CN107255659B - Fe3O4Nanoparticle-short carbon nanometer tube/poly- (2,6- pyridine) dioctyl phthalate composite membrane and its preparation method and application - Google Patents
Fe3O4Nanoparticle-short carbon nanometer tube/poly- (2,6- pyridine) dioctyl phthalate composite membrane and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of Fe3O4Nanoparticle-short carbon nanometer tube/poly- (2,6- pyridine) dioctyl phthalate composite membrane and its preparation method and application.The short carbon nanometer tube of preparation method of the invention to cut acidification adheres to Fe by sedimentation in situ as support frame3O4Fe is made in its surface in ultramicron3O4Nanoparticle-short carbon nanometer tube compound；In poly- (2,6- pyridine) dioctyl phthalate electropolymerization film surface, by pi-pi accumulation principle, fixed a certain amount of Fe3O4Nanoparticle-short carbon nanometer tube compound obtains the tri compound film with excellent electrocatalysis characteristic with this.Composite material of the invention is used for the measurement of Omeprazole drug sample, there is high electro catalytic activity to the oxidation of Omeprazole, can be used for modified glassy carbon electrode, realize the super sensitivity detection to the drug sample of Omeprazole.
Description
Technical field
The invention belongs to technical field of analysis and detection, and in particular to a kind of Fe3O4Nanoparticle-short carbon nanometer tube/poly- (2,
6- pyridine) dioctyl phthalate compound and its preparation method and application, and by magnetic nanometer-short carbon nanometer tube/poly- (2,6- pyridine)
Dioctyl phthalate compound is applied to the detection of Omeprazole drug sample.
Background technique
Omeprazole is a kind of derivative of benzimidazole, as H in stomach+-,K+Atpase inhibitor, it can be effective
Gastric acid is controlled, therefore can be used for treating duodenal ulcer, gastroesophageal reflux disease, erosive esophagitis and Zhuo -- Emhorn is comprehensive
The stomach trouble such as disease.In addition, it and antibiotic combinations can also effectively kill helicobacter pylori.So far, Omeprazole is detected
Method mainly have high performance liquid chromatography, spectroscopic methodology, capillary electrophoresis, capillary chromatography, although these methods have
Its unique advantage, but the sample treatment of expensive instrument and complexity is needed, which has limited them to be further widely used.
In contrast, electrochemical method is received significant attention because of its simple, low consumption, good stability and flexibility.Although
It is proposed the electrochemical methods of some detection Omeprazoles, but highly sensitive, easy to operate, inexpensive detection method is still a big need
It wants.
Carbon nanotube (CNTs) is because of its big surface area, excellent electric conductivity and catalytic, good bio-compatibility, easily
Preparation can form three-dimensional conductive matrices and be widely used in electrochemical research field.Although long carbon nanotube has both ends to open
Mouthful, but its active function is still limited to superficies.Due to weak ion permeability, in electrolyte ion is difficult to enter by inner hole
Surface, so their interior surface area is seldom utilized.Research thinks that the surface defect of carbon nanotube not only influences its catalysis
Ability changes its physical property, but also can adjust the chemical reactivity of carbon nanotube.And centainly degree of cutting and functionalization
Short carbon pipe have more defects and open end than long carbon pipe, can for catalysis reactant molecule more catalytic reaction activities are provided
Site, and provide short perforation channels for electrolyte ion and catalysis reactant molecule and easily enter surface of internal cavity to improve
Catalytic capability.
Fe3O4Super micro nano particle has the ability for improving electric conductivity and accelerating electron transmission.But due to its specific surface area
Greatly, chemical activity is high, therefore, pure Fe3O4Super micro nano particle is easily assembled and is aoxidized, this makes its bad dispersibility, thus one
Determine to limit its use in degree.But it is Fe3O4Super micro nano particle introduces certain support matrix, carries out to nanoparticle
Hydridization or surface modification can all prevent it from assembling and improve its stability and dispersibility, can also expand its actual use value.
