CN105806923A - Preparation method and application of carbon nanotube/ titanium dioxide/carboxymethyl chitosan nanometer composite electrochemical sensing material - Google Patents
Preparation method and application of carbon nanotube/ titanium dioxide/carboxymethyl chitosan nanometer composite electrochemical sensing material Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a carbon nanotube/ titanium dioxide/carboxymethyl chitosan nanometer composite electrochemical sensing material. In the method, the electrochemical performance of multi-walled carbon nanotubes (MWCNTs), the electro-catalytic performance of nanometer titanium dioxide (TiO2) and film-forming capacity of carboxymethyl chitosan (CMCS) are combined, and the MWCNTs@TiO2/CMCS nanometer composite material is prepared through an in-situ sol/gel reaction and a solution blending method. An MWCNTs@TiO2 nanometer composite is prepared from MWCNTs and tetrabutyl titanate first, then the prepared nanometer composite and CMCS are compounded and assembled into a thin film according to a certain proportion, the thin film is used as a sensing element for detecting the residual amount of pesticide in food, and finally the electrochemical sensor material capable of detecting the residual amount of dipterex in food is obtained by adjusting and regulating the proportion of carbon nanotubes and titanium dioxide in the conductive composite material.
Description
Technical field
The invention belongs to nano composite material and technical field of function materials, be specifically related to a kind of utilize colloidal sol-solidifying in situ
Glue method prepares MWCNTs TiO2The methods and applications of/CMCS nano combined electrochemical sensing material.
Background technology
Metrifonate is wide variety of a kind of organophosphorus pesticide in agricultural production, and it can be with the work of acetylcholine esterase inhibition
Property, cause a large amount of accumulations of nerves within the body transmitter acetylcholine, thus cause a series of nerves reaction, such as produce feel sick,
Headache, the poisoning symptom such as unable, uncomfortable in chest, serious can cause death.After using metrifonate pesticide, it is impossible to by alkalescence such as soap
Detergent washes one's face and washes one's hands, and otherwise can cause poisoning, thus dead, this is because metrifonate becomes volatility in alkaline solution
The strongest dichlorvos, the toxicity of dichlorvos big more than 10 times than metrifonate.Therefore, if metrifonate is residual in environment and food
Staying accumulation, the health of the mankind being caused direct or potentially hazardous, so it being used for quickly detecting extremely important.Traditional
Detection method is mainly chromatography, such as, and gas chromatogram 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, time-consumingly, is unsuitable for carrying out Site Detection etc..And electrochemical sensing utensil
Have highly sensitive, simple to operate, and spend the advantages such as less, be widely used in the quick detection of pollutant.In addition, it
Also there is instrument and be prone to miniaturization, intellectuality, provide possibility for on-the-spot detection analysis.Chemically modified electrode is current electrification
Learn, the most active research field of Electroanalytical Chemistry aspect, therefore, the research of various electrode modified materials is the most just arisen at the historic moment.
Nano-TiO2Have that granule is little, specific surface area is big, absorbent properties are good and the advantage such as photocatalysis performance is good, also have table concurrently
Face activity is big, good dispersion, thermal conductance are good and prepared effect suspension stabilization and do not have many Optimalities such as harm to human body
Energy.TiO2As a kind of important semi-conducting material, because of the process based prediction model of its uniqueness, it is widely used in high activity
The fields such as the preparation of modified electrode, solaode assembling and photocatalytic degradation Organic substance.Multi-walled carbon nano-tubes (MWCNTs) has
Excellent mechanical performance, chemical stability, chemical property, optical property, heat-conductive characteristic etc., specific surface area is big, inhales
Attached property is strong, and stability is high, receives extensive concern in fields such as materialogy and biomedicines.But owing to CNT neutralizes at water
In organic solvent, dispersibility is poor, uses TiO2Come carbon nano-tube modified, be not only exaggerated this feature of CNT, but also
The electrically separated of CNT and electrocatalysis characteristic are combined with the identification ability of biopolymer, by original position sol-gel
Reaction method can prepare highly sensitive MWCNTs@TiO2Nano electrochemical sensor material.IN-SITU SOL-GEL has instead
Answering mild condition two-phase mixtures than more uniform advantage, processing ease, just can react under room temperature, condition is easy to control, and synthesis is produced
Article matter is high, and composition organic with inorganic in compound reaction can accurately control, and the interpenetrating networks knot formed
Structure can play the strongest restrictive function to separating between organic facies with inorganic phase, by changing the ratio of organic and inorganic component
Example to synthesize a small amount of inorganic material-modified organic material or a series of composites of a small amount of organic material modified inorganic material, this
A little advantages show huge potentiality at the aspect preparing functional composite material.
