CN107328831A - A kind of preparation method of the residues of organophosphate pesticides detection sensor based on copper/cupric oxide nano line - Google Patents
A kind of preparation method of the residues of organophosphate pesticides detection sensor based on copper/cupric oxide nano line Download PDFInfo
- Publication number
- CN107328831A CN107328831A CN201710315045.1A CN201710315045A CN107328831A CN 107328831 A CN107328831 A CN 107328831A CN 201710315045 A CN201710315045 A CN 201710315045A CN 107328831 A CN107328831 A CN 107328831A
- Authority
- CN
- China
- Prior art keywords
- cupric oxide
- copper
- electrode
- oxide nano
- wire
- 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.)
- Pending
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
Abstract
The invention discloses a kind of preparation method of the residues of organophosphate pesticides detection sensor based on copper/cupric oxide nano line, this method comprises the following steps：(1) copper nano-wire is synthesized；(2) high-temperature calcination prepares cupric oxide nano line；(3) copper nano-wire/graphene/chitosan complexes are prepared；(4) cupric oxide nano line/single-wall carbon nanotube composite is prepared；(5) modified electrode is prepared；(6) Electrochemical Detection residues of organophosphate pesticides content；Utilize the good catalytic performance of Cu/CuO nano materials and superior sensing capabilities, there is special compatibility to sulfur alcohol compound and there is single-minded detection to organophosphorus pesticide, and Cu/CuO costs of material are low, simple and easy to get, detection method is quick, sensitive, convenient；More simplify the step of electrode surface in addition, chitosan good filming causes composite to be modified, substantially reduce the preparation cost of electrode；Organophosphorus pesticide is effectively adsorbed in electrode material surface by single-walled carbon nanotube, is formed one layer of barrier and is hindered electron transmission to realize the detection to agricultural chemicals.
Description
Technical field
The invention belongs to technical field of food detection, and in particular to a kind of organophosphor agriculture based on copper/cupric oxide nano line
The preparation method of residual detection sensor.
Background technology
Agricultural chemicals is widely used in agricultural production with eliminating corps diseases, but it is in environment, water, crops, food
Residual in product endangers the healthy of the mankind, the problems such as having triggered serious ecology, environment, food security.Current China
The use of most common agricultural chemical insecticide is Organophosphorus and carbamate pesticides class agricultural chemicals, once into human body, cholinester will be produced
The suppressed side effect of enzymatic activity, causes a large amount of accumulations of substrate acetyl choline on nerve synapse, and then destroy nerve impulse
Normal conduction, it is even lethal when serious, great threat is caused to human health, it is sanitary inspection field to study its detection method
Study hotspot.The conventional detection method of these residues of pesticides is gas phase, liquid chromatography, mass spectrography and spectral method etc., generally
Time-consuming, cost high, it is difficult to the need for meeting field quick detection.Therefore, it is badly in need of research some are quick, sensitive, easily examine
Survey method, the agricultural product of high residues of pesticides are blocked in outside market, to prevent the generation of food security accident.
In recent years, electrochemical analysis techniques are also increasing day by day applied to the research of Detecting Pesticide.Report at present
The residual detection electrochemical sensor of agriculture mainly has enzyme type and the major class of non-enzyme type two, though the development of enzyme type agriculture residual electrochemical sensor compared with earlier than
Non-enzyme type, but its popularization and application still receive poor enzyme self stability, it is severe reaction conditions, whard to control and expensive etc.
The limitation of shortcoming.Based on the reason for such, the development of the residual electrochemical sensor of non-enzyme type agriculture is gradually of concern.
Lot of documents report is related to various metal/metal oxides, metal/metal oxide-carbon nanotube composite
Material, bimetal nano material etc. are applied to the research of the residual detection sensor of agriculture, and these research majorities concentrate on the noble metals such as Ag, Au
Or ZrO2On the metal oxide cumbersome etc. preparation method, there is low, the simple and easy to get gold of suitable performance, cost for other
The research of category/metal oxide is less.
The content of the invention
It is an object of the invention to provide a kind of system of the residues of organophosphate pesticides detection sensor based on copper/cupric oxide nano line
Preparation Method, using the good catalytic performance of Cu/CuO nano materials and superior sensing capabilities, has spy to sulfur alcohol compound
Different compatibility, the detection for phosphorus sulphur organophosphorus residues of pesticides provides technique direction.
