CN109374707A - A method of with carboxylated carbon nanosheet@carboxylated graphene composite film electrochemical sensor trace fluoride worm nitrile - Google Patents
A method of with carboxylated carbon nanosheet@carboxylated graphene composite film electrochemical sensor trace fluoride worm nitrile Download PDFInfo
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- CN109374707A CN109374707A CN201811365038.3A CN201811365038A CN109374707A CN 109374707 A CN109374707 A CN 109374707A CN 201811365038 A CN201811365038 A CN 201811365038A CN 109374707 A CN109374707 A CN 109374707A
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Abstract
The present invention relates to a kind of methods with carboxylated carbon nanosheet@carboxylated graphene composite film electrochemical sensor trace fluoride worm nitrile.The present invention uses carboxylated carbon nanosheet@carboxylated graphene composite film modified glassy carbon electrode, and constructed sensor is used for the direct measurement of Fipronil.When Fipronil is in 10.0nM~700.0nM concentration range, the concentration of electrochemical signals response and Fipronil is in good linear relationship, and method detection is limited to 3.7nM.Invention significantly improves the sensitivity of Fipronil detection, and the detection of low-concentration fipronil nitrile is easy to automate.
Description
Technical field
The invention belongs to new function materials, electrochemical sensing detection technique field, are related to a kind of detection trace Fipronil
Method, especially it is a kind of use carboxylated carbon nanosheet@carboxylated graphene composite film electrochemical sensor trace fluoride worm
The method of nitrile.
Background technique
Fipronil (fipronil) also known as Frontline, chemical name (R, S) -5- amino -1- (2,6- bis- chloro- a, a, a-
Trifluoro-p-tolyl) -4- trifluoromethyl sulfinyl pyrazole -3- nitrile was French rhone-poulenc agro-chemical companies in 1987
The phenyl pyrazoles novel high-activity insecticide developed.Effective drug spectrum is wide, has stomach poison function to pest, has concurrently and tag
With certain systemic action, there is very high kill to important pests such as aphid, leafhopper, plant hopper, lepidopterous larvae, flies and coleopteras
Worm activity, and to crop nonhazardous.But since Fipronil is easy to develop drug resistance, residual and ecological risk are many national by it
It is classified as forbidden drugs.
Some researches show that Fipronil may be enriched with accumulation in human body after long-term use, cause slow poisoning or even cancer
Become, security risk is caused to human health.Currently, some developed countries remain the Fipronil highest of poultry and aquatic products
Limitation is made that strict regulations, and China forbids using Fipronil in poultry and aquatic products.Therefore, it finds a kind of quick and easy, high
The method of sensitive, low detection limits detection trace Fipronil is of great significance.
The analysis method for measuring Fipronil in various complex matrices at present mainly has high performance liquid chromatography (HPLC), liquid phase
Chromatography-tandem mass spectrometry (LC-MS-MS) etc. needs large-scale high although these methods have very high sensitivity and accuracy
The Sample Purification on Single preparation procedure of expensive instrument and equipment and complexity, analysis program is complicated, and detection cycle is long, and testing cost is high, and
It is higher to detection technique level requirement, need technical professional to complete, it is big to popularize difficulty in grass-roots unit, it is difficult to
Overall monitor is carried out to the cultivation, processing, intermediate links of poultry and aquatic products.Therefore, development it is easy, quickly, it is economical, be suitable for
The method of on-site test will be one of the effective way for solving current Fipronil residual excessive problem.
Electrochemical sensor is a kind of sensor based on principle of electrochemical reaction come examination target object, it using electrode as
Sensor conversion element modifies material on the electrode as sensing element, the lewis' acid of sensing element and measured matter
It contacts and chemical reaction or variation occurs, conversion element is by this reaction or changes the direct or indirect electric signal that is converted into, and establishes
The relationship of the chemical quantities such as concentration, the ingredient of subject matter and output electric signal, to realize the device of the quantitative detection of subject matter.Electricity
Chemical sensor due to its with high sensitivity, selectivity it is good, easy to operate, detection quickly, easily micromation, can be in complication system
In monitor on-line the even superiority such as in-vivo analysis, oneself becomes research field very active in Electroanalytical Chemistry, and
Clinical examination, food and drugs analysis, environmental monitoring, in terms of be widely used.
The advantages of carboxylated grapheme material has high-specific surface area, is easy to save and improves electric conductivity, energy and electrode material
Covalent bond is more preferably scattered in solvent.Carbon nanosheet is due to also having abundant surface and superior electrical conductivity, and different occasions
Two-dimensional Carbon nanostructured morphologies are also had with different requirements, also shows that its significant application value in many fields.But
By carboxylated graphene, there is not been reported with carboxylated carbon nanosheet Application of composite.
