CN105806923B - A kind of preparation method and application of the nano combined electrochemical sensing material of carbon nano-tube/titanic oxide/carboxymethyl chitosan - Google Patents
A kind of preparation method and application of the nano combined electrochemical sensing material of carbon nano-tube/titanic oxide/carboxymethyl chitosan Download PDFInfo
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- CN105806923B CN105806923B CN201610156827.0A CN201610156827A CN105806923B CN 105806923 B CN105806923 B CN 105806923B CN 201610156827 A CN201610156827 A CN 201610156827A CN 105806923 B CN105806923 B CN 105806923B
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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
- 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
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Abstract
The invention discloses a kind of preparation method and application of the nano combined electrochemical sensing material of carbon nano-tube/titanic oxide/carboxymethyl chitosan, this method is by the chemical property and nano-titanium dioxide (TiO of multi-walled carbon nanotube (MWCNTs)2) electrocatalysis characteristic and the film forming ability of carboxymethyl chitosan (CMCS) be combined, MWCNTs@TiO have been prepared by solgel reaction in situ and solution blended process2/ CMCS nanocomposites.MWCNTs and butyl titanate are first prepared into MWCNTs@TiO by the present invention2Nanocomposite, it is again that the nanocomposite of preparation and CMCS is compound and be assembled into film with certain proportion, it is applied to the detection of persticide residue in food as sensing element, by regulating and controlling the ratio of carbon nanotube and titanium dioxide in conducing composite material, the electrochemical sensor material that can detect metrifonate residual quantity in food is finally obtained.
Description
Technical field
The invention belongs to nanocomposites and technical field of function materials, and in particular to a kind of solidifying using colloidal sol-in situ
Glue method prepares MWCNTs TiO2The methods and applications of the nano combined electrochemical sensing materials of/CMCS.
Background technology
Metrifonate is widely applied a kind of organophosphorus pesticide in agricultural production, it can be with the work of acetylcholine esterase inhibition
Property, lead to a large amount of accumulations of nerves within the body transmitter acetylcholine, so as to cause a series of nerves reaction, for example, generate nausea,
The poisoning symptoms such as headache, inability, uncomfortable in chest, it is serious to lead to death.After metrifonate pesticide, the alkalinity such as soap cannot be used
Detergent, which washes one's face, washes one's hands, and otherwise can cause to be poisoned, thus it is dead, this is because metrifonate becomes volatility in alkaline solution
Very strong DDVP, 10 times bigger than metrifonate of toxicity of DDVP or more.Therefore, if metrifonate is residual in environment and food
Stay accumulation, the health of the mankind can be caused it is direct or potentially hazardous, so being used for quickly detecting to it extremely important.Traditional
Detection method is mainly chromatography, for example, gas-chromatography and flame spectrometry (GC-FPD), gas chromatography-mass spectrography (GC-
MS), high performance liquid chromatography diode array (HPLC-DAD), liquid-phase chromatographic analysis-mass spectrography (LC-MS) etc., but these
Method needs professional to operate, and sample treatment is complicated, takes, and is unsuitable for carrying out Site Detection etc..And electrochemical sensing utensil
There is high sensitivity, easy to operate, and spend the advantages that less, is widely used in the quick detection of pollutant.In addition to this, it
Also there is instrument to be easy to micromation, intelligence, the detection and analysis for scene provide possibility.Chemically modified electrode is current electrification
It learns, research field very active in terms of Electroanalytical Chemistry, therefore, the research of various electrode modified materials is also just come into being.
