CN106442668B - A kind of preparation method of carbon nano tube modified electrode - Google Patents
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- 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
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- G—PHYSICS
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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Abstract
The present invention relates to electrochemical field, a kind of preparation method of carbon nano tube modified electrode and the application of the electrode are specifically disclosed.The present invention, as bridge, successfully realizes carbon nanotube orderly controllable growth on GCE by ethylenediamine, forms single-layer carbon nano-tube array.The present invention does not use any amidation chemical reagent, simple electric cyclic voltammetry is only used only, solid carbon nanotube is bonded in electrode surface, single-wall carbon nanotube synthesizing from (v-SWCNT) to glass-carbon electrode (GCE) in a manner of being chemically bonded.Electrode prepared by the present invention is high to the detection sensitivity of clenbuterol hydrochloride, and detection speed is fast, is detected in the buffer solution that pH is 1, and the peak current response of clenbuterol hydrochloride is best.The modified electrode preparation method is novel, and decorative material is simple, safe operation.
Description
Technical field
The present invention relates to electrochemical fields, specifically, being related to a kind of preparation method of carbon nano tube modified electrode.
Background technique
Clenbuterol hydrochloride retention analysis is most important in the application of field of food safety, currently, having perhaps for clenbuterol hydrochloride analysis
Multi-method, conventional has high performance liquid chromatography, gas chromatography-mass spectrography etc..Recently, electrochemical method is also concerned, electricity
Chemical method is at low cost since its is easy to operate, and high sensitivity and by favor.With nano material and nanoaperture skill
The development of art, research has found that it is likely that by constructing electronics accelerated passage, carrys out the small electrical signal of releasing organics matter.
Wherein, carbon nanotube (CNT) is that common electrode prepares material, carbon nanotube (CNT) also known as Baji-tube
It (buckytubes), is to be found at high-resolution-ration transmission electric-lens (HRTEM) by Japanese Scientists Iijima (Iijirna) for 1991
A kind of needle-shaped tubular carbon, carbon nanotube then start from 1996 as electrode material for electrochemical research, and Britto studies DOPA
The electro-catalysis voltammetric behaviors of amine, cytochrome c and oxygen etc., it was confirmed that carbon nanotube can accelerate the electronics transfer on its interface.
Carbon nanotube shows the reactionlessness of similar graphite in the chemically, but this inertia be it is opposite, under certain condition
Biochemical reaction can also occur for carbon nanotube.
Carbon nanotube often carries out electrode modification with physical absorption or coherent condition, and this method of modifying makes carbon nanotube
It is disorderly arranged in electrode surface, what the electronics accelerated passage or catalytic channels that this non-directional arrangement is formed were contacted with organic matter
Chance is smaller, reduces the utilization efficiency of material.Compared to disorderly arranged carbon nanotube, the carbon nano-pipe array of ordered arrangement can
To improve many chemical properties and space performance, it is based on its minor diameter, high-specific surface area and good electric conductivity.Therefore it is formed
It is the hot spot studied at present that the single layer wall carbon nano tube clump (v-SWCNT) being vertically oriented, which is used as modified electrode,.But how it fills
It fits on modification of surfaces position, and is the difficult point of research with controllable density and orientation.Two methods are usually used in preparing v-
SWCNTs.One is the single-walled carbon nanotubes that vertical arrangement is directly generated on substrate, are formed using CVD method.This method system
Standby condition is harsh, and temperature is high, it is difficult to control.The other is being formed by the way that carbon nanotube is carried out oxidation truncation and containing a large amount of carboxylics
Then carbon nanotube is chained matrix using chemical synthesis process by base functional group.Link method mainly passes through Au-S, amide
Key, Si-O etc. are completed.Chemical synthesis is currently used v-SWCNTs preparation method, however, chemical synthesis process is excessively multiple
It is miscellaneous, (12 hours, 24 hours) the time progress self assembly of overlength is usually wanted, or need the operation of absolute anaerobic.
Therefore, need to develop that a kind of condition is simple and easy to control, single layer wall carbon nano tube clump (v-SWCNT) of strong operability
The preparation method of modified electrode.