Summary of the invention
To solve the deficiencies in the prior art, the invention reside in provide a kind of carboxylated carbon nanosheet@carboxylated graphene
The method of composite membrane electrochemical sensor trace fluoride worm nitrile, this method utilize carboxylated carbon nanosheet and carboxylated graphene
Double enlarge-effects, can be used to detect trace Fipronil in high sensitivity.
It is of the present invention to detect Trace Fluoride with carboxylated carbon nanosheet@carboxylated graphene composite film electrochemical sensor
The method of worm nitrile, comprising the following steps:
A. the processing of glass-carbon electrode:
0.05 μm of gama-alumina of glass-carbon electrode (Φ=3mm) is polished, after secondary water ultrasonic cleaning, is dried at room temperature
It is spare；
B. carboxylated graphene modified electrode is constructed:
It takes a certain amount of carboxylated graphene dispersion drop-coated in electrode surface, is placed in infrared lamp according to lower drying to get carboxylic
Base graphite alkene modified electrode；
C. carboxylated carbon nanosheet modified electrode is constructed:
It takes a certain amount of ultrasonic electrolytic process to obtain carboxylated carbon nanosheet and is applied to electrode surface, be placed in infrared lamp according to lower dry
It is dry to get carboxylated carbon nanosheet modified electrode；
D. carboxylated carbon nanosheet@carboxylated graphene composite film modified electrode is constructed:
A certain amount of carboxylated graphene is pipetted respectively and carboxylated carbon nanosheet is applied to electrode surface, is placed in infrared lamp photograph
Lower drying is to get carboxylated carbon nanosheet@carboxylated graphene composite film modified electrode；
E. the building of electrochemical sensor:
Carboxylated carbon nanosheet@carboxylated graphene composite film modified electrode is placed in certain density PBS buffer solution
Middle to make its stabilization using Differential Pulse Voltammetry scanning, potential region when scanning is 0.7V~1.2V, between twice sweep between
Every 1min.Constant potential enrichment is then carried out under 1000rpm magnetic agitation, potential region is -0.4V~-0.7V, enrichment time
0-40min。
F. the detection of Fipronil:
Electro-chemical test uses three-electrode system: working electrode is carboxylated carbon nanosheet@carboxylated graphene composite film
Complex film modified electrode is hollow stud to electrode, and reference electrode is saturated calomel electrode.Electro-chemical test is in self-control electrolytic cell
Middle progress.Make by oneself electrolytic cell volume be 25mL, every time test when load electrolyte product be 20mL, using magnetic stirrer into
Row stirring.Electrolyte is PBS buffer solution, and high pure nitrogen 3min is passed through before use sufficiently to eliminate dissolved oxygen therein.
The further feature of electrochemical sensor according to the present invention, in the step D, carboxylated carbon nanosheet and
The dosage of carboxylated graphene is respectively 2 μ L and 2 μ L.
The further feature of electrochemical sensor according to the present invention, it is molten in the electrolytic cell in the step E
Liquid is adjusted to pH=8.0.
The further feature of electrochemical sensor according to the present invention, it is molten in the electrolytic cell in the step E
The concentration of liquid buffer solution PBS is 0.2M.
The further feature of electrochemical sensor according to the present invention, in the step E, the accumulating potential is
0.3V。
The further feature of electrochemical sensor according to the present invention, in the step E, the enrichment time is
5min。
Electrochemical sensor of the present invention for detecting trace Fipronil overcomes prior art in detection fluorine worm
It is excessively cumbersome that there are methods when nitrile, and the shortcomings such as step complexity preferably improve the sensitivity of detection, for Trace Fluoride worm
The detection of nitrile is easy to automate.
Detailed description of the invention
Fig. 1 is the differentiated pulse volt-ampere curve of Different electrodes, and in figure, (a) bare electrode, (b) carboxylated carbon nanosheet is modified
Electrode, (c) carboxylated graphene composite film modified electrode, (d)) modification of carboxylated carbon nanosheet@carboxylated graphene composite film
Electrode.
Fig. 2 is sensor standard absorption curve of the present invention.
Fig. 3 is the selective figure of sensor of the present invention.Chaff interferent in figure, on horizontal axis to be added.