A kind of preparation method of the residues of organophosphate pesticides detection sensor based on copper/cupric oxide nano line, this method is included such as
Lower step：
(1) synthesis of copper nano-wire：20mL concentration is first preheated to 60 DEG C for 15mol/L NaOH solution, sequentially added
1mL concentration is 0.1mol/l Cu (NO3)2, 0.16mL ethylenediamines (EDA), 25uL concentration is 35wt% N2H4Solution, and hold
Continuous stirring 2h obtains the bright red product of cake shape and flown in solution；Then wash above-mentioned red with ultra-pure water, absolute ethyl alcohol successively
Color product, Centrifugal dispersion is handled 3-5 times, removes inorganic ions and water soluble compound and the EDA and N of residual2H4；Finally use
Dry Cu nano wire powder after ultra-pure water ultrasonic disperse；
(2) preparation of cupric oxide nano line：By red Cu nano wire powder in step (1) it is vacuum dried after be contained in tin
In foil paper, it is put into Muffle furnace, cools down black after 400 DEG C, high-temperature calcination 5-8h are warming up to by 20-40 DEG C/min of programming rate
Color CuO nano wire powder；
(3) preparation of copper nano-wire/graphene/chitosan complexes：Red Cu nano wire powder in step (1) is dissolved in
The nanowire suspended liquid of Cu that concentration is 2mg/ml is made in absolute ethyl alcohol, 10mg graphene powder ultrasonic disperses are weighed dense in 5mL
Spend in the chitosan solution for 0.05wt% and obtain 2mg/ml graphene dispersing solution, by the nanowire suspended liquid of Cu and graphene dispersion
Liquid is according to volume ratio 1:0.5-2 is mixed, and ultrasonically treated 30-60min is well mixed it, obtains copper nano-wire/graphene/chitosan
Compound dispersion liquid；
(4) preparation of cupric oxide nano line/single-wall carbon nanotube composite：By black CuO nano wire powder in step (2)
The nanowire suspended liquid of CuO for being made that concentration is 2mg/ml in absolute ethyl alcohol is dissolved in, 4-6mg single-walled carbon nanotube powder ultrasonics are weighed
It is scattered in the single-walled carbon nanotube point that 0.4-0.6mg/ml is obtained in the sodium dodecyl sulfate solution that 10mL concentration is 0.05wt%
Dispersion liquid, by the nanowire suspended liquid of CuO and single-walled carbon nanotube dispersion liquid according to volume ratio 1:0.4-2 is mixed, ultrasonically treated 30-
60min is well mixed it, obtains cupric oxide nano line/single-wall carbon nanotube composite dispersion liquid；
(5) preparation of modified electrode：Glass-carbon electrode is processed by shot blasting, cleaned and is dried, the copper nano-wire/stone is taken
Black alkene/chitosan complexes dispersion liquid or cupric oxide nano line/single-wall carbon nanotube composite dispersant liquid drop are added to after processing
It is multiple after producing copper nano-wire/graphene/chitosan after the drying of electrode surface solution evaporation under glassy carbon electrode surface, room temperature condition
Compound modified electrode or cupric oxide nano line/single-wall carbon nanotube composite modified electrode；
(6) Electrochemical Detection residues of organophosphate pesticides content：Using modified electrode in step (5) as working electrode, Ag/AgCl makees
For reference electrode, platinum electrode is as to electrode, and it is 0.1mol/l's that 5mL concentration is added dropwise into electrochemical reaction cell at room temperature
Disodium hydrogen phosphate-citric acid solution is measured as electrolyte, and residues of organophosphate pesticides is detected.
Described copper nano-wire/graphene/chitosan complexes are overhead fine and close network structure.
Described cupric oxide nano line/single-wall carbon nanotube composite is the cellular network structure mutually wound.
Described copper nano-wire/graphene/chitosan complexes modified electrode is to methyl in the residual organophosphor of the agriculture to sulphur
The dynamic detection range of phosphorus is 0.1-10ppm, and detection sensitivity is 471.0 μ Acm-2·ppm-1。
It is preferred that, described copper nano-wire/graphene/chitosan complexes modified electrode is to the residual organophosphor methyl of the agriculture
The dynamic detection range of parathion is 0.2-5ppm, and the dynamic detection range is linear detection range.
Described cupric oxide nano line/single-wall carbon nanotube composite modified electrode is to horse traction sulphur in the residual organophosphor of the agriculture
The detection range of linearity of phosphorus is 180-200ppb, and detection sensitivity is 628.51 μ Acm-2·ppb-1, test limit is as little as
0.1ppb。
The invention has the advantages that：
The present invention utilizes the good catalytic performance of Cu/CuO nano materials and superior sensing capabilities, to sulfur alcohol compound
There is single-minded detection with special compatibility and phosphorus sulphur organophosphorus residues of pesticides；And Cu/CuO costs of material it is low,
Simple and easy to get, detection method is quick, sensitive, convenient；In addition, in terms of modified electrode preparation, chitosan good filming is caused
Composite is modified more to be simplified the step of electrode surface, substantially reduces the preparation cost of electrode；Single-walled carbon nanotube it is many
Organophosphorus pesticide malathion is effectively adsorbed in electrode material surface by mesh network structure, is formed one layer of barrier and is hindered electricity
Son transmission, the detection to agricultural chemicals is realized by the combination of organophosphorus pesticide and modified electrode.
