CN108287186A - A kind of device of detection lead ion - Google Patents
A kind of device of detection lead ion Download PDFInfo
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- CN108287186A CN108287186A CN201710013266.3A CN201710013266A CN108287186A CN 108287186 A CN108287186 A CN 108287186A CN 201710013266 A CN201710013266 A CN 201710013266A CN 108287186 A CN108287186 A CN 108287186A
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Abstract
The invention discloses a kind of detection Pb2+Device, the device use three-electrode system, working electrode be polypyrrole coat Co3O4The cubical array electrode of nano wire, auxiliary electrode are Pt electrodes, and reference electrode is Ag/AgCl electrodes, selects acetic acid sodium acetate for buffer solution, and wherein polypyrrole coats Co3O4The cubical array electrode of nano wire loads polypyrrole cladding Co using foam copper as substrate in substrate3O4The cubical array of nano wire, Co3O4The length of nano wire is 1~1.8 μm, a diameter of 100~130nm, and the thickness of polypyrrole clad is 10~15nm, Co3O4Nano wire has polycrystalline structure.Present invention reduces experimental costs, easy to operate, and Co is improved using three-dimensional matrix structure3O4Electric conductivity, increase the specific surface area and active site of electrode material, introducing nitrogenous polypyrrole further improves the electric conductivity of electrode material, nitrogen-containing group can effectively and Pb2+Complexing is conducive to Pb when detection2+Enrichment, further improves sensor to Pb2+The reduction of the raising and detection limit of detection sensitivity.
Description
Technical field
The present invention relates to heavy metal analysis fields, more specifically to a kind of detection Pb2+Device.
Background technology
The method of detection heavy metal mainly has at present：Flame emission spectrometry (FES), electricity Gan Teeth close Plasma-Atomic hair
Penetrate spectroscopic methodology (ICP-AES), hydride generated atomic absorption spectrum (HG-AAS), cold vapor atoms absorption spectrum (CV-AAS)
Deng, but these traditional method equipment are expensive, and detection cycle is long, and equipment volume is huge, the factors such as more to detection sample limitation,
It is greatly limited the detection of lead ion.And electrochemical method is due to its quick, sensitive, accurate, simple operation and easily
In the series of characteristics such as miniaturization and networking, become the important research method for carrying out concentration of heavy metal ion detection.
Co3O4It is a kind of p-type semiconductor material, extensive concern has been had received in various fields.Co3O4Nanometer sheet, receive
Rice spherical structure has been applied to heavy metal analysis field, but these structures are easy to happen stacking, are unfavorable for the enrichment of heavy metal, nothing
Method obtains high sensitivity and low detection limit simultaneously.Doped polypyrrole has higher as a kind of conducting polymer
Conductivity (10~100Scm-1) and film forming, it is controllable to utilize it as covering material thickness, while polypyrrole also can be used as weight
The detection materials'use of metal lead ion.Therefore there is an urgent need for inventing new detection material, to reach low detection limit, highly sensitive inspection
Survey target.
Invention content
Present invention aims to overcome that the prior art, provides a kind of detection Pb2+Device.
The purpose of the present invention is achieved through the following technical solutions.