Such as using carbon nanotube as Fe3O4The stabilization support frame of magnetic nanometer is with regard to existing research.The Fe studied3O4Nanoparticle
Son-carbon nanotube supramolecular system mainly passes through in-situ synthesis or rear fixation, the used original system of carbon Guan Douwei
Standby length, and using the functionalized carbon nano-tube of cutting as skeleton adulteration Fe3O4There is not been reported for the method for nanoparticle.
Summary of the invention
It is an object of that present invention to provide a kind of Fe3O4Nanoparticle-short carbon nanometer tube/poly- (2,6- pyridine) dioctyl phthalate is compound
Object and its preparation method and application.
The present invention is to cut the short carbon nanometer tube of acidification as support frame, by co sendimentation in situ, in short carbon nanometer
Pipe surface, which is stablized, adheres to a certain amount of Fe3O4Nanoparticle and be made Fe3O4Nanoparticle-short carbon nanometer tube compound；Pass through π-
Pi accumulation principle, on poly- (2,6- pyridine) dioctyl phthalate electropolymerization film, fixed Fe3O4Nanoparticle-short carbon nanometer tube compound, with
The tri compound film with excellent electrocatalysis characteristic, i.e. Fe is made in this3O4Nanoparticle-short carbon nanometer tube compound/poly- (2,6-
Pyridine) dioctyl phthalate.Compound analyte detection Omeprazole drug sample accuracy that the present invention obtains is high, high sensitivity.
The technical solution of the present invention is as follows:
A kind of Fe3O4Nanoparticle-short carbon nanometer tube/poly- (2,6- pyridine) dioctyl phthalate compound, which is characterized in that poly-
(2,6- pyridine) dioctyl phthalate electropolymerization film surface, Fe of the stable bond using short carbon nanometer tube as support matrix3O4It is nano combined
Material.
Further, it is combined between short carbon nanometer tube and poly- (2,6- pyridine) dioctyl phthalate by pi-pi accumulation effect.
Further, Fe3O4Nanoparticle is attached to short carbon nanometer tube surface by co sendimentation in situ.
Above-mentioned Fe3O4The preparation method of nanoparticle-short carbon nanometer tube/poly- (2,6- pyridine) dioctyl phthalate compound, including
Following steps:
(1) cutting and functionalization of carbon nanotube skeleton: carbon nanotube-sample after purification is taken, dense HNO is added to3With it is dense
H2S04Nitration mixture in, be placed in supersonic generator, under water bath condition carry out ultrasound, be then centrifuged for separating, obtain carbon nanotube
Skeleton；
(2)Fe3O4Nanoparticle-short carbon nanometer tube compound preparation: by FeCl3·6H2O and FeCl2·4H2O is being protected
It is thoroughly mixed under shield gas and is configured to mixed liquor, then short carbon nanometer tube is added in mixed solution and obtains short carbon nanometer tube dispersion
Liquid comes into full contact with, and metal ion is made sufficiently to be adsorbed in the surface of short carbon pipe by electrostatic attraction；Ammonium hydroxide is added, adjusts pH value, so
Afterwards under the conditions of 30~90 DEG C (preferably 30~70 DEG C, more preferably 30~50 DEG C) react 10~300min (preferably 20~
100min, more preferably 30~60min), then in 40~100 DEG C of (preferably 40~85 DEG C, more preferably 50~65 DEG C) conditions
10~150 min of lower reaction (preferably 20~100min, more preferably 30~60min)；Finally, it is cooling, after separation and washing
Drying is to get Fe3O4Nanoparticle-short carbon nanometer tube compound；
(3) preparation of the tri compound film based on poly- (2,6- pyridine) dioctyl phthalate: with 2,6- pyridinedicarboxylic acid for polymer fluid,
Using cyclic voltammetry, in glassy carbon electrode surface polymerization film formation, Fe then is added dropwise in poly- (2,6- pyridine) dioctyl phthalate film surface3O4
Nanoparticle-short carbon nanometer tube compound dispersion liquid is dried to obtain the tri compound film based on poly- (2,6- pyridine) dioctyl phthalate
That is Fe3O4Nanoparticle-short carbon nanometer tube/poly- (2,6- pyridine) dioctyl phthalate compound.