Summary of the invention
In order to solve the problems in the existing technology, the object of the present invention is to provide a kind of carbon nano tube modified electrodes
The application of preparation method and the electrode in terms of detecting clenbuterol hydrochloride.
In order to achieve the object of the present invention, technical scheme is as follows:
In a first aspect, including the following steps: the present invention provides a kind of preparation method of carbon nano tube modified electrode
1) by glass-carbon electrode in potassium bichromate solution with cyclic voltammetry scanning 1~20 circle, scanning range be 0V~
1.6V, scanning speed are 0.1~0.5V/s；
2) step 1) the electrode obtained is enclosed in ethylenediamine solution with cyclic voltammetry scanning 5~25, scanning range 0V
~2.0V, scanning speed are 0.1~0.5V/s；
3) step 2) the electrode obtained is enclosed in carbon nano-tube solution with cyclic voltammetry scanning 5~25, scanning range is
0V~2.0V, scanning speed are 0.1~0.5V/s.
Wherein, carbon nanotube can accelerate transfer velocity of the electronics on electrode interface.The amino of ethylenediamine is respectively and electrode
The carboxyl on surface, the carboxyl of carboxylation carbon nanotube react, and carbon nanotube is incorporated in electrode surface in an orderly manner.
Preferably, more preferably showing to have the electrode in peak current response and appearance situation, the present invention is excellent
The scanning circle number changed in above-mentioned steps is as follows: being enclosed in potassium bichromate solution with cyclic voltammetry scanning 4~5, in ethylenediamine
With 20 circle of cyclic voltammetry scanning in solution, enclosed in carbon nano-tube solution with cyclic voltammetry scanning 20.
It should be noted that selecting one in the above optimization or selecting secondly carry out, protection scope of the present invention is also belonged to.
Further, the glass-carbon electrode use preceding carry out grinding process, and with cyclic voltammetry scanning (- 1.0V~
1.0V) stablize to curve, take out electrode and clean, is put into potassium ferricyanide solution and is characterized (- 0.2V~0.6V), characterization
It is required that being Δ E < 64V.
The potassium ferricyanide solution the preparation method comprises the following steps: by 0.1M KCl and 0.05mM k3Fe(CN)6Mixing, is configured to iron
Potassium cyanide solution, the transparent bright green of solution.
Further, conventional method can be used in the grinding process, it also may be preferable for following polishing process:
With 0.3mm Al2O31:1 EtOH Sonicate 2-3min is used after glass-carbon electrode 3-5min is polished on smooth deerskin surface,
It is clean to take out electrode distilled water flushing, then with 0.05mm Al2O3Polish 3-5min, uses 1:1HNO3Solution, distilled water surpass respectively
Sound 2-3min.
Further, the concentration of the potassium bichromate solution is 2.5~10%, preferably 2.5%；The ethylenediamine solution
Concentration is 5~15mM, preferably 5mM；The concentration of the carbon nano-tube solution is 2.5~10g/L, preferably 4g/L.
Second aspect, the carbon nano tube modified electrode being prepared the present invention provides preceding method and the carbon are received
Application of the mitron modified electrode in terms of detecting clenbuterol hydrochloride.
The application specifically may be embodied in a kind of method for detecting clenbuterol hydrochloride, specifically, sample to be tested is dissolved in pH1~8
Buffer solution in, with cyclic voltammetry or square wave voltammetry, Scanning Detction under the conditions of -1.0V~1.2V.
The present invention is preferably a kind of optimal after contrasting detection method and pH value of buffer solution are to the influence of testing result
Detection scheme are as follows: sample to be tested is dissolved in the sulfuric acid buffer solution of pH1, with square wave voltammetry, under the conditions of -0.4V~1.2V
Scanning Detction.
The buffer solution can be buffer solution commonly used in the art.