A kind of detection Pb2+Device, using three-electrode system, working electrode is that polypyrrole coats Co3O4The three of nano wire
Array electrode is tieed up, auxiliary electrode is Pt electrodes, and reference electrode is Ag/AgCl electrodes, selects the pH to be for 5 Acetic acid-sodium acetate
Buffer solution, wherein polypyrrole coat Co3O4The cubical array electrode of nano wire loads poly- pyrrole using foam copper as substrate in substrate
Cough up cladding Co3O4The cubical array of nano wire, Co3O4The length of nano wire is 1~1.8 μm, a diameter of 100~130nm, poly- pyrrole
The thickness for coughing up clad is 10~15nm, Co3O4There is nano wire polycrystalline structure, the polypyrrole to coat Co3O4Nano wire
Cubical array is prepared as steps described below：
Step 1, cobalt nitrate, ammonium fluoride and urea is evenly dispersed in distilled water, and the mixing liquid after stirring is transferred to
Foam copper is suspended in mixing liquid and carries out hydro-thermal reaction by water heating kettle；The substance of the cobalt nitrate, ammonium fluoride, urea
The ratio of amount is (1~3)：(2~5)：(5~15), mixing time are 10~25min；The temperature of the hydro-thermal reaction be 80~
140 DEG C, the time is 4~8h, adheres to pink mass in foam copper substrate after hydro-thermal reaction；
Step 2 after reaction kettle is cooled to room temperature, is taken out foam copper substrate, is rinsed repeatedly with distilled water and ethyl alcohol, room temperature
It is dry, foam copper substrate is transferred in Muffle furnace and is calcined, gained Co3O4Nano-wire array；The calcination temperature is 200
~500 DEG C, calcination time is 2~4h；
Step 3, ammonium persulfate and SDS is evenly dispersed in distilled water, by Co3O4Nano-wire array is put into above-mentioned mixing
It is impregnated in solution, so that ammonium persulfate and SDS are distributed in Co3O4In nano-wire array；The substance of the ammonium persulfate and SDS
Amount ratio be (1~3)：(0.01~0.05), the soaking time are 15~30min.
Step 4, by the Co after being impregnated in step 33O4Nano-wire array takes out and places it in culture dish, is cultivating
Pyrrole monomer is added in ware, the two is not directly contacted with, sealing culture dish, pyrrole monomer volatilization generation pyrroles's steam in culture dish,
Pyrroles's steam and Co3O4Ammonium persulfate and SDS are contacted and in Co in nano-wire array3O4Nanowire surface in-situ polymerization generates poly-
Pyrroles forms polypyrrole and coats Co3O4The cubical array of nano wire.
Preferably, Co3O4The length of nano wire is 1~1.2 μm, a diameter of 115~120nm, the thickness of polypyrrole clad
For 12~15nm.
Preferably, the size of the foam copper is (1~1.5) × (2~2.5) cm2。
Preferably, in step 1, the amount of the cobalt nitrate is 1~3mmol, and the amount of ammonium fluoride is 2~5mmol, urea
Amount be 5~15mmol, mixing time is 10~20min, and the mixed liquor be the uniform pink colour liquid of becoming clear.
Preferably, in step 1, the temperature of the hydro-thermal reaction is 90~120 DEG C, and the time is 5~7h.
Preferably, in step 2, the calcination temperature is 200~400 DEG C, and calcination time is 2~3h.
Preferably, in step 3, the amount of the ammonium persulfate is 1~3mmol, the amount of the SDS is 0.01~
0.05mmol；Co3O4Nano-wire array soaking time in the mixed solution of ammonium persulfate and SDS is 15~25min.
Preferably, in step 4, the amount of the pyrrole monomer is 10~30 μ L, pyrrole monomer and Co3O4Nano-wire array
Reaction time in culture dish is 3~10min, and the heating temperature to culture dish is 20~40 DEG C；By regulating and controlling pyrrole monomer
Dosage, reaction time and temperature are to adjust the thickness of polypyrrole clad.
When carrying out lead ion detection using above equipment, Pb is added dropwise into buffer solution2+Aqueous solution utilizes SWASV methods
Current-responsive is measured, the linear equation measured is y=85.5x+0.38, and the range of linearity is 0.024 μM~0.48 μM, related coefficient
It is 0.99, sensitivity is 85.5 μ A μM-1, detect and be limited to 0.58nM (S/N=3).
The present invention greatly reduces experimental cost, and operating method is easy, and obtained modified electrode has excellent electrochemistry
Performance has broad application prospects in lead ion monitoring etc..The present invention utilizes the advantage of three-dimensional matrix structure, improves Co3O4
Electric conductivity, increase the specific surface area and active site of electrode material, improve Co3O4For Pb2+Detectability；Introducing contains
The polypyrrole of nitrogen further improves the electric conductivity of electrode material, and nitrogen-containing group being capable of effective and Pb2+Complexing, when being conducive to detection
Pb2+Enrichment, further improves sensor to Pb2+The reduction of the raising and detection limit of detection sensitivity.