Further, in step (1), dense HNO3With dense H2S04Volume ratio be preferably 1:3.
Further, in step (1), preferably 60~90 DEG C of bath temperature, ultrasonic time preferably 2~6 hours.
Further, the mixed liquor of step (2) is prepared using hydrochloric acid solution, and the concentration of hydrochloric acid solution preferably 0.1~
0.3mol/L, more preferably 0.1mol/L.
Further, in short carbon nanometer tube dispersion liquid, the concentration of short carbon nanometer tube is 0.1~3.0mg/mL (short carbon nanometer
Dispersion concentration of the pipe in mixed liquor), preferably 0.5~2.0mg/mL, more preferable 0.8~1.5mg/mL.
Further, in short carbon nanometer tube dispersion liquid, FeCl3Concentration be 0.1~6.0mmoL/mL, preferably 0.3~4.0
MmoL/mL, more preferable 0.5~2.0mmoL/mL.
Further, in short carbon nanometer tube dispersion liquid, FeCl2Concentration be 0.1~6.0mmoL/mL, preferably 0.3~4.0
MmoL/mL, more preferable 0.5~2.0mmoL/mL.
Further, FeCl3·6H2O and FeCl2·4H2O mole dosage ratio (the ratio between amount of substance) is 1~6, preferably 1
~4, more preferable 2~3.
Further, in step (2), prepare mixed liquor incorporation time be 10~300min, preferably 20~100min,
More preferably 30~60min.
Further, in step (2), time of contact be 10~300min, preferably 20~100min, more preferably 30~
60 min。
Further, in step (2), the preferred concentrated ammonia liquor of ammonium hydroxide, pH value adjusts preferably 6~12, more preferably 7~10,
Further preferably 8-9.
Further, the separation of step (2), separate number preferably 3~5 times, separation method be filtering, filter, centrifugation or
Sedimentation, more preferably revolving speed are the centrifuge separation of 3000~18000rmp, and further preferably revolving speed is 5000~10000rmp
Centrifuge separation, disengaging time be 5~60min, preferably 10~40min, more preferably 15~30min.
Further, Fe3O4In nanoparticle-short carbon nanometer tube compound dispersion liquid, decentralized medium is water, preferably
Secondary distilled water, Fe3O4Nanoparticle-short carbon nanometer tube compound concentration is 0.1-3.0mg/mL, preferably 0.5-2.0mg/
ML, more preferable 0.8-1.5mg/mL.
Further, the cyclic voltammetry of step (3), specifically:
It is to the calomel electrode of electrode, saturation for reference electrode by working electrode, platinum filament of glass-carbon electrode, with 2,6- pyridine
Dioctyl phthalate is polymer fluid, in the electrolytic solution, using cyclic voltammetry, in potential range (the preferably potential range of -0.8~+2.5V
For -0.5~+2.0V, more preferably -0.1~+1.7V), to sweep speed be that (preferably sweep speed is 10-40mV/s to 5-50mV/s, more preferably
Under the conditions of 15-30mV/s), circulating polymerization 2-20 scan period (preferably 3-15 scan period, more preferably 5-10
A scan period), in glassy carbon electrode surface polymerization film formation, obtain poly- (2,6- pyridine) diformazan sorrel.
Further, the electrolyte is Klorvess Liquid, sodium chloride solution, potassium phosphate-phosphoric acid hydrogen potassium solution, di(2-ethylhexyl)phosphate
One or more of hydrogen sodium-sodium radio-phosphate,P-32 solution, sodium nitrate solution, potassium nitrate solution, the concentration of electrolyte are 0.01-
0.5mol/L, preferably 0.05-0.4mol/L, more preferably 0.1-0.3mol/L.