Embodiment
Following examples are used to illustrate the present invention, but are not limited to the scope of the present invention.
The preparation of 1 copper nano-wire of embodiment/graphene/chitosan complexes modified electrode and the dynamic of parathion-methyl
Detection.
A kind of preparation method of the residues of organophosphate pesticides detection sensor based on copper/cupric oxide nano line, this method is included such as
Lower step：
(1) 20mL concentration is first preheated to 60 DEG C for 15mol/L NaOH solution, sequentially adds 1mL concentration for 0.1mol/
L Cu (NO3)2, 0.16mL ethylenediamines (EDA), 25uL concentration is 35wt% N2H4Solution, and continue stirring 2h obtain cake shape
Bright red product is flown in solution；Then washed successively with ultra-pure water, absolute ethyl alcohol at above-mentioned red product, Centrifugal dispersion
Reason 3 times, removes inorganic ions and water soluble compound and the EDA and N of residual2H4；Finally dried with after ultra-pure water ultrasonic disperse
Obtain Cu nano wire powder；
(2) red Cu nano wire powder in step (1) is dissolved in and the Cu nanometers that concentration is 2mg/ml is made in absolute ethyl alcohol
Line suspension, weighs 10mg graphene powders ultrasonic disperse and obtains 2mg/ml in 5mL concentration is 0.05wt% chitosan solution
Graphene dispersing solution, by the nanowire suspended liquid of Cu and graphene dispersing solution according to volume ratio 1:0.5 mixing, it is ultrasonically treated
30min is well mixed it, obtains copper nano-wire/graphene/chitosan complexes dispersion liquid of overhead fine and close network structure；
(3) glass-carbon electrode is processed by shot blasting, cleaned and dried, take the copper nano-wire/graphene/chitosan to be combined
Thing dispersant liquid drop is added under the glassy carbon electrode surface after processing, room temperature condition, and copper is produced after electrode surface solution evaporation is dried
Nano wire/graphene/chitosan complexes modified electrode；
(4) using copper nano-wire/graphene/chitosan complexes modified electrode as working electrode, Ag/AgCl is used as reference
The phosphoric acid hydrogen that 5mL concentration is 0.1mol/l is added dropwise as to electrode in electrode, platinum electrode into electrochemical reaction cell at room temperature
Disodium-citric acid solution is measured as electrolyte, to the dynamic detection range of parathion-methyl in the residual organophosphor of agriculture
For 0.1-10ppm, detection sensitivity is 471.0 μ Acm-2·ppm-1。
The preparation of 2 copper nano-wires of embodiment/graphene/chitosan complexes modified electrode and the dynamic of parathion-methyl
Detection.
A kind of preparation method of the residues of organophosphate pesticides detection sensor based on copper/cupric oxide nano line, this method is included such as
Lower step：
(1) 20mL concentration is first preheated to 60 DEG C for 15mol/L NaOH solution, sequentially adds 1mL concentration for 0.1mol/
L Cu (NO3)2, 0.16mL ethylenediamines (EDA), 25uL concentration is 35wt% N2H4Solution, and continue stirring 2h obtain cake shape
Bright red product is flown in solution；Then washed successively with ultra-pure water, absolute ethyl alcohol at above-mentioned red product, Centrifugal dispersion
Reason 5 times, removes inorganic ions and water soluble compound and the EDA and N of residual2H4；Finally dried with after ultra-pure water ultrasonic disperse
Obtain Cu nano wire powder；
(2) red Cu nano wire powder in step (1) is dissolved in and the Cu nanometers that concentration is 2mg/ml is made in absolute ethyl alcohol
Line suspension, weighs 10mg graphene powders ultrasonic disperse and obtains 2mg/ml in 5mL concentration is 0.05wt% chitosan solution
Graphene dispersing solution, by the nanowire suspended liquid of Cu and graphene dispersing solution according to volume ratio 1:2 mixing, ultrasonically treated 60min
It is well mixed, copper nano-wire/graphene/chitosan complexes dispersion liquid of overhead fine and close network structure is obtained；
(3) glass-carbon electrode is processed by shot blasting, cleaned and dried, take the copper nano-wire/graphene/chitosan to be combined
Thing dispersant liquid drop is added under the glassy carbon electrode surface after processing, room temperature condition, and copper is produced after electrode surface solution evaporation is dried
Nano wire/graphene/chitosan complexes modified electrode；
(4) using copper nano-wire/graphene/chitosan complexes modified electrode as working electrode, Ag/AgCl is used as reference
The phosphoric acid hydrogen that 5mL concentration is 0.1mol/l is added dropwise as to electrode in electrode, platinum electrode into electrochemical reaction cell at room temperature
Disodium-citric acid solution is measured as electrolyte, to the dynamic detection range of parathion-methyl in the residual organophosphor of agriculture
For 0.1-5ppm, detection sensitivity is 471.0 μ Acm-2·ppm-1。
The preparation of 3 copper nano-wires of embodiment/graphene/chitosan complexes modified electrode and the dynamic of parathion-methyl
Detection.