Chitosan because of its except have good biocompatibility and biodegradability and antibacterial, stop blooding, promote wound
Preferable film property, breathability and adsorptivity is also had outside the various functions such as healing.In medicine, environment, cosmetics, food service industry,
And each field such as chemical industry, agricultural is widely used.But owing to it is only soluble in diluted acid, water insoluble and alkaline solution, the most insoluble
In common are machine solvent, cause its application by certain restriction.For changing its solubility property, many researcheres are tied
Structure is modified, and utilizes the chemical property of chitosan can prepare a series of chitosan derivatives.As chitosan is carried out carboxylic
Methylate, its dissolubility can be substantially improved.Present invention utilizes the good water solublity of carboxymethyl chitosan (CMCS) and film forming
Property with MWCNTs@TiO2Nano composite material combines, and is prepared for MWCNTs@TiO2This novel nano composite material of/CMCS
And be assembled into thin film and the residual quantity of metrifonate is detected.
Summary of the invention
It is an object of the invention 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 CNT in nano composite material by the method for sol gel reaction
In easily reunite, bad dispersibility, thus electrochemical sensing difference etc. shortcoming；By changing CNT and titanium dioxide at composite wood
Mass fraction in material, it is thus achieved that the electrochemical sensing material of optkmal characteristics, finally gives and can detect metrifonate residual in food
The electrochemical sensor material of amount detection.
To achieve these goals, the technical solution adopted in the present invention is: a kind of carbon nano-tube/titanic oxide/carboxylic first
The preparation method of base enclosure polysaccharide nano combined electrochemical sensing material, concrete preparation process is as follows:
Step (1): prepare multi-walled carbon nano-tubes/titanium dioxide (MWCNTs@TiO by original position sol gel reaction2) nanometer is multiple
Condensation material, wherein raw material MWCNTs is 25% ~ 75%:75% ~ 25% with the adding proportion of butyl titanate；
Step (2): by the MWCNTs@TiO of preparation in step (1)2Composite is dispersed in the water of carboxymethyl chitosan (CMCS)
In solution, obtain MWCNTs@TiO at 60 DEG C through ultrasonication2/ CMCS nano combined electrochemical sensing material, wherein many walls carbon
Nanotube, nano titanium oxide, the adding proportion of carboxymethyl chitosan are 5% ~ 30%:15% ~ 10%:80% ~ 60% or 15% ~ 10%:
5%~30%:80%~60%；Or MWCNTs@TiO2It is 20% ~ 40%:80% ~ 60% with the adding proportion of CMCS.
Above-mentioned a kind of carbon nano-tube/titanic oxide/carboxymethyl chitosan (MWCNTs@TiO2/ CMCS) nano combined electrification
Learn the preparation method of sensing material, described MWCNTs@TiO2The optimal set of/CMCS electrochemical sensing material becomes multi-wall carbon nano-tube
Pipe 10%, nano titanium oxide 10%, carboxymethyl chitosan 80%.
A kind of carbon nano-tube/titanic oxide/carboxymethyl chitosan (MWCNTs@TiO2/ CMCS) nano combined electrochemistry biography
The application of sense material, by above-mentioned a kind of carbon nano-tube/titanic oxide/carboxymethyl chitosan (MWCNTs@TiO2/ CMCS) nanometer is multiple
Close the MWCNTs@TiO prepared by step (2) in the preparation method of electrochemical sensing material2/ CMCS electrochemical sensing material can group
Dress is electrochemical sensing thin-film component, and is applied to the detection of the residual quantities such as food Pesticides metrifonate, its detection limit as little as 3.3
×10-12Mol/L, has the highest sensitivity to trace residue pesticide.