Nano-TiO2Have many advantages, such as that small particle, large specific surface area, absorbent properties are good and photocatalysis performance is good, also has both table
The Optimality that face activity is big, good dispersion, thermal conductance good and obtained effect suspension stabilization and does not have harm etc. many human body
Energy.TiO2As a kind of important semi-conducting material high activity is widely used in because of its unique physical and chemical properties
The fields such as preparation, solar cell assembling and the photocatalytic degradation organic matter of modified electrode.Multi-walled carbon nanotube (MWCNTs) has
Excellent mechanical performance, chemical stability, chemical property, optical property, heat-conductive characteristic etc., large specific surface area, suction
Attached property is strong, and stability is high, is had received widespread attention in the fields such as materialogy and biomedicine.But due to carbon nanotube in water and
Dispersibility is poor in organic solvent, uses TiO2It is next carbon nano-tube modified, it is not only exaggerated this feature of carbon nanotube, but also
The electrically separated and electrocatalysis characteristic of carbon nanotube is combined with the recognition capability of boiomacromolecule, passes through sol-gel in situ
Reaction method can prepare highly sensitive MWCNTs@TiO2Nano electrochemical sensor material.IN-SITU SOL-GEL has anti-
The advantage for answering mild condition two-phase mixtures relatively uniform, operation are easy, can react at room temperature, and condition is easy to control, synthesis production
Article matter is high, and the interpenetrating networks knot that can be accurately controlled, and be formed with inorganic composition organic in recombination reaction
Structure can play very strong restrictive function to the separation between organic phase and inorganic phase, by the ratio for changing organic and inorganic component
Example to synthesize a series of composite materials of a small amount of inorganic material-modified organic material or a small amount of organic material modified inorganic material, this
A little advantages show huge potentiality in terms of preparing functional composite material.
Chitosan is because it is in addition to good biocompatibility and biodegradability and antibacterial, hemostasis, promoting wound
There are preferable film forming, gas permeability and adsorptivity outside the various functions such as healing.In medicine, environment, cosmetics, food service industry,
And it is widely used in each field such as chemical industry, agricultural.But since it is only soluble in diluted acid, not soluble in water and alkaline solution is also insoluble
In common organic solvent, cause its application by certain restriction.For the solubility property for changing it, many researchers are tied
Structure is modified, and a series of chitosan derivatives can be prepared using the chemical property of chitosan.Chitosan is such as subjected to carboxylic
It methylates, its dissolubility can be substantially improved.Present invention utilizes the good water solubility of carboxymethyl chitosan (CMCS) and film forming
Property with MWCNTs@TiO2Nanocomposite is combined, and is prepared for MWCNTs@TiO2This novel nanocomposites of/CMCS
And it is assembled into film and the residual quantity of metrifonate is detected.
Invention content
The purpose of the present invention is to provide a kind of nano combined electrochemistry of carbon nano-tube/titanic oxide/carboxymethyl chitosan
The preparation method and application of sensing material improve carbon nanotube in nanocomposite by the method for sol gel reaction
In easily reunite, bad dispersibility, thus the shortcomings of electrochemical sensing is poor；By changing carbon nanotube and titanium dioxide in composite wood
Mass fraction in material obtains the electrochemical sensing material of optkmal characteristics, and metrifonate in food can be detected by, which finally obtaining, remains
Measure the electrochemical sensor material of detection.
To achieve the goals above, the technical solution adopted in the present invention is：A kind of carbon nano-tube/titanic oxide/carboxylic first
The preparation method of the nano combined electrochemical sensing material of base enclosure glycan, specific preparation process are as follows：
Step（1）：Multi-walled carbon nanotube/titanium dioxide (MWCNTs@TiO are made by sol gel reaction in situ2) receive
Nano composite material, the wherein adding proportion of raw material MWCNTs and butyl titanate are 25% ~ 75%:75%~25%；
Step（2）：By step（1）The MWCNTs@TiO of middle preparation2Composite material is dispersed in carboxymethyl chitosan (CMCS)
Aqueous solution in, obtain MWCNTs@TiO through ultrasonication at 60 DEG C2The nano combined electrochemical sensing materials of/CMCS, wherein more
Wall carbon nano tube, nano-titanium dioxide, carboxymethyl chitosan adding proportion be 5% ~ 30%:15%~10%:80% ~ 60% or 15% ~
10%:5%~30%:80%~60%；Or MWCNTs@TiO2Adding proportion with CMCS is 20% ~ 40%:80%~60%.