Description of the drawings
Fig. 1 is Co3O4The scanning electron microscope (SEM) photograph of nano needle arrays electrode.
Fig. 2 is that polypyrrole coats Co3O4The transmission electron microscope picture of nano line array electrode.
Fig. 3 is that polypyrrole coats Co3O4Nano line array electrode X ray diffracting spectrum.
Fig. 4 is foam copper, Co3O4Co is coated with polypyrrole3O4The CV curve comparison figures of nano line array electrode.
Fig. 5 is Co3O4Co is coated with polypyrrole3O4The SWASV curve comparison figures of nano line array electrode.
Fig. 6 is that polypyrrole coats Co3O4Nano line array electrode is in various concentration Pb2+SWASV current-responsives in solution
Curve.
Fig. 7 is that polypyrrole coats Co3O4Nano line array electrode is in various concentration Pb2+SWASV current-responsives in solution
The corresponding canonical plotting of curve.
Specific implementation mode
The instrument and medicine information used in the embodiment of the present invention are as shown in the table：
Electro-chemical test is carried out to sample using three electrode test systems：
Wherein working electrode is that polypyrrole coats Co3O4Nano line array electrode, auxiliary electrode are Pt electrode (diameters
1mm), reference electrode is Ag/AgCl electrodes, is set in scanning voltage ranging from -0.2~0.6V, in the K of 5nM3[Fe(CN)6] and
The K of 5nM4[Fe(CN)6] 0.1M KCl solution in carry out CV cyclic voltammetry scans.
Polypyrrole coats Co3O4Nano line array electrode is in three-electrode system, the Acetic acid-sodium acetate buffer solution for being 5 in pH
In be added dropwise Pb2+ solution, carry out SWASV methods and measure current-responsive under various concentration.
Embodiment 1
Foam copper is immersed in successively in hydrochloric acid, acetone, distilled water and absolute ethyl alcohol, is cleaned by ultrasonic, is removed on foam copper
Greasy dirt, oxide layer, insoluble matter etc., will be dried for standby in vacuum drying chamber that foam copper is placed at 60 DEG C.
It is 1 × 2cm having been subjected to pretreated foam copper to be cut to size2As substrate, Co is grown in this substrate3O4
Presoma nanowire array structure.Cobalt nitrate 0.58g, ammonium fluoride 0.1389g, urea 0.56g are weighed, is added to 40ml distilled water
In, 10min is stirred, bright uniform pink colour liquid is obtained.This pink colour liquid is poured into water heating kettle, foam copper is suspended in powder
In color liquid.At a temperature of 100 DEG C, hydro-thermal reaction 8h takes out reaction kettle and is cooled to room temperature, it is copper-based to take out foam after reaction
Bottom, it can be seen that be attached to pink mass in foam copper substrate, rinsed repeatedly with distilled water and ethyl alcohol, drying at room temperature.
Sample is transferred in Muffle furnace, 2h is calcined in air, 200 DEG C of calcination temperature obtains Co3O4Nano-wire array.
Using the method for chemical vapor deposition polymerization in Co3O4Nano-wire array surface coats one layer of ultra-thin polypyrrole
(PPy) film：It weighs 0.66g ammonium persulfates and 0.01g SDS is added in distilled water, ultrasound makes it fully dissolve.By Co3O4Nanometer
Linear array, which is put into above-mentioned mixed solution, impregnates 30min, and taking-up is placed in culture dish, and it is single that 30 μ L pyrroles are added in culture dish
Body, the two are not directly contacted with, and cover culture dish, in culture dish pyrrole monomer volatilization generate pyrroles's steam.It takes out, uses after 10min
Distilled water and ethyl alcohol rinse surface repeatedly, obtain Co3O4@PPy nano line array electrodes.
In Fig. 1 it can be seen that being evenly distributed of nanometer needle construction, consistency are preferable, the diameter of nanoneedle in 120nm or so,
1.5 μm of length can obviously observe acicular pattern.Fig. 2 explanations are successfully prepared polypyrrole cladding Co3O4Nano-wire array electricity
Pole, transmission plot show PPy layer of thickness in 12nm or so, it was demonstrated that can be obtained using the method for chemical gaseous phase polymerization very thin
Polypyrrole layer.