Compared with prior art, present invention have the advantage that 1, the present invention utilizes carboxymethyl chitosan CMCS good
Water solublity and film property and MWCNTs@TiO2Nano composite material is combined mutually, is prepared for MWCNTs@TiO2/ CMCS novel nano is multiple
Condensation material, CNT or MWCNTs@TiO2Nano composite material is able in system stably dispersing well；2, by regulation and control
Titanium dioxide, CNT, the proportion of composing of carboxymethyl chitosan, regulate and control and optimize the electrification of nano composite material well
Learn performance, find the optimum amount that electrochemical behavior is good；Particularly, present invention incorporates TiO2Electric catalyticing characteristic so that it is
Chemical property is optimized, it is thus achieved that the electrochemical sensing thin film of optkmal characteristics.；3, nano compound film element of the present invention can be used
In the detection of food Pesticide Residues, its detection limit as little as 3.3 × 10-12Mol/L, has the highest to trace residue pesticide
Sensitivity；And in the range of comparatively wide pesticide concentration, modified electrode oxidation peak current and metrifonate concentration present good line
Sexual relationship.
Accompanying drawing explanation
Below by accompanying drawing and specifically describe the present invention in conjunction with the embodiments, wherein shown in accompanying drawing, content is only used for the present invention
Explanation, and do not constitute the restriction gone up in all senses to the present invention.
Fig. 1 is MWCNTs@TiO of the present invention2The synthesis schematic diagram of/CMCS nano composite material.
Fig. 2 is (a) MWCNTs in the embodiment of the present invention, (b) MWCNTs@TiO2, (c) MWCNTs@TiO2/ CMCS is multiple
Condensation material dispersion stabilization measurement result.
Fig. 3 (A) is Differential Pulse Voltammetry (DPV) curve of variable concentrations metrifonate solution in the embodiment of the present invention, Fig. 3
(B) it is 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 (B) are the MWCNTs@TiO of different proportion composition2/CMCS/GCE nano composite material modified electrode
Electrochemical behavior testing result.
Fig. 6 (A) and (B) are the electrochemical behavior testing result in the embodiment of the present invention in different pH electrolyte solutions.
Fig. 7 (A) and (B) are MWCNTs@TiO of the present invention2/ CMCS/GCE composite is electrolysed at 0.2M PBS (pH=7)
Linear relationship between electrochemical behavior under different scanning rates and peak current and sweep speed in liquid.
Table 1 is MWCNTs@TiO in the present invention2/ CMCS/GCE nano composite material modified electrode is for authentic sample
Testing result.
Detailed description of the invention
Below embodiments of the invention are elaborated: the present embodiment enters under premised on technical solution of the present invention
Row is implemented, and gives detailed embodiment and concrete operating process.It should be pointed out that, the ordinary skill people to this area
For Yuan, without departing from the inventive concept of the premise, it is also possible to make some modification and improvement, these broadly fall into present invention guarantor
Protect scope.