A kind of preparation method of the residues of organophosphate pesticides detection sensor based on copper/cupric oxide nano line, this method is included such as
Lower step：
(1) 20mL concentration is first preheated to 60 DEG C for 15mol/L NaOH solution, sequentially adds 1mL concentration for 0.1mol/
L Cu (NO3)2, 0.16mL ethylenediamines (EDA), 25uL concentration is 35wt% N2H4Solution, and continue stirring 2h obtain cake shape
Bright red product is flown in solution；Then washed successively with ultra-pure water, absolute ethyl alcohol at above-mentioned red product, Centrifugal dispersion
Reason 4 times, removes inorganic ions and water soluble compound and the EDA and N of residual2H4；Finally dried with after ultra-pure water ultrasonic disperse
Obtain Cu nano wire powder；
(2) red Cu nano wire powder in step (1) is dissolved in and the Cu nanometers that concentration is 2mg/ml is made in absolute ethyl alcohol
Line suspension, weighs 10mg graphene powders ultrasonic disperse and obtains 2mg/ml in 5mL concentration is 0.05wt% chitosan solution
Graphene dispersing solution, by the nanowire suspended liquid of Cu and graphene dispersing solution according to volume ratio 1:1 mixing, ultrasonically treated 45min
It is well mixed, copper nano-wire/graphene/chitosan complexes dispersion liquid of overhead fine and close network structure is obtained；
(3) glass-carbon electrode is processed by shot blasting, cleaned and dried, take the copper nano-wire/graphene/chitosan to be combined
Thing dispersant liquid drop is added under the glassy carbon electrode surface after processing, room temperature condition, and copper is produced after electrode surface solution evaporation is dried
Nano wire/graphene/chitosan complexes modified electrode；
(4) using copper nano-wire/graphene/chitosan complexes modified electrode as working electrode, Ag/AgCl is used as reference
The phosphoric acid hydrogen that 5mL concentration is 0.1mol/l is added dropwise as to electrode in electrode, platinum electrode into electrochemical reaction cell at room temperature
Disodium-citric acid solution is measured as electrolyte, to the dynamic detection range of parathion-methyl in the residual organophosphor of agriculture
For 0.1-8ppm, detection sensitivity is 471.0 μ Acm-2·ppm-1。
The preparation of the cupric oxide nano line of embodiment 4/single-wall carbon nanotube composite modified electrode and residues of organophosphate pesticides horse
Draw the dynamic detection of sulphur phosphorus.