Embodiment 2
Foam copper is immersed in successively in hydrochloric acid, acetone, distilled water and absolute ethyl alcohol, is cleaned by ultrasonic, is removed on foam copper
Greasy dirt, oxide layer, insoluble matter etc., will be dried for standby in vacuum drying chamber that foam copper is placed at 60 DEG C.
It is 1 × 2cm having been subjected to pretreated foam copper to be cut to size2As substrate, Co is grown in this substrate3O4
Presoma nanowire array structure.Cobalt nitrate 0.29g, ammonium fluoride 0.1389g, urea 0.3g are weighed, is added to 40ml distilled water
In, 10min is stirred, bright uniform pink colour liquid is obtained.This pink colour liquid is poured into water heating kettle, foam copper is suspended in powder
In color liquid.At a temperature of 120 DEG C, hydro-thermal reaction 5h takes out reaction kettle and is cooled to room temperature, it is copper-based to take out foam after reaction
Bottom, it can be seen that be attached to pink mass in foam copper substrate, rinsed repeatedly with distilled water and ethyl alcohol, drying at room temperature.
Sample is transferred in Muffle furnace, 2h is calcined in air, 400 DEG C of calcination temperature obtains Co3O4Nano-wire array.
Using the method for chemical vapor deposition polymerization in Co3O4Nano-wire array surface coats one layer of ultra-thin polypyrrole
(PPy) film：It weighs 0.23g ammonium persulfates and 0.03g SDS is added in distilled water, ultrasound makes it fully dissolve.By Co3O4Nanometer
Linear array, which is put into above-mentioned mixed solution, impregnates 20min, and taking-up is placed in culture dish, and it is single that 10 μ L pyrroles are added in culture dish
Body, the two are not directly contacted with, and cover culture dish, in culture dish pyrrole monomer volatilization generate pyrroles's steam.It takes out, uses after 10min
Distilled water and ethyl alcohol rinse surface repeatedly, obtain Co3O4@PPy nano line array electrodes.
In order to study Co3O4The crystalline structure of@PPy nano-wire arrays, to the Co of the growth of foam copper substrate3O4@PPy receive
Nanowire arrays have carried out XRD tests, are the feature of foam copper substrate as shown in figure 3,2 θ=43.3 ° of characteristic peak, at 50.3 °, 74 °
Peak, 2 θ=31.1 ° of diffractive features peak correspond to Co at 36.6 °, 59.3 °, 65.1 ° respectively3O4(220), (311), (511),
(440) crystal face, this result proof successfully synthesize Co3O4Polycrystalline structure.
Fig. 4 is three kinds of electrode foam copper, Co3O4And Co3O4All there is CV in the CV curve graphs of@PPy, three kinds of electrode curves
Redox peaks, and it is essentially identical to go out peak position, and foam copper grows Co3O4After nanoneedle, under redox peak current occurs
Drop, this is because Co3O4For semiconductor, electric conductivity is poorer than foam copper, so the decline of peak current is caused, but due to
Co3O4Nano needle arrays structure adds somewhat to active catalyst sites so that the decline of peak current is not apparent.It is poly-
The Co obtained after pyrroles's cladding3O4There is apparent growth in the CV peak currents of@PPy nano-wire arrays, this is because polypyrrole packet
The electric conductivity of material, Co are increased after covering3O4@PPy nano-wire arrays have good catalytic activity.
Embodiment 3
Foam copper is immersed in successively in hydrochloric acid, acetone, distilled water and absolute ethyl alcohol, is cleaned by ultrasonic, is removed on foam copper
Greasy dirt, oxide layer, insoluble matter etc., will be dried for standby in vacuum drying chamber that foam copper is placed at 70 DEG C.