Specific embodiment
Embodiment 1: of the present invention for detecting constructing for the electrochemical sensor of micro Fipronil
A kind of side with carboxylated carbon nanosheet carboxylated graphene composite film electrochemical sensor detection trace Fipronil
Method, which comprises the following steps:
(1) processing of glass-carbon electrode:
0.05 μm of gama-alumina of glass-carbon electrode (Φ=3mm) is polished, after secondary water ultrasonic cleaning, is dried at room temperature
It is spare；
(2) carboxylated graphene modified electrode is constructed:
It takes a certain amount of carboxylated graphene dispersion drop-coated in electrode surface, is placed in infrared lamp according to lower drying to get carboxylic
Base graphite alkene modified electrode；
(3) carboxylated carbon nanosheet modified electrode is constructed:
It takes a certain amount of ultrasonic electrolytic process to obtain carboxylated carbon nanosheet and is applied to electrode surface, be placed in infrared lamp according to lower dry
It is dry to get carboxylated carbon nanosheet modified electrode；
(4) carboxylated carbon nanosheet@carboxylated graphene composite film modified electrode is constructed:
A certain amount of carboxylated graphene is pipetted respectively and carboxylated carbon nanosheet is applied to electrode surface, is placed in infrared lamp photograph
Lower drying is to get carboxylated carbon nanosheet@carboxylated graphene composite film modified electrode；
(5) building of electrochemical sensor:
Carboxylated carbon nanosheet@carboxylated graphene composite film modified electrode is placed in certain density PBS buffer solution
Middle to make its stabilization using Differential Pulse Voltammetry scanning, potential region when scanning is 0.7V~1.2V, between twice sweep between
Every 1min.Constant potential enrichment is then carried out under 1000rpm magnetic agitation, potential region is -0.4V~-0.7V, enrichment time
0-40min。
(6) detection of Fipronil:
Electro-chemical test uses three-electrode system: working electrode is carboxylated carbon nanosheet@carboxylated graphene composite film
Complex film modified electrode is hollow stud to electrode, and reference electrode is saturated calomel electrode.Electro-chemical test is in self-control electrolytic cell
Middle progress.Make by oneself electrolytic cell volume be 25mL, every time test when load electrolyte product be 20mL, using magnetic stirrer into
Row stirring.Electrolyte is PBS buffer solution, and high pure nitrogen 3min is passed through before use sufficiently to eliminate dissolved oxygen therein.
Embodiment 2: the electrochemical sensor differentiated pulse volt-ampere characterization of the present invention for detecting trace Fipronil
Using Differential Pulse Voltammetry observation Fipronil in bare electrode (a), carboxylated graphene (b), carboxylated carbon nanometer
Electrochemical reaction on piece (c) and carboxylated carbon nanosheet@carboxylated graphene (d) modified electrode.As shown in Figure 1, naked
On electrode, the peak current of 2 μM of Fipronil ethanol solution is 0.3307 μ A, and after carboxylated graphene modified electrode, entirely without
Oxidation, reduction peak generate.In carboxylated carbon nanosheet, (under modification, up to 3.486 μ A are caused, 10 times of peak current increases peak current
Width.And under equal conditions, it uses instead under carboxylated carbon nanosheet@carboxylated graphene modified, peak current is reachable to cause 6.611 μ A,
Opposite bare electrode has 20 times of amplification.
Embodiment 3: the range of linearity and detection limit are tested
Based on carboxylated carbon nanosheet@carboxylated graphene (d) modified electrode to the extremely strong electro-catalysis of Fipronil electroreduction
Effect can establish the hypersensitive electrochemical detection method of Fipronil.When Fipronil is in 10nM~700.0nM concentration range,
The concentration of electrochemical signals response and Fipronil is in good linear relationship (referring to fig. 2), and equation of linear regression is I (μ A)
=-0.0218C (nM)+2.1439, R=0.9992, detection are limited to 3.7nM.Invention significantly improves the spirits of Fipronil detection
Sensitivity is easy to automate for the detection of low-concentration fipronil nitrile.
Embodiment 4: the influence of chaff interferent
Selectivity tests this experiment by comparing sensor peak current ratio (I/I0) interference experiment is carried out, as shown in figure 3, working as
When Fipronil concentration is 50nM, the glucose of 100 times of concentration, ascorbic acid, riboflavin, Nitenpyram, Diacloden, acetic acid dimension life
The chaff interferents such as plain A, thiamine hydrochloride are noiseless to it.
Embodiment 5: actual sample measurement
After treatment by actual sample, its extracting solution is taken, electrochemical gaging is carried out, measurement result is shown in Table 1.It can by table 1
The rate of recovery of perception method is 89.75%~105.38%, relative standard deviation 9.87-4.23%.