The beneficial effects of the present invention are:
The present invention is pioneering not to use any amidation chemical reagent, simple electric cyclic voltammetry is only used only, by solid-state
Carbon nanotube be bonded in electrode surface in a manner of being chemically bonded, synthesis v-SWCNT to glass-carbon electrode (GCE).Carbon nanotube
Ethylenediamine is successfully passed as bridge, the orderly controllable growth on GCE forms single-layer carbon nano-tube array.
Electrode prepared by the present invention is high to the detection sensitivity of clenbuterol hydrochloride, and detection speed is fast.The modified electrode preparation side
Method is novel, and decorative material is simple, safe operation.Application of the electrode in the residual detection of practical agriculture will be attempted in next step.
Detailed description of the invention
Fig. 1 is the circle detection of potassium bichromate solution oxidizing electrode 5,10,15,20 clenbuterol hydrochloride (SWV method button background).
Fig. 2 is the circle detection of potassium bichromate solution oxidizing electrode 1,2,3,4,5 clenbuterol hydrochloride (SWV method button background).
Fig. 3 is the circle detection of ethylenediamine solution modified electrode 5,10,15,20 clenbuterol hydrochloride (SWV method button background).
Fig. 4 is the circle detection of ethylenediamine solution modified electrode 20,25 clenbuterol hydrochloride (SWV method button background).
Fig. 5 is the circle detection of carbon nano tube modified electrode 5,10,15,20 clenbuterol hydrochloride (SWV method button background).
Fig. 6 is the circle detection of carbon nano tube modified electrode 20,25 clenbuterol hydrochloride (SWV method button background).
Fig. 7 is that carbon nano tube modified electrode detects clenbuterol hydrochloride (SWV reduction method button background) in pH1-8 environment.
Fig. 8 is that carbon nano tube modified electrode detects clenbuterol hydrochloride (SWV method button background) in pH1-8 environment.
Fig. 9 is that carbon nano tube modified electrode detects 16ppm clenbuterol hydrochloride (CV method) in pH1 environment.
Figure 10 is that carbon nano tube modified electrode detects 16ppm clenbuterol hydrochloride (SWV reduction method) in pH1 environment.
Figure 11 is that carbon nano tube modified electrode detects 16ppm clenbuterol hydrochloride (SWV oxidizing process) in pH1 environment.
Figure 12 be detection 10,30,60,90, (A be that SWV is restored for 120ppb clenbuterol hydrochloride its carbon nanotube peak current response condition
Figure, B are button background SWV also original image).
Figure 13 be detection 10,30,60,90, (A be that SWV is aoxidized for 120ppb clenbuterol hydrochloride its carbon nanotube peak current response condition
Figure, B are button background SWV oxidation figure).
Figure 14 be detect 10,30,60,90, (SWV is also for the linear relationship of 120ppb clenbuterol hydrochloride its carbon nanotube peak point current
Former method button background).
Figure 15 be detect 10,30,60,90, linear relationship (the SWV oxygen of 120ppb clenbuterol hydrochloride its carbon nanotube peak point current
Change method button background).
It is thin that Figure 16 is GCE, ethylenediamine/GCE, carbon nanotube/tri- kinds of ethylenediamine/GCE modified electrode method detect 16ppm
Meat essence (SWV reduction method).
It is thin that Figure 17 is GCE, ethylenediamine/GCE, carbon nanotube/tri- kinds of ethylenediamine/GCE modified electrode method detect 16ppm
Meat essence (SWV oxidizing process).
Figure 18 is modified electrode mirror surface photo.
Figure 19 is that SEM characterizes carbon nanotube/ethylenediamine/glass-carbon electrode.
Figure 20 is the preparation method flow diagram of carbon nano tube modified electrode of the present invention.
Specific embodiment
The preferred embodiment of the present invention is described in detail below in conjunction with embodiment.It will be appreciated that following real
Providing merely to play the purpose of explanation for example is applied, is not used to limit the scope of the present invention.The skill of this field
Art personnel without departing from the spirit and purpose of the present invention, can carry out various modifications and replace to the present invention.
