Preparation and application of CS/IL-GR modified bovine serum albumin molecular imprinting electrode | |
| CN103940867B (en) | A kind of preparation method of the photoelectricity aptamer sensor for detecting 17 beta estradiols | |
| CN108445057A (en) | A kind of preparation and analysis method for detecting the electrochemical sensor of heavy metal ion | |
| CN107179348B (en) | A kind of double-template trace electrochemical sensor and its preparation method and application | |
| CN102636537A (en) | Enzyme-free methyl parathion detection sensor, and preparation and application methods thereof | |
| CN102435656A (en) | Sensor array and method for quickly detecting soil nitrate nitrogen | |
| CN107449815A (en) | It is a kind of available for the electric potential type microelectrode sensors of Single cell analysis and its application | |
| CN106556638B (en) | One kind being based on MnO2The electrochemical sensor and the preparation method and application thereof of@Ag core-shell type nano material | |
| CN105806915B (en) | A kind of nutrient solution potassium, Na ion concentration detector and detection method | |
| CN103421878A (en) | Preparation of polyphenol oxidase biosensor and detection of polyphenol oxidase biosensor to pesticide residues | |
| CN101750442B (en) | Monodispersive bimetal Au/Pt nano-particle modified electrode for detecting mercury in water and preparation method thereof | |
| CN102654476A (en) | Lead-ion-selective electrode with self-repairing function and preparation method thereof | |
| CN107121484B (en) | A kind of electrochemical method of Sensitive Detection glyphosate | |
| CN108776160A (en) | Method that is a kind of while detecting bisphenol-A and bisphenol S | |
| Liu et al. | Sensitive determination of pesticide imidacloprid using a glassy carbon electrode modified with a film composed of multi-walled carbon nanotubes and poly (aspartic acid) | |
| CN103454327B (en) | P3MT/N-GE modified glassy carbon electrode and the application in detection pesticide phoxim | |
| CN101532987B (en) | Method for measuring chlorotoluron content | |
| CN109752417B (en) | Method for detecting diethyl chlorophosphonate gas and/or sarin poison gas based on charge transfer compound | |
| CN105223260B (en) | Electrochemical sensor of trace quick detection butyl p-hydroxybenzoate and preparation method thereof | |
| Zhao et al. | Synthesis and characterization of a single-walled carbon nanotubes/l-cysteine/Nafion-ionic liquid nanocomposite and its application in the ultrasensitive determination of Cd (II) and Pb (II) | |
| Xu et al. | The electrochemical oxidation of pentachlorophenol and its sensitive determination at chitosan modified carbon paste 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 |