Further, the concentration of 2,6- pyridinedicarboxylic acid be 0.5-10mmol/L, preferably 2-7mmol/L, more preferably
4-5 mmol/L。
Above-mentioned Fe3O4Nanoparticle-short carbon nanometer tube/poly- (2,6- pyridine) dioctyl phthalate compound or above-mentioned preparation method
Obtained Fe3O4Nanoparticle-short carbon nanometer tube/poly- (2,6- pyridine) dioctyl phthalate compound answering in measurement Omeprazole
With.
The present invention obtains the Fe of stable dispersion by matching dosage, the selection in reaction time and pH in step (2)3O4Nanometer
Particle-short carbon nanometer tube compound；Pass through the polymerizing conditions such as electrolyte, polymerization time and polymer raw dosage in step (3)
Selection, fixed Fe3O4The selection of nanoparticle-short carbon nanometer tube compound dosage, it is controllable to synthesize thickness, high catalytic performance
Tri compound nanometer system, gained composite properties are excellent, using the nanometer system realize to Omeprazole drug sample
Detection, accuracy is high, high sensitivity.
Preparation method provided by the invention is simple, conveniently, it is easily operated.Wherein, Fe3O4Nano-particles size is uniform, disperses
Degree is high, because of Fe3O4Nanoparticle-short carbon nanometer tube and poly- (2,6- pyridine) dioctyl phthalate of substrate have interaction can stable dispersion and
Self aggregation will not be generated；Certain cutting degree and the short carbon pipe of functionalization have many defect and open end, can mention for catalysis reaction
For more active sites, and short perforation channels are provided for catalysis reactant molecule and makes it into inner cavity and improves catalysis energy
Power；By the pi-pi accumulation effect between magnetic nanometer-short carbon nanometer tube and poly- (2,6- pyridine) dioctyl phthalate, nanometer can be made to answer
The surface for being attached to polymeric membrane can be stablized without falling off by closing object；Poly- (2,6- pyridine) dioctyl phthalate has very strong surface rich base
Product ability, plays a very important role the oversoul sensitive detection of Omeprazole；There is also mutual catalyzing cooperations between ternary component
Effect can preferably improve electrocatalysis characteristic.
In the present invention, carbon nanotube: Nanjing Xian Feng Nono-material Science & Technology Ltd..The cutting and acidification of carbon nanotube
With reference to: Ng CM, Manickam S, Improved functionalization and recovery of
carboxylated carbon nanotubes using the acoustic cavitation approach,
Chem.Phys.Lett.557(2013)97–101。
In the present invention, scanning electron microscope, model: JEOL-7800F, Amada Co., Ltd.'s factory.X- powder diffraction
Instrument, model: XRD-6000, Japanese Shimadzu Corporation's factory.Transmission electron microscope, model: Tecnai G2F20, FEI Co. go out
Factory.Thermogravimetric analyzer, model: STA409PC/4/H, German Nai Chi company factory.Electrochemical workstation, model: CHI 760C,
The factory of Shanghai Chen Hua company.
In the present invention, centrifuge, ultrasonic device, heating device, vacuum drier, constant temperature incubator are that this field is existing
There is the commonly used equipment in technology, as long as can be realized corresponding function, can be suitably used for the present invention.
Compared with prior art, the present invention has following advantageous effects:
1, the present invention utilizes non-covalent pi-pi accumulation principle, on poly- (2,6- pyridine) dioctyl phthalate electropolymerization film, stablizes solid
Determine magnetic nanometer-short carbon nanometer tube compound.
2, in the present invention, Fe3O4Magnetic nanometer is of uniform size, dispersion degree is high, because having interaction with substrate polymeric membrane
Energy stable dispersion is without generating self aggregation；Certain cutting degree and the short carbon pipe of functionalization have many defect and open end, can
There is provided more active sites for catalysis reaction, and for be catalyzed reactant molecule provide short perforation channels make it into inner cavity and
Improve catalytic capability；By the pi-pi accumulation effect between short carbon nanometer tube and poly- (2,6- pyridine) dioctyl phthalate, compound can be enable
Stablize the surface for being attached to polymeric membrane without falling off；Poly- (2,6- pyridine) dioctyl phthalate has very strong surface Fu Jineng to base
Power plays a very important role the oversoul sensitive detection of base；There is also mutual catalyzing cooperation effects between ternary component.