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
Embodiment 1
One, reagent and instrument
Key instrument:
Electrochemical measurement uses CHl420A type electrochemical workstation (Shanghai Chen Hua instrument company)；Three-electrode system: glass carbon
Electrode is working electrode, and Hg/HgCI (saturation KCl solution) electrode is reference electrode, and platinum electrode is to electrode.
Reagent:
1,250 μ g/mL clenobuterol hydrochloride；
2, single-walled carbon nanotube (Shanghai ancient cooking vessel thunderbolt chemical industry)；
3, the sulfuric acid solution of 0.25mol/L；
4, mixed potassium dichromate: 2.5%K2CrO7+ 10%HNO3Solution, the transparent crocus of solution；
5, ethylenediamine mixed solution: 5mM ethylenediamine+0.1M KNO3Aqueous solution, it is whole colorless and transparent；
6, carbon nanotube mixed solution: 100mg SWCNTs passes through 2.6%HNO3Solution is heated to reflux 24 hours, is filtered off
Except nitric acid solution, carbon nanotube is mixed in 10mL 65%HNO3In the mixed solution of concentrated sulfuric acid 1:3 (V/V), ultrasonic treatment,
Ice bath temperature control reacts 4 hours.100mL ice water is poured into after reaction, is centrifugated, three times water cleaning carbon nanotube to neutrality,
105 DEG C dry to obtain functionalized carbon nano-tube；It weighs 2mg functionalization SWCNTs to be dissolved in 5mL water, adds 0.1M KNO3, with envelope
Membrana oralis is sealed, and is put into ultrasound 3-6 minutes in Ultrasound Instrument, is configured to carbon nanotube mixed solution；
7, electrolyte solution (pH1-8 buffer solution): connection pH acidometer power supply cleans glass electrode, with pH=4.0 and
PH=6.86 buffer carries out two o'clock calibration, finishes to instrument calibration, then wash clean glass electrode surveys pH solution.PH1,2 solution
Preparation: 0.1M KCl deionized water solution enriching sulfuric acid prepare；The solution of pH3,4,5,6,7,8 is prepared: 0.1M NaHPO4 3-, add
Enter the concentrated sulfuric acid or sodium hydroxide adjusts corresponding pH；
8, potassium ferricyanide mixed solution: by 0.1M KCl and 0.05mM k3Fe(CN)6Mixing, it is molten to be configured to the potassium ferricyanide
Liquid, the transparent bright green of solution.
Unless stated otherwise, solution used below is all configured mixed solution, and experimental water is deionization water three times.
Two, experimentation
1, it polishes and electrode and characterizes
With 0.3mm Al2O31:1 EtOH Sonicate 2-3min is used after glass-carbon electrode 3-5min is polished on smooth deerskin surface,
It is clean to take out electrode distilled water flushing, then with 0.05mm Al2O3Polish 3-5min, uses 1:1HNO3Solution, distilled water surpass respectively
Sound 2-3min；Take 0.25mol/L sulfuric acid solution 5mL to be put into the liquid bath of bottom, open instrument, connection electrode, with cyclic voltammetry (-
1.0V~1.0V) it scans to curve and stablizes, electrode is then taken out, wash with distilled water completely, is put into the prepared potassium ferricyanide
It is characterized in solution (- 0.2V~0.6V), the requirement of characterization is Δ E < 64V.
2, the pH of the circle number of optimization modification solution and electrolyte solution
Before optimizing electrode, other modification solution circle numbers in addition to optimizing solution are first set as 5 circles, electrolyte solution is
PH1 buffer solution.
The circle number of 2.1 optimization oxidation potassium bichromate solutions
Potassium bichromate solution 5mL is taken, is put into the liquid bath of bottom, connection electrode, the electrode polished is used into cyclic voltammetric respectively
1,2,3,4,5,10,15,20 circle of method (CV method) (0V~1.6V) scanning, ethylenediamine solution, carbon nano-tube solution, electrolyte solution
Etc. optimal conditions it is constant, detect clenbuterol hydrochloride.