Embodiment 1:
A kind of preparation method of carbon nano-tube/titanic oxide/carboxymethyl chitosan nano combined electrochemical sensing material, its feature
Being that it is completed by following multistep reaction, preparation process schematic diagram is as shown in Figure 1.Specifically comprise the following steps that
Step (1): dried a certain amount of multi-walled carbon nano-tubes ultrasonic disperse 1-2h in dehydrated alcohol is formed A liquid, will
A certain amount of butyl titanate is dissolved in dehydrated alcohol formation B liquid, is added drop-wise to lentamente in A liquid by B liquid, in the process of dropping
In, it being sequentially added into a certain amount of glacial acetic acid solution, the ethanol of 95% and 0.1M salpeter solution, dropping ammonia regulation pH is about 7, holds
Continuous stirring 6 h, form uniform nanometer MWCNTs@TiO2Mixed solution, is stood 24h, after solvent volatilizees, is needed
The gel wanted；Being collected on culture dish by gel, be placed on 80 DEG C of drying in air dry oven, grind, horse takes 450 DEG C of calcinings in stove
4h；Obtain the MWCNTs@TiO of black powder2Nano composite material；The concrete consumption of each raw material and preparation technology parameter are such as
Under:
A, the preparation of nano titanium oxide
A liquid: measure 3.4ml butyl titanate, is added thereto to 16ml dehydrated alcohol, stir about 30min so that it is fully mix；
B liquid: add the glacial acetic acid of 3ml in the nitric acid of 5ml 0.1M, adds the ethanol of 16.5ml 95%, stir about 30min,
Make it mix；
A liquid is joined in constant pressure funnel, while stirring A liquid is added slowly in B liquid, add ammonia regulation pH value of solution and be about 7, continue
Continuous stirring 60min forms the leucosol of homogeneous transparent, and after stirring 6h, room temperature places 24h, after solvent volatilizees, is needed
Gel.Being collected on culture dish by gel, be placed on 80 DEG C of drying in air dry oven, grind, horse takes 450 DEG C of calcinings in stove
4h；Obtain the nano-TiO of white powder2。
B, with reference to nano-TiO prepared above2Process, by a certain amount of MWCNTs(and nano titanium oxide precentagewise 25% ~
75%:75% ~ 25%) ultrasonic disperse 1 ~ 2h in dehydrated alcohol, obtain C solution, a certain amount of butyl titanate is dissolved in anhydrous
In ethanol, stirring so that it is mixing, obtain D liquid.D liquid is placed in constant pressure funnel, is slowly dropped in C liquid, is stirred continuously, then add
Entering a certain amount of acetic acid solution, the ethanol of 95% and 0.1M salpeter solution, dropping ammonia regulation pH is about 7, continuously stirred 60h, shape
Uniformly nanometer MWCNTs@TiO2Mixed solution, is stood 24h, after solvent volatilizees, obtains the gel needed.Will be solidifying
Glue is collected on culture dish, is placed on 80 DEG C of drying in air dry oven, grinds, and horse takes 450 DEG C of calcining 4h in stove；Obtain black powder
The nanometer MWCNTs@TiO of powder2Composite.
Step (2): by the MWCNTs@TiO of preparation in step (1)2Nano composite material 0.03g ~ 0.08g be distributed to 0.17g ~
(MWCNTs@TiO in the aqueous solution of 0.12g carboxymethyl chitosan (CMCS)2Addition accounts for the 15% ~ 40% of total amount, the addition of CMCS
Amount is the 85% ~ 60% of total amount), ultrasonic disperse 1 ~ 2h under the conditions of 60 DEG C, obtain finely dispersed mixed liquor, its dispersion stabilization
As in figure 2 it is shown, then produce different material composition according to the difference ratio of taking of multi-walled carbon nano-tubes and nano titanium oxide
The target sample of ratio, is assembled into electrochemical sensing thin film, study each raw material optimum amount corresponding to its optimum chemical property and
Detection to pesticide residues composition.
Wherein, the concrete preparation process of CMCS is: the chitosan of 10.0g joins the NaOH solution that 50mL mass fraction is 50%
In, alkalize under room temperature 12h, then removes too much aqueous slkali, is joined by the chitosan of alkalization in the flask of 250mL, simultaneously
The chloroacetic acid of 10.0g is dissolved in the isopropanol of 40.0mL, is dropwise added drop-wise in the flask containing chitosan；Formed
Mixed solution stirs at 60 DEG C, reflux 4h, then neutralizes with dilute hydrochloric acid；Mixed liquor after reaction precipitates and mistake in acetone
Filter；Precipitate cleans repeatedly with the ethanol of 75%, until existing without chloroacetic acid；Again by thick product washes of absolute alcohol, then
It is dried until constant weight at 35 DEG C.