A kind of preparation method of the residues of organophosphate pesticides detection sensor based on copper/cupric oxide nano line, this method is included such as
Lower step：
(1) 20mL concentration is first preheated to 60 DEG C for 15mol/L NaOH solution, sequentially adds 1mL concentration for 0.1mol/
L Cu (NO3)2, 0.16mL ethylenediamines (EDA), 25uL concentration is 35wt% N2H4Solution, and continue stirring 2h obtain cake shape
Bright red product is flown in solution；Then washed successively with ultra-pure water, absolute ethyl alcohol at above-mentioned red product, Centrifugal dispersion
Reason 3 times, removes inorganic ions and water soluble compound and the EDA and N of residual2H4；Finally dried with after ultra-pure water ultrasonic disperse
Obtain Cu nano wire powder；
(2) by red Cu nano wire powder in step (1) it is vacuum dried after be contained in masking foil, be put into Muffle furnace
In, it is warming up to by 20 DEG C/min of programming rate after 400 DEG C, high-temperature calcination 5h and cools down to obtain black CuO nano wire powder；
(3) black CuO nano wire powder in step (2) is dissolved in into obtained concentration in absolute ethyl alcohol to receive for 2mg/ml CuO
Rice noodles suspension, weighs 4mg single-walled carbon nanotube powder ultrasonics and is scattered in the dodecyl sodium sulfonate that 10mL concentration is 0.05wt%
0.4mg/ml single-walled carbon nanotube dispersion liquid is obtained in sodium solution, by the nanowire suspended liquid of CuO and single-walled carbon nanotube dispersion liquid
According to volume ratio 1:0.4 mixing, ultrasonically treated 300min is well mixed it, obtains cupric oxide nano line/single-walled carbon nanotube multiple
Compound dispersion liquid；
(4) glass-carbon electrode is processed by shot blasting, cleaned and dried, take cupric oxide nano line/single wall carbon in step (3) to receive
Mitron compound dispersant liquid drop is added under the glassy carbon electrode surface after processing, room temperature condition, treats that electrode surface solution evaporation is dried
Cupric oxide nano line/single-wall carbon nanotube composite modified electrode of the cellular network structure mutually wound is produced afterwards；
(5) so that modified electrode is as working electrode in step (4), Ag/AgCl is as reference electrode, and platinum electrode is as right
Electrode, is added dropwise disodium hydrogen phosphate-citric acid solution that 5mL concentration is 0.1mol/l into electrochemical reaction cell at room temperature
Measured as electrolyte, the detection range of linearity to malathion in residues of organophosphate pesticides is 180-200ppb, is detected sensitive
Spend for 628.51 μ Acm-2·ppb-1, test limit as little as 0.1ppb.
The preparation of the cupric oxide nano line of embodiment 5/single-wall carbon nanotube composite modified electrode and residues of organophosphate pesticides horse
Draw the dynamic detection of sulphur phosphorus.
A kind of preparation method of the residues of organophosphate pesticides detection sensor based on copper/cupric oxide nano line, this method is included such as
Lower step：
(1) 20mL concentration is first preheated to 60 DEG C for 15mol/L NaOH solution, sequentially adds 1mL concentration for 0.1mol/
L Cu (NO3)2, 0.16mL ethylenediamines (EDA), 25uL concentration is 35wt% N2H4Solution, and continue stirring 2h obtain cake shape
Bright red product is flown in solution；Then washed successively with ultra-pure water, absolute ethyl alcohol at above-mentioned red product, Centrifugal dispersion
Reason 5 times, removes inorganic ions and water soluble compound and the EDA and N of residual2H4；Finally dried with after ultra-pure water ultrasonic disperse
Obtain Cu nano wire powder；
(2) by red Cu nano wire powder in step (1) it is vacuum dried after be contained in masking foil, be put into Muffle furnace
In, it is warming up to by 40 DEG C/min of programming rate after 400 DEG C, high-temperature calcination 8h and cools down to obtain black CuO nano wire powder；
(3) black CuO nano wire powder in step (2) is dissolved in into obtained concentration in absolute ethyl alcohol to receive for 2mg/ml CuO
Rice noodles suspension, weighs 6mg single-walled carbon nanotube powder ultrasonics and is scattered in the dodecyl sodium sulfonate that 10mL concentration is 0.05wt%
0.6mg/ml single-walled carbon nanotube dispersion liquid is obtained in sodium solution, by the nanowire suspended liquid of CuO and single-walled carbon nanotube dispersion liquid
According to volume ratio 1:2 mixing, ultrasonically treated 60min is well mixed it, obtains cupric oxide nano line/single-wall carbon nanotube composite
Dispersion liquid；
(4) glass-carbon electrode is processed by shot blasting, cleaned and dried, take cupric oxide nano line/single wall carbon in step (3) to receive
Mitron compound dispersant liquid drop is added under the glassy carbon electrode surface after processing, room temperature condition, treats that electrode surface solution evaporation is dried
Cupric oxide nano line/single-wall carbon nanotube composite modified electrode of the cellular network structure mutually wound is produced afterwards；
(5) so that modified electrode is as working electrode in step (4), Ag/AgCl is as reference electrode, and platinum electrode is as right
Electrode, is added dropwise disodium hydrogen phosphate-citric acid solution that 5mL concentration is 0.1mol/l into electrochemical reaction cell at room temperature
Measured as electrolyte, the detection range of linearity to malathion in residues of organophosphate pesticides is 180-200ppb, is detected sensitive
Spend for 628.51 μ Acm-2·ppb-1, test limit as little as 0.1ppb.
The preparation of the cupric oxide nano line of embodiment 6/single-wall carbon nanotube composite modified electrode and residues of organophosphate pesticides horse
Draw the dynamic detection of sulphur phosphorus.