A kind of above-mentioned carbon nano-tube/titanic oxide/carboxymethyl chitosan (MWCNTs@TiO2/ CMCS) nano combined electrification
Learn the preparation method of sensing material, the MWCNTs@TiO2The optimal set of/CMCS electrochemical sensing materials becomes multi-wall carbon nano-tube
Pipe 10%, nano-titanium dioxide 10%, carboxymethyl chitosan 80%.
A kind of carbon nano-tube/titanic oxide/carboxymethyl chitosan (MWCNTs@TiO2/ CMCS) nano combined electrochemistry passes
The application for feeling material, by a kind of above-mentioned carbon nano-tube/titanic oxide/carboxymethyl chitosan (MWCNTs@TiO2/ CMCS) nanometer is multiple
Close step in the preparation method of electrochemical sensing material（2）Prepared MWCNTs@TiO2/ CMCS electrochemical sensings material can group
Dress is electrochemical sensing thin-film component, and applied to the detection of the residual quantities such as pesticide metrifonate in food, and detection is limited down to 3.3
×10-12Mol/L has very high sensibility to trace residue pesticide.
Compared with prior art, the invention has the advantages that：1, the present invention is good using carboxymethyl chitosan CMCS
Water-soluble and film forming and MWCNTs@TiO2Nanocomposite is mutually compound, is prepared for MWCNTs@TiO2/ CMCS novel nanos are multiple
Condensation material, carbon nanotube or MWCNTs@TiO2Nanocomposite is able in system stably dispersing well；2, pass through regulation and control
The composition ratio of titanium dioxide, carbon nanotube, carboxymethyl chitosan regulates and controls and optimizes the electrification of nanocomposite well
Performance is learned, the good optimum amount of electrochemical behavior is found；In particular, present invention incorporates TiO2Electric catalyticing characteristic, make it
Chemical property is optimized, and the electrochemical sensing film of optkmal characteristics is obtained.；3, nano compound film element of the present invention is available
The detection of persticide residue in food, detection are limited down to 3.3 × 10-12Mol/L has trace residue pesticide very high
Sensibility；And within the scope of comparatively wide pesticide concentration, good line is presented with metrifonate concentration in modified electrode oxidation peak current
Sexual intercourse.
Description of the drawings
The present invention is specifically described below by attached drawing and in conjunction with the embodiments, wherein content shown in attached drawing is only used for the present invention
Explanation, without constitute to the present invention in all senses on limitation.
Fig. 1 is MWCNTs@TiO of the present invention2The synthesis schematic diagram of/CMCS nanocomposites.
Fig. 2 is (a) MWCNTs, (b) MWCNTs@TiO in the embodiment of the present invention2, (c) MWCNTs@TiO2/ CMCS is multiple
Condensation material dispersion stabilization measurement result.
Fig. 3（A）For Differential Pulse Voltammetry (DPV) curve of various concentration metrifonate solution in the embodiment of the present invention, Fig. 3
（B）For the linear relationship between metrifonate solution concentration and peak current.
Fig. 4 is the electrochemical behavior of different materials modified electrode in the embodiment of the present invention.
Fig. 5 (A) and the MWCNTs@TiO that (B) is different proportion composition2/CMCS/GCE nanocomposite modified electrodes
Electrochemical behavior testing result.
Fig. 6（A）With（B）For the electrochemical behavior testing result in difference pH electrolyte solutions in the embodiment of the present invention.
Fig. 7（A）With（B）For MWCNTs@TiO of the present invention2/ CMCS/GCE composite materials are electrolysed in 0.2M PBS (pH=7)
The linear relationship between electrochemical behavior and peak current and sweep speed in liquid under different scanning rates.
Table 1 is MWCNTs@TiO in the present invention2/ CMCS/GCE nanocomposite modified electrodes are for authentic sample
Testing result.