The circle number of 2.2 optimization ethylenediamine solutions
Take ethylenediamine solution 5mL, be put into the liquid bath of bottom, connection electrode, by the electrode polished use respectively CV method (0V~
2.0V) scanning potassium bichromate solution 4 encloses, and scanning ethylenediamine solution 5,10,15,20,25 encloses, carbon nanotube, electrolyte solution etc.
Optimal conditions are constant, detect clenbuterol hydrochloride.
The circle number of 2.3 optimization carbon nano-tube solutions
CV method (0V~2.0V) scanning potassium bichromate solution 4 circle, ethylenediamine solution 20 is used to enclose respectively at the electrode polished
Afterwards, by carbon nanotube mixed solution in Ultrasound Instrument ultrasound 3-6min, be uniformly dispersed to it, take out 5mL be put into the liquid bath of bottom, even
Receiving electrode is passed through High Purity Nitrogen for bottom liquid bath, and scanning carbon nanotube 5,10,15,20,25 is enclosed, and electrolyte solution optimal conditions are constant,
Detect clenbuterol hydrochloride.
The pH of 2.4 optimization electrolyte solutions
The electrode modified is respectively put into the buffer of 5mL pH1-8, detects clenbuterol hydrochloride.
Three, results and discussion
1, the circle number of optimum optimization modification solution and the pH of electrolyte solution are explored
1.1 oxidation potassium bichromate solution circle numbers
First scanning potassium bichromate solution 5,10,15,20 encloses, and detects 16ppm clenbuterol hydrochloride, and the curve for being detained background carries out pair
Than such as Fig. 1 observes that electrode peak current response of clenbuterol hydrochloride after the circle of scanning 5 is best.Continue to optimize, scanning potassium bichromate is molten
Liquid 1,2,3,4,5 encloses, and detects 16ppm clenbuterol hydrochloride, and the curve for being detained background compares, and finds when scanning 4 is enclosed,
The peak current response of clenbuterol hydrochloride is best, such as Fig. 2, therefore the optimum oxidation circle number of potassium bichromate solution is set to 4 circles.
1.2 optimization ethylenediamine solution circle numbers
The electrode detection 16ppm clenbuterol hydrochloride enclosed with scanning ethylenediamine solution 5,10,15,20 compares it and detains lean meat after background
The peak of essence, when 20 circle, the peak current response of clenbuterol hydrochloride is best, such as Fig. 3 for discovery.Continue to optimize, scans ethylenediamine solution
20,25 circle detects 6ppm clenbuterol hydrochloride, compares its appearance situation, carbon nanotube and clenbuterol hydrochloride bottom peak when 25 circle of discovery is above
It essentially coincides, is unfavorable for detecting, therefore, the optimum optimization circle number of ethylenediamine solution is set to 20 circles, such as Fig. 4
1.3 optimization carbon nano-tube solution circle numbers
It scans carbon nano-tube solution 5,10,15,20 to enclose, detects 6ppm clenbuterol hydrochloride, compare it and detain the appearance situation after background,
It observes when scanning 20 is enclosed, the peak current response of clenbuterol hydrochloride is best, such as Fig. 5.Continue to optimize, scans carbon nano-tube solution
20,25 circle, detects the clenbuterol hydrochloride of 16ppm, observes its appearance situation, discovery is when scanning 20 is enclosed, the peak current of clenbuterol hydrochloride
Response is best, and reason is mainly that the circle number of scanning carbon nanotube is more, and amidation process probability is bigger, and it is full to have reached reaction
With reacting ring number cannot promote to react again, therefore not select 25 circles, such as Fig. 6.
1.4 optimizations electrolyte solution (pH1-8 buffer solution)
The electrode optimized is put into the clenbuterol hydrochloride that 6ppm is detected in the buffer solution of pH1-8, by resulting clenbuterol hydrochloride
Peak deducts blank background, and 8 kinds of peaks compare, and finds in the environment of pH1, and the peak current response of clenbuterol hydrochloride is best, as Fig. 7,
8, it is found that the pH the low more is conducive to detect, it was demonstrated that proton participates in redox, but in view of electrode is bonded with amide
The stability of conjunction, low pH are unfavorable for electrode and stablize, so, pH1 is suitable condition.