3, magnetic nanometer-short carbon nanometer tube prepared by the present invention/poly- (2,6- pyridine) dioctyl phthalate can detect Omeprazole
Drug sample, and accuracy is high, high sensitivity.
4, method of the invention it is simple, conveniently, it is easily operated.
Detailed description of the invention
Fig. 1 is the scanning electron microscope diagram of short carbon nanometer tube after cutting acidification obtained by the embodiment of the present invention 1.
Fig. 2 is 1 gained Fe of the embodiment of the present invention3O4Nanoparticle-short carbon nanometer tube compound transmission electron microscope picture.
Fig. 3 is 1 gained short carbon nanometer tube (S-MCNTs) of the embodiment of the present invention, Fe3O4Nanoparticle and Fe3O4Nanoparticle
Son-short carbon nanometer tube compound (S-MCNTs-Fe3O4) X-ray diffractogram.
Fig. 4 is 1 gained short carbon nanometer tube (S-MCNTs) of the embodiment of the present invention, Fe3O4Nanoparticle and Fe3O4Nanoparticle
Son-short carbon nanometer tube compound (S-MCNTs-Fe3O4) thermal gravimetric analysis curve figure.
Fig. 5 is 1 gained Fe of the embodiment of the present invention3O4Nanoparticle-short carbon nanometer tube/poly- (2,6- pyridine) dioctyl phthalate (curve
F), short carbon nanometer tube/poly- (2,6- pyridine) dioctyl phthalate (curve e), Fe3O4Nanoparticle-short carbon nanometer tube (receive by curve d), short carbon
(curve c), ((curve a) is in Omeprazole solution for curve b), bare glassy carbon electrode for poly- (2,6- pyridine) dioctyl phthalate modified electrode for mitron
In cyclic voltammogram.
Fig. 6 is 1 gained Fe of the embodiment of the present invention3O4Aomei of the nanoparticle-short carbon nanometer tube modified electrode to various concentration
Draw the baseline deduction linear sweep voltammetry figure of azoles.
Specific embodiment
Here is that the double clicks of electroreduction graphene oxide-nickel of the present invention cough up the/tool of the preparation of platinum cluster composite material and application
Body embodiment, following embodiment are further intended to that the present invention will be described in detail, are not intended to limit the present invention.
Embodiment 1
(1) cutting and functionalization of carbon nanotube skeleton: the carbon nanotube that 50mg is newly bought is distributed in the dense nitration mixture of 50mL,
In dense HNO3(68wt.%): dense H2SO4(98wt.%) is mixed with the volume ratio of 1:3, then ultrasound 4 hours under 80 DEG C of water-baths,
Then, the short carbon nanometer tube distilled water of acidification is diluted, is then centrifuged for, and is washed, then be centrifuged, and washing is repeatedly until neutrality, vacuum
It is dry at 60 DEG C in drying box.
(2)Fe3O4Nanoparticle-short carbon nanometer tube compound preparation: the 40ml configured with 0.1mol/L hydrochloric acid
FeCl3·6H2O (2.0mmol/L) and FeCl2·4H2The mixed liquor of O (1.0mmol/L) is sufficiently stirred under nitrogen protection
Then 40mg short carbon nanometer tube is added in mixed liquor, after coming into full contact with 30min, passes through electrostatic to iron metal ion by 30min
Gravitation is sufficiently adsorbed in the surface of short carbon pipe.Mixed liquor is heated to 35 DEG C, ammonium hydroxide, adjusting pH value to 9.0, isothermal reaction 1h is added
Afterwards, then to mixed liquor 50 DEG C are warming up to, rear isothermal reaction 30min.Finally, cooling, repeatedly centrifugation and washing, at 40 DEG C, very
Sky is dry for 24 hours to get required compound.