Specific implementation mode
It elaborates below to the embodiment of the present invention：The present embodiment is carried out lower based on the technical solution of the present invention
Implement, gives detailed embodiment and specific operating process.It should be pointed out that those skilled in the art
For, without departing from the inventive concept of the premise, several variations and modifications can also be made, these belong to protection of the present invention
Range.
Embodiment 1：
A kind of preparation method of the nano combined electrochemical sensing material of carbon nano-tube/titanic oxide/carboxymethyl chitosan,
It is characterized in that it is completed by following multistep reaction, preparation process schematic diagram is as shown in Figure 1.It is as follows：
Step（1）：By a certain amount of multi-walled carbon nanotube after drying, ultrasonic disperse 1-2h forms A in absolute ethyl alcohol
A certain amount of butyl titanate is dissolved in formation B liquid in absolute ethyl alcohol, B liquid is slowly added drop-wise in A liquid, in dropwise addition by liquid
In the process, sequentially add a certain amount of glacial acetic acid solution, 95% ethyl alcohol and 0.1M salpeter solutions, be added dropwise ammonium hydroxide adjust pH be about
7,6 h are persistently stirred, uniform nanometer MWCNTs@TiO are formed2Mixed solution is stood for 24 hours, after the solvent is volatilized, is obtained
To the gel of needs；Gel is collected on culture dish, 80 DEG C of drying in air dry oven, grinding are placed on, horse takes in stove 450 DEG C
Calcine 4h；Obtain the MWCNTs@TiO of black powder2Nanocomposite；The specific dosage and preparation technology parameter of each raw material
It is as follows：
A, the preparation of nano-titanium dioxide
A liquid：3.4ml butyl titanates are measured, 16ml absolute ethyl alcohols are added thereto, stir about 30min keeps it fully mixed
It is even；
B liquid：The glacial acetic acid of 3ml is added in the nitric acid of 5ml 0.1M, adds the ethyl alcohol of 16.5ml 95%, stir about
30min makes its mixing；
A liquid is added in constant pressure funnel, A liquid is added slowly in B liquid while stirring, add ammonium hydroxide adjust pH value of solution be about
7, continue to stir the leucosol that 60min forms homogeneous transparent, after stirring 6h, is placed at room temperature for for 24 hours, after the solvent is volatilized, obtains
The gel needed.Gel is collected on culture dish, is placed on 80 DEG C of drying in air dry oven, grinding, horse, which is taken in stove, forges for 450 DEG C
Burn 4h；Obtain the nano-TiO of white powder2。
B, with reference to nano-TiO prepared above2Process, by a certain amount of MWCNTs（With nano-titanium dioxide precentagewise
25%~75%:75%~25%）1 ~ 2h of ultrasonic disperse in absolute ethyl alcohol, obtains C solution, and a certain amount of butyl titanate is dissolved in
In absolute ethyl alcohol, stirring makes its mixing, obtains D liquid.D liquid is placed in constant pressure funnel, is slowly dropped into C liquid, is stirred continuously,
A certain amount of acetic acid solution is added, 95% ethyl alcohol and 0.1M salpeter solutions, it is about 7 that ammonium hydroxide, which is added dropwise, and adjusts pH, lasting to stir
60h forms uniform nanometer MWCNTs@TiO2Mixed solution is stood for 24 hours, and after the solvent is volatilized, what is needed is solidifying
Glue.Gel is collected on culture dish, 80 DEG C of drying in air dry oven, grinding are placed on, horse takes 450 DEG C of calcining 4h in stove；
To the nanometer MWCNTs@TiO of black powder2Composite material.