Table 1: actual sample mark-on testing result (n=5)
Claims (6)
1. a kind of side with carboxylated carbon nanosheet carboxylated graphene composite film electrochemical sensor detection trace Fipronil
Method, which comprises the following steps:
A. the processing of glass-carbon electrode:
0.05 μm of gama-alumina of glass-carbon electrode (Φ=3mm) is polished, after secondary water ultrasonic cleaning, is dried at room temperature spare；
B. carboxylated graphene modified electrode is constructed:
It takes a certain amount of carboxylated graphene dispersion drop-coated in electrode surface, is placed in infrared lamp according to lower drying to get carboxylated
Graphene modified electrode；
C. carboxylated carbon nanosheet modified electrode is constructed:
It takes a certain amount of ultrasonic electrolytic process to obtain carboxylated carbon nanosheet and is applied to electrode surface, be placed in infrared lamp according to lower drying, i.e.,
Obtain carboxylated carbon nanosheet modified electrode；
D. carboxylated carbon nanosheet@carboxylated graphene composite film modified electrode is constructed:
A certain amount of carboxylated graphene is pipetted respectively and carboxylated carbon nanosheet is applied to electrode surface, is placed in infrared lamp according to lower dry
It is dry to get carboxylated carbon nanosheet@carboxylated graphene composite film modified electrode；
E. the building of electrochemical sensor:
Carboxylated carbon nanosheet@carboxylated graphene composite film modified electrode, which is placed in certain density PBS buffer solution, to be made
Make its stabilization with Differential Pulse Voltammetry scanning, potential region when scanning is 0.7V~1.2V, is spaced between twice sweep
1min；Constant potential enrichment is then carried out under 1000rpm magnetic agitation, potential region is -0.4V~-0.7V, enrichment time 0-
40min；
F. the detection of Fipronil:
Electro-chemical test uses three-electrode system: working electrode is compound for carboxylated carbon nanosheet@carboxylated graphene composite film
Film modified electrode is hollow stud to electrode, and reference electrode is saturated calomel electrode；Electro-chemical test self-control electrolytic cell in into
Row；The volume for making electrolytic cell by oneself is 25mL, and loading electrolyte product when test every time is 20mL, is stirred using magnetic stirrer
It mixes；Electrolyte is PBS buffer solution, and high pure nitrogen 3min is passed through before use sufficiently to eliminate dissolved oxygen therein.
2. according to the method described in claim 1, it is characterized by: in the step D, the dosage of the carboxylated carbon nanosheet
For 2 μ L, the dosage of the carboxylated graphene is 2 μ L.
3. according to the method described in claim 1, it is characterized by: the solution in the electrolytic cell is conditioned in the step E
For pH=8.0.
4. according to the method described in claim 1, it is characterized by: the solution buffering in the electrolytic cell is molten in the step E
The concentration of liquid PBS is 0.2M.
5. according to the method described in claim 1, it is characterized by: the accumulating potential is 0.3V in the step E.
6. according to the method described in claim 1, it is characterized by: the enrichment time is 5min in the step E.
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| CN201811365038.3A CN109374707A (en) | 2018-11-16 | 2018-11-16 | A method of with carboxylated carbon nanosheet@carboxylated graphene composite film electrochemical sensor trace fluoride worm nitrile |
| JP2019167939A JP2020085890A (en) | 2018-11-16 | 2019-09-17 | Method of measuring trace amount of fipronil using electrochemical sensor by carboxy nanosheet @ carboxylated graphite composite film |
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| CN201811365038.3A CN109374707A (en) | 2018-11-16 | 2018-11-16 | A method of with carboxylated carbon nanosheet@carboxylated graphene composite film electrochemical sensor trace fluoride worm nitrile |
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| CN110988075A (en) * | 2019-12-20 | 2020-04-10 | 肇庆学院 | Aminated multi-walled carbon nanotube electrochemical sensor and application thereof in detecting quercetin |
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| US8623196B2 (en) * | 2007-05-16 | 2014-01-07 | Michigan State University | Nanostructured biosensor containing neuropathy target esterase activity |
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| CN103616457A (en) * | 2013-12-12 | 2014-03-05 | 青岛理工大学 | Method of detecting flusilazole, fipronil, chlorfenapyr and fenpyroximate in environmental water sample |
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| CN102288669A (en) * | 2011-05-04 | 2011-12-21 | 青岛大学 | Electrochemical method based on graphene-modified electrode for simultaneous determination of rutin and quercetin |
| CN106018532A (en) * | 2016-06-13 | 2016-10-12 | 山东省科学院新材料研究所 | Preparation of graphene oxide and phytate modified electrode and electrochemical detection device assembled by graphene oxide and phytate modified electrode |
| CN106442672A (en) * | 2016-09-19 | 2017-02-22 | 盐城工学院 | Sulfate ion inhibition type electrochemical biosensor and preparation method thereof |
Non-Patent Citations (3)
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| JIANG, HONGMEI ET AL.: "Graphene-like carbon nanosheets as a new electrode material for electrochemical determination of hydroquinone and catechol", 《TALANTA》 * |
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| MONTES, RODRIGO H. O. ET AL.: "Amperometric determination of the insecticide fipronil using batch injection analysis: comparison between unmodified and carbon-nanotube-modified electrodes", 《JOURNAL OF SOLID STATE ELECTROCHEMISTRY》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110988075A (en) * | 2019-12-20 | 2020-04-10 | 肇庆学院 | Aminated multi-walled carbon nanotube electrochemical sensor and application thereof in detecting quercetin |
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Application publication date: 20190222 |