(3) above-mentioned a kind of MWCNTs@TiO2The preparation method and application of/CMCS nano combined electrochemical sensing material, utilize
To target sample prepare MWCNTs@TiO2/ CMC/GCE modified electrode and relevant comparative's electrode, the embodiment of the present invention uses and follows
The buffer solution (PBS) of ring voltammetric determination is by the H of 0.2M3PO4, the NaH of 0.2M2PO4, the Na of 0.2M2HPO4Preparation, uses 1.0M
HCl and 1.0M NaOH regulate pH；The electrolyte solution PBS buffer solution by 0.2M and the KCl solution composition of 0.2M；Oxidation
Reduction probe solution is by the K of 2.0mmol3Fe(CN)6/K4Fe(CN)6/ KCl (1:1:100, mol:mol:mol) forms.By naked electricity
Pole (GCE) is successively with 0.3 μm and the Al of 0.05 μm2O3Powder is polished to minute surface, stand-by with dehydrated alcohol and distilled water ultrasonic cleaning.
The sample ultrasonic dispersion 30min that will make, takes on the GCE surface that target sample suspension 6 μ l uniformly drips to handle well, stands,
Treat that it dries；In order to distinguish, respectively by nano-TiO2, MWCNTs, CMCS, MWCNTs@TiO2, MWCNTs@CMCS individually divides
Dissipate, prepare TiO as stated above2/ GCE, MWCNTs/GCE, CMCS/GCE, MWCNTs@TiO2/ GCE, MWCNTs@CMCS/
GCE, MWCNTs@TiO2/ CMCS/GCE electrode is stand-by；All detections are all carried out in electrochemical workstation.
Embodiment 2:
On the basis of embodiment 1, MWCNTs used in described experimental procedure (1) b is adjusted to nano titanium oxide ratio
50%:50%；
Step (2): by the MWCNTs@TiO of preparation in step (1)2Nano composite material 0.04g is distributed to 0.16g carboxymethyl shell
In the aqueous solution of polysaccharide (CMCS)；Will MWCNTs@TiO in step (2)2It is adjusted to 20%:80%, other step with the ratio of CMCS
The most same as in Example 1, obtain MWCNTs@TiO2/ CMCS nano combined electrochemical sensing material.
Embodiment 3:
On the basis of embodiment 1, MWCNTs used in described experimental procedure (1) b is adjusted to nano titanium oxide ratio
33%:67%；MWCNTs@TiO in step (2)2Being adjusted to 15%:85% with the ratio of CMCS, other step is same as in Example 1,
Obtain MWCNTs@TiO2/ CMCS nano combined electrochemical sensing material.Test result is shown in the curve a in Fig. 5 (A).
Embodiment 4:
On the basis of embodiment 1, MWCNTs used in described experimental procedure (1) b is adjusted to nano titanium oxide ratio
60%:40%；MWCNTs@TiO in step (2)2Being adjusted to 25%:75% with the ratio of CMCS, other step is same as in Example 1,
Obtain MWCNTs@TiO2/ CMCS nano combined electrochemical sensing material.Test result is shown in the curve c in Fig. 5 (A).
Embodiment 5:
On the basis of embodiment 1, MWCNTs used in described experimental procedure (1) b is adjusted to nano titanium oxide ratio
75%:25%；MWCNTs@TiO in step (2)2Being adjusted to 40%:60% with the ratio of CMCS, other step is same as in Example 1,
Obtain MWCNTs@TiO2/ CMCS nano combined electrochemical sensing material.Test result is shown in the curve d in Fig. 5 (A).
Embodiment 6:
On the basis of embodiment 1, MWCNTs used in described experimental procedure (1) b is adjusted to nano titanium oxide ratio
67%:33%；MWCNTs@TiO in step (2)2Being adjusted to 15%:85% with the ratio of CMCS, other step is same as in Example 1,
Obtain MWCNTs@TiO2/ CMCS nano combined electrochemical sensing material.Test result is shown in the curve a in Fig. 5 (B).
Embodiment 7:
On the basis of embodiment 1, MWCNTs used in described experimental procedure (1) b is adjusted to nano titanium oxide ratio
40%:60%；MWCNTs@TiO in step (2)2Being adjusted to 25%:75% with the ratio of CMCS, other step is same as in Example 1,
Obtain MWCNTs@TiO2/ CMCS nano combined electrochemical sensing material.Test result is shown in the curve c in Fig. 5 (B).