It is 1 × 2cm having been subjected to pretreated foam copper to be cut to size2As substrate, Co is grown in this substrate3O4
Presoma nanowire array structure.Cobalt nitrate 0.87g, ammonium fluoride 0.074g, urea 0.3g are weighed, is added to 40ml distilled water
In, 20min is stirred, bright uniform pink colour liquid is obtained.This pink colour liquid is poured into water heating kettle, foam copper is suspended in powder
In color liquid.At a temperature of 80 DEG C, hydro-thermal reaction 8h takes out reaction kettle and is cooled to room temperature, it is copper-based to take out foam after reaction
Bottom, it can be seen that be attached to pink mass in foam copper substrate, rinsed repeatedly with distilled water and ethyl alcohol, drying at room temperature.
Sample is transferred in Muffle furnace, 2h is calcined in air, 300 DEG C of calcination temperature obtains Co3O4Nano-wire array.
Using the method for chemical vapor deposition polymerization in Co3O4Nano-wire array surface coats one layer of ultra-thin polypyrrole
(PPy) film：It weighs 0.45g ammonium persulfates and 0.02g SDS is added in distilled water, ultrasound makes it fully dissolve.By Co3O4Nanometer
Linear array, which is put into above-mentioned mixed solution, impregnates 30min, and taking-up is placed in culture dish, and it is single that 20 μ L pyrroles are added in culture dish
Body, the two are not directly contacted with, and cover culture dish, in culture dish pyrrole monomer volatilization generate pyrroles's steam.It takes out, uses after 15min
Distilled water and ethyl alcohol rinse surface repeatedly, obtain Co3O4@PPy nano line array electrodes.
Fig. 5 is Co3O4And Co3O4@PPy nano line array electrodes are containing 0.3 μM of Pb2+ABS (pH=5) in
SWASV curves, it can be seen that the peak of current-responsive, Co all occur at -0.59V in two kinds of electrodes3O4Nano needle arrays electrode
Co of the SWASV current-responsives peak after 19 μ A or so, and polypyrrole are coated3O4@PPy nano line array electrodes peak at -0.59V
Current value is 24.8 μ A, this is because after cladding polypyrrole, improves the electric conductivity of electrode material entirety, nitrogenous in polypyrrole
Lead ion can be complexed simultaneously in group, increase the active site of electrode material so that Co3O4The spirit of@PPy nano line array electrodes
Sensitivity is improved, it was demonstrated that Co3O4The structure of@PPy nano-wire arrays can improve the spirit of lead ion detection electrochemical sensor
Sensitivity.
Embodiment 4
Foam copper is immersed in successively in hydrochloric acid, acetone, distilled water and absolute ethyl alcohol, is cleaned by ultrasonic, is removed on foam copper
Greasy dirt, oxide layer, insoluble matter etc., will be dried for standby in vacuum drying chamber that foam copper is placed at 70 DEG C.
It is 1 × 2cm having been subjected to pretreated foam copper to be cut to size2As substrate, Co is grown in this substrate3O4
Presoma nanowire array structure.Cobalt nitrate 0.87g, ammonium fluoride 0.185g, urea 0.9g are weighed, is added to 40ml distilled water
In, 20min is stirred, bright uniform pink colour liquid is obtained.This pink colour liquid is poured into water heating kettle, foam copper is suspended in powder
In color liquid.At a temperature of 140 DEG C, hydro-thermal reaction 4h takes out reaction kettle and is cooled to room temperature, it is copper-based to take out foam after reaction
Bottom, it can be seen that be attached to pink mass in foam copper substrate, rinsed repeatedly with distilled water and ethyl alcohol, drying at room temperature.
Sample is transferred in Muffle furnace, 2h is calcined in air, 200 DEG C of calcination temperature obtains Co3O4Nano-wire array.
Using the method for chemical vapor deposition polymerization in Co3O4Nano-wire array surface coats one layer of ultra-thin polypyrrole
(PPy) film：It weighs 0.66g ammonium persulfates and 0.01g SDS is added in distilled water, ultrasound makes it fully dissolve.By Co3O4Nanometer
Linear array, which is put into above-mentioned mixed solution, impregnates 30min, and taking-up is placed in culture dish, and it is single that 30 μ L pyrroles are added in culture dish
Body, the two are not directly contacted with, and cover culture dish, in culture dish pyrrole monomer volatilization generate pyrroles's steam.It takes out, uses after 20min
Distilled water and ethyl alcohol rinse surface repeatedly, obtain Co3O4@PPy nano line array electrodes.