Step（2）：By step（1）The MWCNTs@TiO of middle preparation2Nanocomposite 0.03g ~ 0.08g is distributed to
0.17g ~ 0.12g carboxymethyl chitosans（CMCS）Aqueous solution in (MWCNTs@TiO2Addition accounts for 15% ~ 40%, CMCS of total amount
Addition be total amount 85% ~ 60%）, 1 ~ 2h of ultrasonic disperse under the conditions of 60 DEG C obtains finely dispersed mixed liquor, disperses
Then stability according to the difference ratio of taking of multi-walled carbon nanotube and nano-titanium dioxide as shown in Fig. 2, produce different originals
The target sample for expecting ratio of components, is assembled into electrochemical sensing film, and it is best to study the corresponding each raw material of its optimal chemical property
Dosage and detection to pesticide residue ingredient.
Wherein, the specific preparation process of CMCS is：The chitosan of 10.0g is added to the NaOH that 50mL mass fractions are 50%
In solution, alkalize 12h at room temperature, then removes excessive aqueous slkali, and the chitosan of alkalization is added in the flask of 250mL,
The chloroacetic acid of 10.0g is dissolved into the isopropanol of 40.0mL simultaneously, is dropwise added drop-wise in the flask containing chitosan；Shape
At mixed solution stirred at 60 DEG C, flow back 4h, then neutralized with dilute hydrochloric acid；Mixed liquor after reaction precipitates in acetone
And filtering；Sediment is cleaned repeatedly with 75% ethyl alcohol, until no chloroacetic acid exists；Again by crude product washes of absolute alcohol,
Then it is dried until constant weight at 35 DEG C.
（3）A kind of above-mentioned MWCNTs@TiO2The preparation method and application of the nano combined electrochemical sensing materials of/CMCS, profit
MWCNTs@TiO are prepared with obtained target sample2/ CMC/GCE modified electrodes and relevant comparative's electrode, the embodiment of the present invention are adopted
With the buffer solution of cyclic voltammetry（PBS）By the H of 0.2M3PO4, the NaH of 0.2M2PO4, the Na of 0.2M2HPO4It prepares, uses
The NaOH of the HCl and 1.0M of 1.0M adjust pH；Electrolyte solution by 0.2M PBS buffer solutions and 0.2M KCl solution compositions；
Redox probe solution by 2.0mmol K3Fe(CN)6/K4Fe(CN)6/KCl(1:1:100,mol:mol:Mol it) forms.It will
Bare electrode（GCE）Successively with 0.3 μm and 0.05 μm of Al2O3Powder is polished to minute surface, is waited for absolute ethyl alcohol and distilled water ultrasonic cleaning
With.The sample ultrasonic made is disperseed into 30min, 6 μ l of target sample suspension is taken uniformly to drip on the surfaces GCE handled well, it is quiet
It sets, waits for that it is dried；In order to be distinguished, respectively by nano-TiO2, MWCNTs, CMCS, MWCNTs@TiO2, MWCNTs@CMCS are mono-
Solely dispersion, prepares TiO as stated above2/ GCE, MWCNTs/GCE, CMCS/GCE, MWCNTs@TiO2/ GCE, MWCNTs@
CMCS/GCE, MWCNTs@TiO2/ CMCS/GCE electrodes are for use；All detections carry out all in electrochemical workstation.
Embodiment 2：
On the basis of embodiment 1, by the experimental procedure（1）MWCNTs and nano-titanium dioxide ratio tune used in b
Whole is 50%:50%；
Step（2）：By step（1）The MWCNTs@TiO of middle preparation2Nanocomposite 0.04g is distributed to 0.16g carboxylic first
Base enclosure glycan（CMCS）Aqueous solution in；I.e. by step（2）Middle MWCNTs@TiO2It is adjusted to 20% with the ratio of CMCS:80%,
Its step is same as Example 1, obtains MWCNTs@TiO2The nano combined electrochemical sensing materials of/CMCS.
Embodiment 3：
On the basis of embodiment 1, by the experimental procedure（1）MWCNTs and nano-titanium dioxide ratio tune used in b
Whole is 33%:67%；Step（2）Middle MWCNTs@TiO2It is adjusted to 15% with the ratio of CMCS:85%, other steps and 1 phase of embodiment
Together, MWCNTs@TiO are obtained2The nano combined electrochemical sensing materials of/CMCS.Test result is shown in the curve a in Fig. 5 (A).