Embodiment 8:
On the basis of embodiment 1, MWCNTs used in described experimental procedure (1) b is adjusted to nano titanium oxide ratio
25%:75%；MWCNTs@TiO in step (2)2Being adjusted to 40%:60% with the ratio of CMCS, other step is same as in Example 1,
Obtain MWCNTs@TiO2/ CMCS nano combined electrochemical sensing material.Test result is shown in the curve d in Fig. 5 (B).
In order to prove beneficial effects of the present invention, inventor uses the CHI660E that Shanghai Chen Hua Instrument Ltd. produces
Chemical property and the practical application of embodiment sample can be detected by type electrochemical workstation, experimental result such as Fig. 3
～shown in 7.
Fig. 3 (A) uses Differential Pulse Voltammetry (DPV) to be detected certain density metrifonate solution.At pH=7
PBS electrolyte in, when accumulating potential is 0.9 ~ 1.15V, current potential increment 0.001V, amplitude 0.025V, pulse width 0.5s, arteries and veins
When rushing cycle 0.5s, the oxidation peak current of metrifonate and its concentration are 1 × 10-5~1×10-11In good in the range of mol/L
Linear relationship, linear equation is iP (μ A)=0.5077logC-6.3407；Correlation coefficient is 0.9915, as shown in Fig. 3 (B).
Use MWCNTs@TiO2/ CMCS/GCE modified electrode under optimal condition to Fructus Mali pumilae, Lentinus Edodes and three samples of Fructus Cucumidis sativi
Product use standard curve method to carry out DPV mensuration, each sample determination 5 times, average, and measurement result is as shown in table 1.By table 1
Visible, MWCNTs@TiO disclosed by the invention2/ CMCS nano combined electrochemical sensing material is in Fructus Mali pumilae, mushroom and Fructus Cucumidis sativi
The mensuration of pesticide metrifonate content, has low standard deviation (Fructus Mali pumilae 0.7% ~ 3.9%；Lentinus Edodes 0.8 ~ 8.1%；Fructus Cucumidis sativi 0.6% ~
7.3%) and the high response rate (Fructus Mali pumilae 82.0 ~ 96.5%；Lentinus Edodes 72.0 ~ 96.0%；Fructus Cucumidis sativi 78.0 ~ 98.0%).Therefore, the present invention is public
The MWCNTs@TiO opened2/ CMCS nano combined electrochemical sensing material may be used for the inspection of metrifonate residual quantity in authentic sample
Survey.
The measurement result of metrifonate content in table 1 authentic sample
A and b is the number of times of horizontal survey, in this experiment (a=5)
In order to study the electrocatalysis characteristic of different composite material, Fig. 4 gives the modified electrode prepared by these materials and exists
PBS(pH=7) cyclic voltammetry curve in electrolyte solution, under the sweep speed of 40 mV/ s.From fig. 4, it can be seen that probe from
Son is at MWCNTs@TiO2Oxidoreduction peak current on/CMCS/GCE is obvious, and MWCNTs/GCE, CMCS/GCE,
MWCNTs@TiO2Almost without redox current on/GCE and MWCNTs/CMCS/GCE.This explanation electronics is at MWCNTs@
TiO2Transfer rate on/CMCS laminated film modified electrode is the fastest, beneficially active substance generation redox reaction, thus
Oxidoreduction peak current is sharply increased.Meanwhile, it can be observed that at MWCNTs@TiO2/ CMCS/GCE modified electrode
On oxidation and reduction peak current symmetrical, spike potential difference is less, illustrates that probe ion electrochemistry on this modified electrode is anti-
It should be a reversible process.And at TiO2Despite obvious redox current on/GCE modified electrode, but oxidation and reduction
Peak current symmetry is poor, and spike potential difference is relatively big, and therefore the reversibility of probe ion electrochemical reaction on this modified electrode is not
And MWCNTs@TiO of the present invention2/ CMCS/GCE modified electrode.