In order to study Co3O4The range of linearity, sensitivity and detection limit of the@PPy nano-wire arrays when heavy metal lead detects.
Selection Acetic acid-sodium acetate be buffer solution (ABS), adjust pH of buffer be 5, deposition voltage be -1.2V, sedimentation time 120s,
Frequency is 25Hz, and amplitude 25mV, step voltage 1mV add the Pb of various concentration2+Solution utilizes anodic stripping voltammetry
Study detection performance.If Fig. 6 is various concentration Pb2+The SWASV current-responsive curves of solution, the plumbum ion concentration of addition is ranging from
0.024 μM~0.48 μM, with the increase of plumbum ion concentration, SWASV current-responsive values are also linearly increasing, and spike potential is always
It is maintained at -0.59V, peak position does not deviate.In -0.4V or so, there are one the weaker small peaks of peak value, this is because lead ion is heavy
Different crystal forms is formd when accumulating on the electrode.Fig. 7 is Co3O4@PPy nano line array electrode various concentrations Pb2+Solution
Corresponding canonical plotting (the linear equation of SWASV current-responsive curves：Y=85.5x+0.38), it is known that in concentration range 0.024
When μM -0.48 μM (5 μ g/L-100 μ g/L), Co3O4@PPy nano line array electrodes have good line for the detection of lead ion
Sexual intercourse, the range of linearity are 0.024 μM~0.48 μM, and related coefficient 0.99, sensitivity is 85.5 μ A μM-1, according to LOD=
3SD/S (SD is standard deviation, and S is sensitivity) can be calculated detection and be limited to 0.58nM (S/N=3).Demonstrate Co3O4@PPy
Nanowire array structure can realize while have higher sensitivity and lower detection to limit, and have the wide range of linearity.
All methods and applications that the present invention is disclosed and proposed, those skilled in the art can be fitted by using for reference present disclosure
When the realization of the links such as feed change and process route, although the methods and applications of the present invention are carried out by preferred embodiment
Description, related technical personnel obviously can not depart from the content of present invention, in spirit and scope to method described herein and application
It is modified or reconfigures, to realize final technology of preparing.In particular, it should be pointed out that all similar replacements and changing
Dynamic apparent to those skilled in the art, they are considered as being included in spirit of that invention, range and content.
Claims (7)
1. a kind of detection Pb2+Device, it is characterised in that：Using three-electrode system, working electrode is that polypyrrole coats Co3O4It receives
The cubical array electrode of rice noodles, auxiliary electrode be Pt electrodes, reference electrode be Ag/AgCl electrodes, select pH for 5 acetic acid-
Sodium acetate is buffer solution, and wherein polypyrrole coats Co3O4The cubical array electrode of nano wire is using foam copper as substrate, in substrate
It loads polypyrrole and coats Co3O4The cubical array of nano wire, Co3O4The length of nano wire be 1~1.8 μm, a diameter of 100~
The thickness of 130nm, polypyrrole clad are 10~15nm, Co3O4Nano wire has polycrystalline structure, polypyrrole cladding
Co3O4The cubical array electrode of nano wire is prepared as steps described below：
Step 1, cobalt nitrate, ammonium fluoride and urea is evenly dispersed in distilled water, and the mixing liquid after stirring is transferred to hydro-thermal
Foam copper is suspended in mixing liquid and carries out hydro-thermal reaction by kettle；The cobalt nitrate, ammonium fluoride, urea substance amount
Than for (1~3)：(2~5)：(5~15), mixing time are 10~25min；The temperature of the hydro-thermal reaction is 80~140
DEG C, the time is 4~8h, adheres to pink mass in foam copper substrate after hydro-thermal reaction；
Step 2 after reaction kettle is cooled to room temperature, is taken out foam copper substrate, is rinsed repeatedly with distilled water and ethyl alcohol, drying at room temperature,
Foam copper substrate is transferred in Muffle furnace and is calcined, gained Co3O4Nano-wire array；The calcination temperature is 200~500
DEG C, calcination time is 2~4h；
Step 3, ammonium persulfate and lauryl sodium sulfate (SDS) is evenly dispersed in distilled water, by Co3O4Nano-wire array
It is put into above-mentioned mixed solution and impregnates, so that ammonium persulfate and SDS are distributed in Co3O4In nano-wire array；The ammonium persulfate
Amount ratio with the substance of SDS is (1~3)：(0.01~0.05), the soaking time are 15~30min.