Embodiment 4：
On the basis of embodiment 1, by the experimental procedure（1）MWCNTs and nano-titanium dioxide ratio tune used in b
Whole is 60%:40%；Step（2）Middle MWCNTs@TiO2It is adjusted to 25% with the ratio of CMCS:75%, other steps and 1 phase of embodiment
Together, MWCNTs@TiO are obtained2The nano combined electrochemical sensing materials of/CMCS.Test result is shown in the curve c in Fig. 5 (A).
Embodiment 5：
On the basis of embodiment 1, by the experimental procedure（1）MWCNTs and nano-titanium dioxide ratio tune used in b
Whole is 75%:25%；Step（2）Middle MWCNTs@TiO2It is adjusted to 40% with the ratio of CMCS:60%, other steps and 1 phase of embodiment
Together, MWCNTs@TiO are obtained2The nano combined electrochemical sensing materials of/CMCS.Test result is shown in the curve d in Fig. 5 (A).
Embodiment 6：
On the basis of embodiment 1, by the experimental procedure（1）MWCNTs and nano-titanium dioxide ratio tune used in b
Whole is 67%:33%；Step（2）Middle MWCNTs@TiO2It is adjusted to 15% with the ratio of CMCS:85%, other steps and 1 phase of embodiment
Together, MWCNTs@TiO are obtained2The nano combined electrochemical sensing materials of/CMCS.Test result is shown in the curve a in Fig. 5 (B).
Embodiment 7：
On the basis of embodiment 1, by the experimental procedure（1）MWCNTs and nano-titanium dioxide ratio tune used in b
Whole is 40%:60%；Step（2）Middle MWCNTs@TiO2It is adjusted to 25% with the ratio of CMCS:75%, other steps and 1 phase of embodiment
Together, MWCNTs@TiO are obtained2The nano combined electrochemical sensing materials of/CMCS.Test result is shown in the curve c in Fig. 5 (B).
Embodiment 8：
On the basis of embodiment 1, by the experimental procedure（1）MWCNTs and nano-titanium dioxide ratio tune used in b
Whole is 25%:75%；Step（2）Middle MWCNTs@TiO2It is adjusted to 40% with the ratio of CMCS:60%, other steps and 1 phase of embodiment
Together, MWCNTs@TiO are obtained2The nano combined electrochemical sensing materials of/CMCS.Test result is shown in the curve d in Fig. 5 (B).
In order to prove that beneficial effects of the present invention, inventor use the CHI660E of Shanghai Chen Hua Instrument Ltd. production
Type electrochemical workstation detects the chemical property and practical application performance of embodiment sample, experimental result such as Fig. 3
Shown in~7.
Fig. 3（A）Certain density metrifonate solution is detected using Differential Pulse Voltammetry (DPV).In pH=7
PBS electrolyte in, when accumulating potential be 0.9 ~ 1.15V, current potential increment 0.001V, amplitude 0.025V, pulse width 0.5s, arteries and veins
When rushing period 0.5s, the oxidation peak current of metrifonate is with its concentration 1 × 10-5~1×10-11In good in the range of mol/L
Linear relationship, linear equation are iP (μ A)=0.5077logC-6.3407；Related coefficient is 0.9915, such as Fig. 3（B）It is shown.
Use MWCNTs@TiO2/ CMCS/GCE modified electrodes are under optimal condition to three apple, mushroom and cucumber samples
Product carry out DPV measurement using calibration curve method, and each sample is measured 5 times, is averaged, measurement result is as shown in table 1.By table 1
As it can be seen that MWCNTs@TiO disclosed by the invention2The nano combined electrochemical sensing materials of/CMCS are used in apple, mushroom and cucumber
The measurement of pesticide metrifonate content has low standard deviation (apple 0.7% ~ 3.9%；Mushroom 0.8 ~ 8.1%；Cucumber 0.6% ~
And the high rate of recovery (apple 82.0 ~ 96.5% 7.3%)；Mushroom 72.0 ~ 96.0%；Cucumber 78.0 ~ 98.0%).Therefore, the present invention is public
The MWCNTs@TiO opened2The nano combined electrochemical sensing materials of/CMCS can be used for the inspection of metrifonate residual quantity in authentic sample
It surveys.