MWCNTs@TiO2The electrocatalysis characteristic of/CMCS nano combined electrochemical sensing material is by system proportion of composing
Impact, as shown in Figure 5.Can be it is clear to see that keep TiO from Fig. 5 (A)2Content is constant, and nanotube content is special to oxidoreduction
Property has a significant impact.The CNT (5%) of low content does not produce redox current, and too high content of carbon nanotubes (30%)
Also redox current is made to reduce.There is explanation in the peak current strong when content of carbon nanotubes is at 10% and 15%, at this composition
Easily there is electrochemical oxidation or reduction reaction in lower composite.Due to b curve reduction peak electromotive force (0.211V) less than c curve also
Parent peak electromotive force (0.256V), reduction peak is substantially negative has 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 reversibility
Well.From Fig. 5 (B) can with find out, four curves all create oxidoreduction peak, it is evident that c curve oxidoreduction peak is more weak, and
The oxidoreduction peak current of b curve is the highest, and oxidation peak is good with reduction peak symmetry, and between electric potential difference only have 100mV, this
The good reversibility of the electrochemical sensor of the electrochemical copolymerization thin-film material that this ratio forms is described, electrocatalysis characteristic is good.Cause
This, 10% MWCNTs is combined 10% TiO2, and add the MWCNTs@TiO that 80% CMCS prepares2/ CMCS nano compound film is repaiied
Decorations anodizing reduction peak current is obvious, and good reversibility, chemical property is good.
Composite modified electrode electrocatalysis characteristic in the PBS electrolyte solution of different pH is as shown in Figure 6.At pH=7
Electrolyte solution in, i.e. shown in (c) curve, composite modified electrode has an obvious oxidoreduction peak, and aoxidize and
Reduction peak current is symmetrical, and spike potential difference is less, illustrate probe ion electrochemical reaction on this modified electrode be one can
Inverse process.It is therefore preferable that pH=7 electrolyte solution is as supporting electrolyte.
The electrocatalysis characteristic of composite modified electrode is had an impact by sweep speed.Fig. 7 is MWCNTs@TiO2/CMCS/
GCE composite modified electrode is the cyclic voltammogram under difference sweeps speed and peak current in 0.2M PBS (pH=7) electrolyte
And the 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 there occurs to be shuffled；And 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,
Sweeping the rate of hastening when 40mV/s, the electrochemical catalysis performance of composite is best.
Therefore, multi-walled carbon nano-tubes, nano titanium oxide, the usage amount of carboxymethyl chitosan are followed successively by 10%, and 10%, 80%
Time, the MWCNTs@TiO of preparation2/ CMCS nano compound film modified electrode oxidoreduction peak is obvious, good reversibility, electrochemistry
Can be good；Probe ion electrochemical reaction on this modified electrode is a reversible process.Find in 40mV/s electric scanning simultaneously
Under speed, under conditions of the electrolyte solution of pH=7 is as supporting electrolyte, the electrochemistry of composite prepared by the present invention is urged
Change performance best.
The above is the advantageous applications example of the present invention, and not limitation of the present invention is every according to the technology of the present invention
Within the change change of simple modification that main points are made, structure belongs to protection scope of the present invention.
Claims (3)
1. carbon nano-tube/titanic oxide/carboxymethyl chitosan (MWCNTs TiO2/ CMCS) nano combined electrochemical sensing material
The preparation method of material, it is characterised in that concrete preparation process is as follows:
Step (1): prepare multi-walled carbon nano-tubes/titanium dioxide (MWCNTs@TiO by original position sol gel reaction2) nanometer is multiple
Condensation material, wherein raw material MWCNTs is 25%～75%:75%～25% with the adding proportion of butyl titanate；
Step (2): by the MWCNTs@TiO of preparation in step (1)2Composite is dispersed in the water-soluble of carboxymethyl chitosan (CMCS)
In liquid, obtain MWCNTs@TiO at 60 DEG C through ultrasonication2/ CMCS nano combined electrochemical sensing material, wherein many walls carbon is received
Mitron, nano titanium oxide, the adding proportion of carboxymethyl chitosan be 5%～30%:15%～10%:80%～60% or
15%～10%:5%～30%:80%～60%；Or MWCNTs@TiO2It is 20%～40% with the adding proportion of CMCS:
80%～60%.