(3) electropolymerization (2,6- pyridine) dioctyl phthalate
Three-electrode system are as follows: using glass-carbon electrode as working electrode, platinum filament to be to the calomel electrode of electrode, saturation be reference electricity
Pole, brand-new 0.1mol/L KCl and 5mmol/L (2,6- pyridine) dioctyl phthalate mixed solution as polymer fluid, utilize cyclic voltammetric
Method is swept under the conditions of speed is 20mV/s, 6 scan periods of circulating polymerization in -0.1V~+1.7V potential range；In glass-carbon electrode
The polymerizable layers of polymer film in surface.
(4) preparation of tri compound film modified electrode
The Fe that 1.0mg step (2) are obtained3O4Nanoparticle-short carbon nanometer tube is dispersed in 1mL secondary distilled water, is pipetted
The 5 μ L dispersion liquids, drop coating are dried in poly- (2,6- pyridine) dioctyl phthalate membrane electrode surface prepared by step (2), room temperature, obtain whole production
Product, i.e. Fe3O4Nanoparticle-short carbon nanometer tube/poly- (2,6- pyridine) dioctyl phthalate compound.
(5) characterization of 1 gained nano material of embodiment
As seen from Figure 1, the length range that the short carbon nanometer tube after ultrasound acidification has is 100~400 nanometers, short carbon nanometer
Pipe is uniformly dispersed, and does not wind mutually.As it is clear from fig. 2 that Fe3O4Particle has nanoscale, and particle size is about 5-10nm, by
In Fe3+and Fe2+Electrostatic Absorption between ion and acidification short carbon nanometer tube, once coprecipitation reaction starts to carry out, Fe3O4's
Nucleus will be carried out first in short carbon pipe surface, so Fe3O4Particle is effectively deposited on the surface of short carbon nanometer tube, is uniformly dispersed, nothing
It significantly builds up.As seen from Figure 3, magnetic nanometer-short carbon nanometer tube compound not only includes Fe3O46 diffractive features peaks, 2
θ is respectively 30.10 °, and 35.45 °, 43.09 °, 53.46 °, 56.98 °, and 62.57 °, respectively correspond Fe3O4(220) of crystal,
(311), (400), (422), (511) and (440) crystal face, also 2 containing short carbon nanometer tube, 2 θ characteristic peak (25.84 ° and
43.03°).Fig. 4 is that figure is compared in the thermogravimetric analysis of several nano materials.The initial temperature (480 of the nano-complex weightlessness of preparation
DEG C) than (550 DEG C) of short carbon nanometer tube 70 DEG C are reduced, this is because Fe3O4Nanoparticle has the oxidation of short carbon nanometer tube
Caused by catalytic action.This shows Fe3O4Nanoparticle-short carbon nanometer tube compound is successfully prepared.According to thermal gravimetric analysis curve,
The Fe in nano-complex prepared under the experiment condition3O4The loading content of magnetic particle is about 17.3%.Being compared by Fig. 5 can
Know, Fe3O4(curve f) has more Omeprazole to dioctyl phthalate film modified electrode to nanoparticle-short carbon nanometer tube/poly- (2,6- pyridine)
High electrocatalytic oxidation, with short carbon nanometer tube/poly- (2,6- pyridine) dioctyl phthalate (curve e), Fe3O4Nanoparticle-short carbon nanometer tube
(curve d), short carbon nanometer tube (curve c), poly- (2,6- pyridine) dioctyl phthalate modified electrode (curve b), bare glassy carbon electrode (curve a)
It compares, the peak current of the former catalysis oxidation Omeprazole is respectively 1.6,1.8,2.1,11.2 and 19.3 times of the latter.