2, carbon nano tube modified electrode detects clenbuterol hydrochloride
Take 5mL pH1 blank buffer solvent, with cyclic voltammetry (CV method), square wave voltammetry (SWV method) (- 1.0V~
It 1.2V) scans, obtains blank control, add 16ppm clenbuterol hydrochloride and scan respectively, obtain the response condition at clenbuterol hydrochloride peak, such as scheme
9,10,11.For carbon nano tube modified electrode at pH 1, clenbuterol hydrochloride has a pair of of redox peaks in 0.42V or so.Using SWV method,
It was found that the sensitivity at SWV method peak rises significantly, this is because noise is less when scanning using SWV method, therefore, selection is used
SWV method is detected.
3, the peak that detection its carbon nanotube of various concentration clenbuterol hydrochloride goes out
(- 0.4V~1.2V) is scanned with SWV method, detects 10ppb, 30ppb, 60ppb, 90ppb, 120ppb clenbuterol hydrochloride, it is right
Than the peak of its carbon nanotube, such as Figure 12,13.
4, carbon nano tube modified electrode detection various concentration clenbuterol hydrochloride obtains linear according to the response of its carbon nanotube peak current
Relationship.
10ppb, 30ppb, 60ppb, 90ppb, 120ppb clenbuterol hydrochloride are detected respectively, and carbon nanotube peak has to be closed with lower linear
System, Figure 14,15.
The experimental results showed that the redox summit of carbon nanotube itself is increased with the addition of clenbuterol hydrochloride, and the two is in
Existing good linear relationship.In the clenobuterol hydrochloride Concentration Testing of 10-120ppb, peak current increases, and the R2 value of the two exists
99.4% or more.
5, GCE, ethylenediamine/GCE, carbon nanotube/ethylenediamine/GCE modified electrode detect clenbuterol hydrochloride, observe its appearance situation
PH1 blank buffer solvent is taken, the electrode of three kinds of distinct methods modification is scanned with SWV method (- 0.4V~1.2V), is obtained
Blank control out adds 16ppm clenbuterol hydrochloride, result is compared, such as Figure 16,17.
The experimental results showed that carbon nano tube modified electrode detects clenbuterol hydrochloride, peak current is responded relative to bare electrode, second two
Amine-modified electrode etc. greatly improves, and is stablized using the electrode that chemical synthesis mode is modified, not easily to fall off.Modified electrode is maintained at
After refrigerator one month, electrode is almost unchanged to clenbuterol hydrochloride testing result.
6, during modified glassy carbon electrode electrode characterization
Such as Figure 18, electrode surface color is completely different after bare electrode is modified ethylenediamine and carbon nanotube.Bare electrode is
Metallic silver color, dark yellow is presented after linking top electrode in ethylenediamine, and presents after carbon nanotube and ethylenediamine crosslinking sapphire blue
Non-ferrous metal gloss.The process of entire color change demonstrates ethylenediamine and has linked top electrode with carbon nanotube.In order to further demonstrate,prove
The carbon nano-tube modified validity of real electrosynthesis is attempted to directly link carbon nanotube, as a result without ethylenediamine link step
Electrode surface fails that royalblue metallic luster is presented.Experimental result again shows that the core of electro synthesis is the formation of amido bond.
Figure 19 is SEM characterization carbon nanotube/ethylenediamine/glass-carbon electrode, it is seen that the apparent carbon pipe of electrode surface exists.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, fall within the scope of the claimed invention without departing from theon the basis of the spirit of the present invention.
Claims (6)
1. a kind of preparation method of carbon nano tube modified electrode, which comprises the steps of:
1) glass-carbon electrode is enclosed in potassium bichromate solution with cyclic voltammetry scanning 4~5, scanning range is 0V~1.6V, is swept
Retouching speed is 0.1~0.5V/s；
2) step 1) the electrode obtained to be enclosed in ethylenediamine solution with cyclic voltammetry scanning 20, scanning range is 0V~2.0V,
Scanning speed is 0.1~0.5V/s；
3) by step 2) the electrode obtained in carbon nano-tube solution with cyclic voltammetry scanning 20 circle, scanning range be 0V~
2.0V, scanning speed are 0.1~0.5V/s；
The concentration of the potassium bichromate solution is 2.5~10%, and the concentration of the ethylenediamine solution is 5~15mM, and the carbon is received
The concentration of mitron solution is 2.5~10g/L.