A kind of preparation method of the residues of organophosphate pesticides detection sensor based on copper/cupric oxide nano line, this method is included such as
Lower step：
(1) 20mL concentration is first preheated to 60 DEG C for 15mol/L NaOH solution, sequentially adds 1mL concentration for 0.1mol/
L Cu (NO3)2, 0.16mL ethylenediamines (EDA), 25uL concentration is 35wt% N2H4Solution, and continue stirring 2h obtain cake shape
Bright red product is flown in solution；Then washed successively with ultra-pure water, absolute ethyl alcohol at above-mentioned red product, Centrifugal dispersion
Reason 3-5 times, removes inorganic ions and water soluble compound and the EDA and N of residual2H4；Finally done with after ultra-pure water ultrasonic disperse
It is dry to obtain Cu nano wire powder；
(2) by red Cu nano wire powder in step (1) it is vacuum dried after be contained in masking foil, be put into Muffle furnace
In, it is warming up to by 30 DEG C/min of programming rate after 400 DEG C, high-temperature calcination 6h and cools down to obtain black CuO nano wire powder；
(3) black CuO nano wire powder in step (2) is dissolved in into obtained concentration in absolute ethyl alcohol to receive for 2mg/ml CuO
Rice noodles suspension, weighs 5mg single-walled carbon nanotube powder ultrasonics and is scattered in the dodecyl sodium sulfonate that 10mL concentration is 0.05wt%
0.5mg/ml single-walled carbon nanotube dispersion liquid is obtained in sodium solution, by the nanowire suspended liquid of CuO and single-walled carbon nanotube dispersion liquid
According to volume ratio 1:1 mixing, ultrasonically treated 40min is well mixed it, obtains cupric oxide nano line/single-wall carbon nanotube composite
Dispersion liquid；
(4) glass-carbon electrode is processed by shot blasting, cleaned and dried, take cupric oxide nano line/single wall carbon in step (3) to receive
Mitron compound dispersant liquid drop is added under the glassy carbon electrode surface after processing, room temperature condition, treats that electrode surface solution evaporation is dried
Cupric oxide nano line/single-wall carbon nanotube composite modified electrode of the cellular network structure mutually wound is produced afterwards；
(5) so that modified electrode is as working electrode in step (4), Ag/AgCl is as reference electrode, and platinum electrode is as right
Electrode, is added dropwise disodium hydrogen phosphate-citric acid solution that 5mL concentration is 0.1mol/l into electrochemical reaction cell at room temperature
Measured as electrolyte, the detection range of linearity to malathion in residues of organophosphate pesticides is 180-200ppb, is detected sensitive
Spend for 628.51 μ Acm-2·ppb-1, test limit as little as 0.1ppb.
Although above with general explanation and specific embodiment, the present invention is described in detail, at this
On the basis of invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Therefore,
These modifications or improvements, belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (6)
1. a kind of preparation method of the residues of organophosphate pesticides detection sensor based on copper/cupric oxide nano line, it is characterised in that the party
Method comprises the following steps：
(1) synthesis of copper nano-wire：20mL concentration is first preheated to 60 DEG C for 15mol/L NaOH solution, 1mL is sequentially added dense
Spend the Cu (NO for 0.1mol/l3)2, 0.16mL ethylenediamines, 25uL concentration is 35wt% N2H4Solution, and continue stirring 2h obtain
The bright red product of cake shape is flown in solution；Then above-mentioned red product is washed with ultra-pure water, absolute ethyl alcohol successively, centrifuged
Decentralized processing 3-5 times, removes inorganic ions and water soluble compound and the ethylenediamine and N of residual2H4；It is finally super with ultra-pure water
Dry Cu nano wire powder after sound is scattered；
(2) preparation of cupric oxide nano line：By red Cu nano wire powder in rapid (1) it is vacuum dried after be contained in tinfoil paper
In paper, it is put into Muffle furnace, black is cooled down to obtain after 400 DEG C, high-temperature calcination 5-8h are warming up to by 20-40 DEG C/min of programming rate
CuO nano wire powder；
(3) preparation of copper nano-wire/graphene/chitosan complexes：Red Cu nano wire powder in the step (1) is dissolved in
The nanowire suspended liquid of Cu that concentration is 2mg/ml is made in absolute ethyl alcohol, 10mg graphene powder ultrasonic disperses are weighed dense in 5mL
Spend in the chitosan solution for 0.05wt% and obtain 2mg/ml graphene dispersing solution, by the nanowire suspended liquid of Cu and graphene dispersion
Liquid is according to volume ratio 1:0.5-2 is mixed, and ultrasonically treated 30-60min is well mixed it, obtains copper nano-wire/graphene/chitosan