(6) measurement of Omeprazole:
Test condition is as follows: three-electrode system, containing securing Fe3O4Nanoparticle-short carbon nanometer tube/poly- (2,6- pyridine)
The glass-carbon electrode of diformazan sorrel is working electrode, platinum filament be reference electrode, the phosphorus of 0.1mol/L to electrode, saturated calomel electrode
Hydrochlorate buffer solution is electrolyte, and pH value 6.0, test method is linear sweep voltammetry, application potential range+0.4~+
1.1V。
The method for detecting Omeprazole is as follows: in the Omeprazole solution liquid of various concentration, being inserted into three-electrode system, adopts
With linear sweep voltammetry, the oxidation peak current value of Omeprazole under various concentration, as seen from Figure 6, the peak of Omeprazole are recorded
Electric current increases with concentration, and in certain concentration range, linear corresponding relationship can draw electric current -- the standard curve of concentration.
When detecting sample, the oxidation peak current value and standard curve control that will be measured obtain the concentration of corresponding test sample.
It is tested in addition, also having carried out interference, stability, service life and sample recovery rate to detection method, experiments have shown that
The modification membrane stability is good, service life is long, anti-interference, can drug sample detection of the modified glassy carbon electrode for Omeprazole.
Embodiment, 2
(1) cutting and functionalization of carbon nanotube skeleton: the carbon nanotube that 25mg is newly bought is distributed in the dense nitration mixture of 50mL,
In dense HNO3(68wt.%): dense H2SO4(98wt.%) is mixed with the volume ratio of 1:3, then ultrasound 6 hours under 60 DEG C of water-baths,
Then, the short carbon nanometer tube distilled water of acidification is diluted, is then centrifuged for, and is washed, then be centrifuged, and washing is repeatedly until neutrality, vacuum
It is dry at 80 DEG C in drying box.
(2)Fe3O4Nanoparticle-short carbon nanometer tube compound preparation: the 40ml configured with 0.2mol/L hydrochloric acid
FeCl3·6H2O (3.0mmol/L) and FeCl2·4H2The mixed liquor of O (3.0mmol/L) is sufficiently stirred under nitrogen protection
Then 40mg short carbon nanometer tube is added in mixed liquor, after coming into full contact with 50min, passes through electrostatic to iron metal ion by 60min
Gravitation is sufficiently adsorbed in the surface of short carbon pipe.Mixed liquor is heated to 40 DEG C, ammonium hydroxide, adjusting pH value to 8.0, isothermal reaction is added
After 50min, then 55 DEG C are warming up to mixed liquor, rear isothermal reaction 25min.Finally, cooling, repeatedly centrifugation and washing, in 40 DEG C
Under, it is dried in vacuo for 24 hours to get required compound.
(3) electropolymerization (2,6- pyridine) dioctyl phthalate
Three-electrode system are as follows: using glass-carbon electrode as working electrode, platinum filament to be to the calomel electrode of electrode, saturation be reference electricity
Pole, 0.2mol/L NaCl and 2mmol/L (2,6- pyridine) dioctyl phthalate mixed solution are as polymer fluid, using cyclic voltammetry,
In -0.1 V~+1.7V potential range, sweep under the conditions of speed is 30mV/s, 5 scan periods of circulating polymerization；In glass-carbon electrode table
The polymerizable layers of polymer film in face.
(4) preparation of tri compound film modified electrode
The Fe that 2.0mg step (2) are obtained3O4Nanoparticle-short carbon nanometer tube is dispersed in 1mL secondary distilled water, is pipetted
The 5 μ L dispersion liquids, drop coating are dried in poly- (2,6- pyridine) dioctyl phthalate membrane electrode surface prepared by step (2), room temperature, obtain whole production
Product, i.e. Fe3O4Nanoparticle-short carbon nanometer tube/poly- (2,6- pyridine) dioctyl phthalate compound.