A kind of carbon nano-tube/titanic oxide/carboxymethyl chitosan (MWCNTs@TiO the most according to claim 12/CMCS)
The preparation method of nano combined electrochemical sensing material, it is characterised in that: described MWCNTs@TiO2/ CMCS electrochemical sensing material
The optimal set of material becomes multi-walled carbon nano-tubes 10%, nano titanium oxide 10%, carboxymethyl chitosan 80%.
3. carbon nano-tube/titanic oxide/carboxymethyl chitosan (MWCNTs TiO2/ CMCS) nano combined electrochemical sensing material
The application of material, it is characterised in that: by the MWCNTs@TiO prepared by step in claim 1 (2)2/ CMCS electrochemical sensing material
Material can be assembled into electrochemical sensing thin-film component, and is applied to the detection of the residual quantities such as food Pesticides metrifonate, and it detects limit
As little as 3.3 × 10-12Mol/L, has the highest sensitivity to trace residue pesticide.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111413381A (en) * | 2020-03-26 | 2020-07-14 | 上海大学 | Biosensor for detecting organophosphorus pesticide and preparation method thereof |
| CN112763560A (en) * | 2020-12-04 | 2021-05-07 | 陕西师范大学 | Preparation method of electrochemical biosensor based on Hemin @ CNF composite material and method for detecting bisphenol A in wine by using electrochemical biosensor |
| CN113866251A (en) * | 2021-09-18 | 2021-12-31 | 中北大学 | Preparation method of high-sensitivity quebrachitol molecularly imprinted electrochemical sensor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101224434A (en) * | 2007-12-29 | 2008-07-23 | 中国科学院长春应用化学研究所 | Preparing method of nanometer particle carbon nanotube compound catalyst |
| CN101851343A (en) * | 2010-05-19 | 2010-10-06 | 湖南大学 | Composite film with photocatalytic oxidability and preparation method thereof |
| CN102850576A (en) * | 2012-09-07 | 2013-01-02 | 中国科学技术大学 | Nanometer composite scaffolds assembled by adopting chitosan scaffold, preparation method and applications thereof |
-
2016
- 2016-03-18 CN CN201610156827.0A patent/CN105806923B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101224434A (en) * | 2007-12-29 | 2008-07-23 | 中国科学院长春应用化学研究所 | Preparing method of nanometer particle carbon nanotube compound catalyst |
| CN101851343A (en) * | 2010-05-19 | 2010-10-06 | 湖南大学 | Composite film with photocatalytic oxidability and preparation method thereof |
| CN102850576A (en) * | 2012-09-07 | 2013-01-02 | 中国科学技术大学 | Nanometer composite scaffolds assembled by adopting chitosan scaffold, preparation method and applications thereof |
Non-Patent Citations (1)
| Title |
|---|
| LIU, WANG ET AL.: "Composite membranes of chitosan and titania-coated carbon nanotubes as promising materials for new proton-exchange membranes", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111413381A (en) * | 2020-03-26 | 2020-07-14 | 上海大学 | Biosensor for detecting organophosphorus pesticide and preparation method thereof |
| CN112763560A (en) * | 2020-12-04 | 2021-05-07 | 陕西师范大学 | Preparation method of electrochemical biosensor based on Hemin @ CNF composite material and method for detecting bisphenol A in wine by using electrochemical biosensor |
| CN112763560B (en) * | 2020-12-04 | 2023-10-03 | 陕西师范大学 | Preparation method of electrochemical biosensor based on Hemin@CNF composite material and method for detecting bisphenol A in wine |
| CN113866251A (en) * | 2021-09-18 | 2021-12-31 | 中北大学 | Preparation method of high-sensitivity quebrachitol molecularly imprinted electrochemical sensor |
| CN113866251B (en) * | 2021-09-18 | 2023-08-15 | 中北大学 | Preparation method of high-sensitivity quebrachitol molecular imprinting electrochemical sensor |
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