The measurement result of metrifonate content in 1 authentic sample of table
A and b is the number of horizontal survey, in the experiment (a=5)
In order to study the electrocatalysis characteristic of different composite material, Fig. 4 gives to be existed by the modified electrode of these material preparations
PBS（pH=7）In electrolyte solution, the cyclic voltammetry curve under the sweep speed of 40 mV/ s.From fig. 4, it can be seen that probe from
Son is in MWCNTs@TiO2Redox peak current on/CMCS/GCE is apparent, and MWCNTs/GCE, CMCS/GCE,
MWCNTs@TiO2Almost without redox current on/GCE and MWCNTs/CMCS/GCE.This illustrates electronics in MWCNTs@
TiO2Transfer rate on/CMCS laminated film modified electrodes is most fast, is conducive to active material and redox reaction occurs, to
So that redox peak current sharply increases.At the same time, it is observed that in MWCNTs@TiO2/ CMCS/GCE modified electrodes
On oxidation and reduction peak current it is symmetrical, spike potential difference is smaller, illustrates that electrochemistry of the probe ion on this modified electrode is anti-
It should be a reversible process.And in TiO2In spite of apparent redox current on/GCE modified electrodes, but aoxidizes and restore
Peak current symmetry is poor, and spike potential difference is larger, therefore the invertibity of electrochemical reaction of the probe ion on this modified electrode is not
And MWCNTs@TiO of the present invention2/ CMCS/GCE modified electrodes.
MWCNTs@TiO2The electrocatalysis characteristic of the nano combined electrochemical sensing materials of/CMCS is by system composition ratio
It influences, as shown in Figure 5.It can be with it is clear to see that keeping TiO from Fig. 5 (A)2Content is constant, and nanotube content is to redox spy
Property has a significant impact.The carbon nanotube (5%) of low content does not generate redox current, and excessively high content of carbon nanotubes (30%)
Also redox current is made to reduce.When content of carbon nanotubes is in 10% and 15%, strong peak current illustrates, in this composition
Electrochemical oxidation or reduction reaction easily occur for lower composite material.Also less than c curves due to b curve reduction peak potentials (0.211V)
Parent peak potential (0.256V), reduction peak are obviously born and have moved 45mV, and oxidation wave is close with reduction wave height, and symmetry is good, shows
The composite film material of content of carbon nanotubes 10% has good electrochemical redox performance, and electroactive material invertibity
Well.From Fig. 5 (B) can with find out, four curves all produce redox peaks, it is evident that c curve redox peaks are weaker, and
The redox peak current highest of b curves, oxidation peak and reduction peak symmetry it is good, and between potential difference there was only 100mV, this
Illustrate that the good reversibility of the electrochemical sensor of the electrochemical copolymerization thin-film material of ratio composition, electrocatalysis characteristic are good.Cause
This, compound 10% TiO of 10% MWCNTs2, and the MWCNTs@TiO that 80% CMCS is prepared are added2/ CMCS nano compound films are repaiied
Decorations anodizing reduction peak current is apparent, good reversibility, and chemical property is good.
Electrocatalysis characteristic of the composite material modified electrode in the PBS electrolyte solutions of different pH is as shown in Figure 6.In pH=7
Electrolyte solution in, i.e., shown in (c) curve, composite material modified electrode have apparent redox peaks, and aoxidize and
Reduction peak current is symmetrical, and spike potential difference is smaller, illustrate electrochemical reaction of the probe ion on this modified electrode be one can
Inverse process.It is therefore preferable that the electrolyte solutions of pH=7 are as supporting electrolyte.