Compound dispersion liquid；
(4) preparation of cupric oxide nano line/single-wall carbon nanotube composite：By black CuO nano wire powder in the step (2)
The nanowire suspended liquid of CuO for being made that concentration is 2mg/ml in absolute ethyl alcohol is dissolved in, 4-6mg single-walled carbon nanotube powder ultrasonics are weighed
It is scattered in the single-walled carbon nanotube point that 0.4-0.6mg/ml is obtained in the sodium dodecyl sulfate solution that 10mL concentration is 0.05wt%
Dispersion liquid, by the nanowire suspended liquid of CuO and single-walled carbon nanotube dispersion liquid according to volume ratio 1:0.4-2 is mixed, ultrasonically treated 30-
60min is well mixed it, obtains cupric oxide nano line/single-wall carbon nanotube composite dispersion liquid；
(5) preparation of modified electrode：Glass-carbon electrode is processed by shot blasting, cleaned and is dried, the copper nano-wire/graphite is taken
Alkene/chitosan complexes dispersion liquid or cupric oxide nano line/single-wall carbon nanotube composite dispersant liquid drop are added to the glass after processing
Under carbon electrodes, room temperature condition, it is combined after producing copper nano-wire/graphene/chitosan after the drying of electrode surface solution evaporation
Thing modified electrode or cupric oxide nano line/single-wall carbon nanotube composite modified electrode；
(6) Electrochemical Detection residues of organophosphate pesticides content：Using modified electrode in the step (5) as working electrode, Ag/AgCl makees
For reference electrode, platinum electrode is as to electrode, and it is 0.1mol/l's that 5mL concentration is added dropwise into electrochemical reaction cell at room temperature
Disodium hydrogen phosphate-citric acid solution is measured as electrolyte, and residues of organophosphate pesticides is detected.
2. a kind of preparation of residues of organophosphate pesticides detection sensor based on copper/cupric oxide nano line according to claim 1
Method, it is characterised in that described copper nano-wire/graphene/chitosan complexes are overhead fine and close network structure.
3. a kind of preparation of residues of organophosphate pesticides detection sensor based on copper/cupric oxide nano line according to claim 1
Method, it is characterised in that described cupric oxide nano line/single-wall carbon nanotube composite is the cellular network knot mutually wound
Structure.
4. a kind of preparation of residues of organophosphate pesticides detection sensor based on copper/cupric oxide nano line according to claim 1
Method, it is characterised in that described copper nano-wire/graphene/chitosan complexes modified electrode is in the residual organophosphor of the agriculture
The dynamic detection range of parathion-methyl is 0.1-10ppm, and detection sensitivity is 471.0 μ Acm-2·ppm-1。
5. a kind of preparation of residues of organophosphate pesticides detection sensor based on copper/cupric oxide nano line according to claim 1
Method, it is characterised in that described copper nano-wire/graphene/chitosan complexes modified electrode is to the residual organophosphor first of the agriculture
The dynamic detection range of base parathion is 0.2-5ppm, and the dynamic detection range is linear detection range.
6. a kind of preparation of residues of organophosphate pesticides detection sensor based on copper/cupric oxide nano line according to claim 1
Method, it is characterised in that described cupric oxide nano line/single-wall carbon nanotube composite modified electrode is to the residual organophosphor of the agriculture
The detection range of linearity of middle malathion is 180-200ppb, and detection sensitivity is 628.51 μ Acm-2·ppb-1, test limit
As little as 0.1ppb.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710315045.1A CN107328831A (en) | 2017-05-07 | 2017-05-07 | A kind of preparation method of the residues of organophosphate pesticides detection sensor based on copper/cupric oxide nano line |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710315045.1A CN107328831A (en) | 2017-05-07 | 2017-05-07 | A kind of preparation method of the residues of organophosphate pesticides detection sensor based on copper/cupric oxide nano line |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107328831A true CN107328831A (en) | 2017-11-07 |
Family
ID=60192690
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710315045.1A Pending CN107328831A (en) | 2017-05-07 | 2017-05-07 | A kind of preparation method of the residues of organophosphate pesticides detection sensor based on copper/cupric oxide nano line |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107328831A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109270228A (en) * | 2018-11-24 | 2019-01-25 | 广西中医药大学附属瑞康医院 | A kind of Monitoring Pesticide Residues method and system based on graphene sensor |