2. the method according to claim 1, wherein the glass-carbon electrode use preceding carry out grinding process, and
It is scanned with cyclic voltammetry to curve and is stablized under the conditions of -1.0V~1.0V, take out electrode and cleaned, be put into potassium ferricyanide solution
In characterized under the conditions of -0.2V~0.6V, the requirement of characterization is Δ E < 64V.
3. according to the method described in claim 2, it is characterized in that, the grinding process specifically:
With 0.3mm Al2O31:1 EtOH Sonicate 2-3min is used after glass-carbon electrode 3-5min is polished on smooth deerskin surface, is taken out
Electrode distilled water flushing is clean, then with 0.05mm Al2O3Polish 3-5min, uses 1:1HNO3Solution, distilled water difference ultrasound 2-
3min。
4. the carbon nano tube modified electrode that the described in any item methods of claims 1 to 3 are prepared.
5. application of the carbon nano tube modified electrode as claimed in claim 4 in terms of detecting clenbuterol hydrochloride, which is characterized in that will be to be measured
Sample is dissolved in the buffer solution of pH1~8, and with cyclic voltammetry or square wave voltammetry, inspection is scanned under the conditions of -1.0V~1.2V
It surveys.
6. application according to claim 5, which is characterized in that sample to be tested is dissolved in the buffer solution of pH1, uses square wave
Voltammetry, Scanning Detction under the conditions of -0.4V~1.2V.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103257167A (en) * | 2012-12-14 | 2013-08-21 | 苏州大学 | Electrode modification method for adopting nucleic acid aptamers for high sensitivity detection of tumor cells |
| CN103854881A (en) * | 2012-11-30 | 2014-06-11 | 海洋王照明科技股份有限公司 | Preparation method for graphene/carbon nano-tube combined electrode |
| CN104846486A (en) * | 2015-03-27 | 2015-08-19 | 江西师范大学 | Preparation of carbon nano fiber composite material coated by nitrogen-doped carbon nanotube and application thereof |
Family Cites Families (1)
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|---|---|---|---|---|
| BR102014001074B1 (en) * | 2014-01-16 | 2021-12-28 | Universidade Federal De Alfenas - Unifal - Mg | CARBON NANOTUBES RESTRICTED TO BINDING WITH MACROMOLECULES THROUGH ALBUMIN COATING (RACNT-BSA) |
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2016
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103854881A (en) * | 2012-11-30 | 2014-06-11 | 海洋王照明科技股份有限公司 | Preparation method for graphene/carbon nano-tube combined electrode |
| CN103257167A (en) * | 2012-12-14 | 2013-08-21 | 苏州大学 | Electrode modification method for adopting nucleic acid aptamers for high sensitivity detection of tumor cells |
| CN104846486A (en) * | 2015-03-27 | 2015-08-19 | 江西师范大学 | Preparation of carbon nano fiber composite material coated by nitrogen-doped carbon nanotube and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| Aligned single-walled carbon nanotubes array electrode:Fabrication, characterization and application;Xu Zhi Zhang et.al;《Chinese Chemical Letters》;20090131;第20卷;第76-78页 |
| Directed Assembly of End-Functionalized Single Wall Carbon Nanotube Segment;Erika Penzo et.al;《NANO LETTERS》;20150904;第15卷;第6547-6552页 |
| Immobilization of Hemoglobin on the Gold Colloid Modified Pretreated Glassy Carbon Electrode for Preparing a Novel Hydrogen Peroxide Biosensor;Yang Liu et.al;《Appl Biochem Biotechnol》;20080830;第152卷;第418、420-421页 |
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