Sweep speed has an impact the electrocatalysis characteristic of composite material modified electrode.Fig. 7 is MWCNTs@TiO2/CMCS/
GCE composite materials modified electrode sweeps cyclic voltammogram and peak current under speed in 0.2M PBS (pH=7) electrolyte in difference
Linear relationship between sweep speed.From figure 7 it can be seen that with the increase of sweep speed, oxidation peak current is weakening, oxidation
The current potential at peak is shuffled；And it is in good linear relationship between peak current and sweep speed, linear equation is respectively Ipc
(μ A)=0.1230V+0.0026 (r=0.9651) and Ipa (μ A)=- 0.1204V-0.0025 (r=0.9912).Comprehensive analysis,
The rate of hastening is swept in 40mV/s, the electrochemical catalysis performance of composite material is best.
Therefore, multi-walled carbon nanotube, nano-titanium dioxide, carboxymethyl chitosan usage amount be followed successively by 10%, 10%, 80%
When, the MWCNTs@TiO of preparation2/ CMCS nano compound film modified electrode redox peaks are apparent, good reversibility, electrochemistry
It can be good；Electrochemical reaction of the probe ion on this modified electrode is a reversible process.It finds simultaneously in 40mV/s electric scannings
Under rate, under conditions of the electrolyte solutions of pH=7 is as supporting electrolyte, the electrochemistry of composite material prepared by the present invention is urged
It is best to change performance.
The above is the preferred exemplary applications of the present invention, and not limitation of the present invention, every according to the technology of the present invention
Main points make it is simple modification, structure change variation all belong to the scope of protection of the present invention within.
Claims (3)
1. a kind of preparation method of the nano combined electrochemical sensing material of carbon nano-tube/titanic oxide/carboxymethyl chitosan, special
Sign is that specific preparation process is as follows：
Step（1）：Multi-walled carbon nanotube/titania gel is made by sol gel reaction in situ, then dries the gel
It is ground after dry, then through 450 DEG C of temperature lower calcinations, 4 hours obtained multi-walled carbon nanotube/titanic oxide nano compound materials, Central Plains
Expect that the adding proportion of multi-walled carbon nanotube and butyl titanate is 25% ~ 75%:75%~25%；
Step（2）：By step（1）Multi-walled carbon nanotube/composite titania material of middle preparation is dispersed in carboxymethyl chitosan
Aqueous solution in, obtain the nano combined electrochemistry of carbon nano-tube/titanic oxide/carboxymethyl chitosan through ultrasonication at 60 DEG C and pass
Feel material, wherein multi-walled carbon nanotube, nano-titanium dioxide, carboxymethyl chitosan adding proportion be 5% ~ 30%:15%~10%:
80% ~ 60% or 15% ~ 10%:5%~30%:80%~60%；Or the addition of multi-walled carbon nanotube/titanium dioxide and carboxymethyl chitosan
Ratio is 20% ~ 40%:80%~60%.
2. a kind of nano combined electrochemical sensing of carbon nano-tube/titanic oxide/carboxymethyl chitosan according to claim 1
The preparation method of material, it is characterised in that：The nano combined electrochemistry of carbon nano-tube/titanic oxide/carboxymethyl chitosan passes
Feeling the optimal set of material becomes multi-walled carbon nanotube 10%, nano-titanium dioxide 10%, carboxymethyl chitosan 80%.
3. a kind of application of the nano combined electrochemical sensing material of carbon nano-tube/titanic oxide/carboxymethyl chitosan, feature
It is：By step in claim 1（2）The prepared nano combined electrochemistry of carbon nano-tube/titanic oxide/carboxymethyl chitosan
Sensing material can be assembled as electrochemical sensing thin-film component, and applied to the detection of pesticide metrifonate residual quantity in food, inspection
Limit is surveyed down to 3.3 × 10-12Mol/L has very high sensibility to trace residue pesticide.
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