| CN110857215A (en) * | 2018-08-22 | 2020-03-03 | 南京理工大学 | Method for preparing low-sensitivity copper azide from composite CNTs and copper nanowires |
-
2017
- 2017-05-07 CN CN201710315045.1A patent/CN107328831A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 李琼: "基于铜纳米材料的非酶有机磷农残电化学传感检测研究", 《重庆大学硕士学位论文》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110857215A (en) * | 2018-08-22 | 2020-03-03 | 南京理工大学 | Method for preparing low-sensitivity copper azide from composite CNTs and copper nanowires |
| CN110857215B (en) * | 2018-08-22 | 2023-08-18 | 南京理工大学 | Method for preparing low-sensitivity copper azide by compounding CNTs and copper nanowires |
| CN109270228A (en) * | 2018-11-24 | 2019-01-25 | 广西中医药大学附属瑞康医院 | A kind of Monitoring Pesticide Residues method and system based on graphene sensor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Rathnakumar et al. | Stalling behaviour of chloride ions: a non-enzymatic electrochemical detection of α-Endosulfan using CuO interface | |
| He et al. | Electrochemical sensor for rapid and sensitive detection of tryptophan by a Cu2O nanoparticles-coated reduced graphene oxide nanocomposite | |
| Huo et al. | A highly efficient organophosphorus pesticides sensor based on CuO nanowires–SWCNTs hybrid nanocomposite | |
| Yuan et al. | The phases of WS2 nanosheets influence uptake, oxidative stress, lipid peroxidation, membrane damage, and metabolism in algae | |
| Luo et al. | Photoelectrochemical detection of circulating tumor cells based on aptamer conjugated Cu2O as signal probe | |
| Judy et al. | Bioaccumulation of gold nanomaterials by Manduca sexta through dietary uptake of surface contaminated plant tissue | |
| Wu et al. | A ratiometric fluorescence-scattered light strategy based on MoS2 quantum dots/CoOOH nanoflakes system for ascorbic acid detection | |
| Singh et al. | Preparation, antibacterial activity, and electrocatalytic detection of hydrazine based on biogenic CuFeO 2/PANI nanocomposites synthesized using Aloe barbadensis miller | |
| Zhou et al. | Simultaneous determination of catechol and hydroquinone using non-enzymatic Co3O4@ carbon core/shell composites based sensor | |
| Kumaravel et al. | Electrochemical detection of fenitrothion usingnanosilver/dodecane modified glassy carbon electrode | |
| CN113390943B (en) | Electrochemical sensor for detecting organophosphorus pesticide and preparation method thereof | |
| CN107328831A (en) | A kind of preparation method of the residues of organophosphate pesticides detection sensor based on copper/cupric oxide nano line | |
| Mehmandoust et al. | A zinc oxide nanorods/molybdenum disulfide nanosheets hybrid as a sensitive and reusable electrochemical sensor for determination of anti-retroviral agent indinavir | |
| CN109490390B (en) | Preparation method of graphene oxide-multiwalled carbon nanotube-Au @ Pt NPs enzyme-free glucose electrochemical sensor | |
| Chen et al. | A sensitive electrochemical determination of chemotherapy agent using graphitic carbon nitride covered vanadium oxide nanocomposite; sonochemical approach | |
| Qileng et al. | Composite films of CdS nanoparticles, MoS2 nanoflakes, reduced graphene oxide, and carbon nanotubes for ratiometric and modular immunosensing-based detection of toxins in cereals | |
| Feng et al. | Hollow C@ MoS2 nanotubes with Hg2+-triggered oxidase-like catalysis: A colorimetric method for detection of Hg2+ ions in wastewater | |
| Wang et al. | Green synthesis of Pd nanoparticles via extracted polysaccharide applied to glucose detection | |
| Wu et al. | Tunable synthesis of CoP and CoP2 decorated 3D carbon Nanohybrids and the application of CoP2 decorated one in electrochemical detection of chloramphenicol in Milk and honey | |
| Naghian et al. | Electrochemical oxidation and determination of antiviral drug acyclovir by modified carbon paste electrode with magnetic CdO nanoparticles | |
| Yang et al. | Bi/BiVO4/NiFe-LDH heterostructures with enhanced photoelectrochemical performance for streptomycin detection | |
| Zhuang et al. | One-step rapid synthesis of Ni 6 (C 12 H 25 S) 12 nanoclusters for electrochemical sensing of ascorbic acid | |
| Ru et al. | Fabrication of octahedral GO/UiO-67@ PtNPs nanocomposites as an electrochemical sensor for ultrasensitive recognition of arsenic (III) in Chinese Herbal Medicine | |
| Kavya et al. | Glassy carbon electrode modified by gold nanofibers decorated iron metal–organic framework nanocomposite for voltammetric determination of acetaminophen | |
| Li et al. | Research progress of nanomaterials-based sensors for food safety |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20171107 |
|
| WD01 | Invention patent application deemed withdrawn after publication |