Step 4, by the Co after being impregnated in step 33O4Nano-wire array takes out and places it in culture dish, in culture dish
Pyrrole monomer is added, the two is not directly contacted with, sealing culture dish, pyrrole monomer volatilization generation pyrroles's steam, pyrroles in culture dish
Steam and Co3O4Ammonium persulfate and SDS are contacted and are generated polypyrrole in Co3O4 nanowire surface in-situ polymerizations in nano-wire array,
Form the cubical array of polypyrrole cladding Co3O4 nano wires.
2. a kind of detection Pb according to claim 12+Device, it is characterised in that：Co3O4The length of nano wire be 1~
1.2 μm, a diameter of 115~120nm, the thickness of polypyrrole clad is 12~15nm；The size of the foam copper be (1~
1.5) × (2~2.5) cm2。
3. a kind of detection Pb according to claim 12+Device, it is characterised in that：In step 1, the cobalt nitrate
Amount is 1~3mmol, and the amount of ammonium fluoride is 2~5mmol, and the amount of urea is 5~15mmol, and mixing time is 10~20min, institute
The mixed liquor stated is bright uniform pink colour liquid；The temperature of the hydro-thermal reaction is 90~120 DEG C, and the time is 5~7h.
4. a kind of detection Pb according to claim 12+Device, it is characterised in that：In step 2, the calcination temperature
It it is 200~400 DEG C, calcination time is 2~3h.
5. a kind of detection Pb according to claim 12+Device, it is characterised in that：The amount of the ammonium persulfate be 1~
The amount of 3mmol, the SDS are 0.01~0.05mmol；Co3O4Nano-wire array is in the mixed solution of ammonium persulfate and SDS
Soaking time is 15~25min.
6. a kind of detection Pb according to claim 12+Device, it is characterised in that：In step 4, the pyrrole monomer
Amount be 10~30 μ L, pyrrole monomer and Co3O4Reaction time of the nano-wire array in culture dish is 3~10min, to culture
The heating temperature of ware is 20~40 DEG C；By regulating and controlling pyrrole monomer dosage, reaction time and temperature to adjust polypyrrole clad
Thickness.
7. utilizing a kind of detection Pb as described in claim 12+Device carry out lead ion detection when, be added dropwise into buffer solution
Enter Pb2+Aqueous solution measures current-responsive using SWASV methods, and the linear equation measured is y=85.5x+0.38, and the range of linearity is
0.024 μM~0.48 μM, related coefficient 0.99, sensitivity is 85.5 μ A μM-1, detect and be limited to 0.58nM (S/N=3).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110887890A (en) * | 2019-12-12 | 2020-03-17 | 淮北师范大学 | Method for electrochemically detecting heavy metal ions by doping modified reinforced nano material |
| CN112919549A (en) * | 2021-01-21 | 2021-06-08 | 邵阳学院 | Pure-phase spinel Co3O4Multistage nanosheet and soft template preparation method thereof and application of multistage nanosheet in supercapacitor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112919549A (en) * | 2021-01-21 | 2021-06-08 | 邵阳学院 | Pure-phase spinel Co3O4Multistage nanosheet and soft template preparation method thereof and application of multistage nanosheet in supercapacitor |
| CN112919549B (en) * | 2021-01-21 | 2024-04-26 | 邵阳学院 | Pure phase spinel Co3O4Multistage nano-sheet, soft template preparation method thereof and application of multistage nano-sheet in super capacitor |
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