Embodiment 3
(1) cutting and functionalization of carbon nanotube skeleton: the carbon nanotube that 5mg is newly bought is distributed in the dense nitration mixture of 50mL,
In dense HNO3(68wt.%): dense H2SO4(98wt.%) is mixed with the volume ratio of 1:3, then ultrasound 2 hours under 90 DEG C of water-baths,
Then, the short carbon nanometer tube distilled water of acidification is diluted, is then centrifuged for, and is washed, then be centrifuged, and washing is repeatedly until neutrality, vacuum
It is dry at 80 DEG C in drying box.
(2)Fe3O4Nanoparticle-short carbon nanometer tube compound preparation: the 40ml configured with 0.1mol/L hydrochloric acid
FeCl3·6H2O (6.0mmol/L) and FeCl2·4H2The mixed liquor of O (2.0mmol/L) is sufficiently stirred under nitrogen protection
Then 40mg short carbon nanometer tube is added in mixed liquor, after coming into full contact with 40min, passes through electrostatic to iron metal ion by 20min
Gravitation is sufficiently adsorbed in the surface of short carbon pipe.Mixed liquor is heated to 50 DEG C, ammonium hydroxide, adjusting pH value to 7.0, isothermal reaction is added
After 30min, then 70 DEG C are warming up to mixed liquor, rear isothermal reaction 45min.Finally, cooling, repeatedly centrifugation and washing, in 50 DEG C
Under, it is dried in vacuo for 24 hours to get required compound.
(3) electropolymerization (2,6- pyridine) dioctyl phthalate
Three-electrode system are as follows: using glass-carbon electrode as working electrode, platinum filament to be to the calomel electrode of electrode, saturation be reference electricity
Pole, 0.3 mol/L potassium phosphate-phosphoric acid hydrogen potassium solution and 6mmol/L (2,6- pyridine) dioctyl phthalate mixed solution are as polymer fluid, benefit
With cyclic voltammetry, in -0.1V~+1.7V potential range, sweep under the conditions of speed is 35mV/s, 8 scan periods of circulating polymerization；
In the polymerizable layers of polymer film of glassy carbon electrode surface.
(4) preparation of tri compound film modified electrode
The Fe that 0.5mg step (2) are obtained3O4Nanoparticle-short carbon nanometer tube is dispersed in 1mL secondary distilled water, is pipetted
The 5 μ L dispersion liquids, drop coating are dried in poly- (2,6- pyridine) dioctyl phthalate membrane electrode surface prepared by step (2), room temperature, obtain whole production
Product, i.e. Fe3O4Nanoparticle-short carbon nanometer tube/poly- (2,6- pyridine) dioctyl phthalate compound.
Embodiment 4
(1) cutting and functionalization of carbon nanotube skeleton: the carbon nanotube that 100mg is newly bought is distributed in the dense nitration mixture of 50mL,
Wherein dense HNO3(68wt.%): dense H2SO4(98wt.%) is mixed with the volume ratio of 1:3, and then ultrasound 5 is small under 70 DEG C of water-baths
When, then, the short carbon nanometer tube distilled water dilution of acidification is then centrifuged for, and is washed, then be centrifuged, washing is repeatedly up to neutral, very
It is dry at 60 DEG C in empty drying box.
(2)Fe3O4Nanoparticle-short carbon nanometer tube compound preparation: the 40ml configured with 0.3mol/L hydrochloric acid
FeCl3·6H2O (2.0mmol/L) and FeCl2·4H2The mixed liquor of O (0.5mmol/L) is sufficiently stirred under nitrogen protection
Then 40mg short carbon nanometer tube is added in mixed liquor, after coming into full contact with 40min, passes through electrostatic to iron metal ion by 20min
Gravitation is sufficiently adsorbed in the surface of short carbon pipe.Mixed liquor is heated to 50 DEG C, ammonium hydroxide, adjusting pH value to 7.0, isothermal reaction is added
After 30min, then 70 DEG C are warming up to mixed liquor, rear isothermal reaction 45min.Finally, cooling, repeatedly centrifugation and washing, in 60 DEG C
Under, 20h is dried in vacuo to get required compound.
(3) electropolymerization (2,6- pyridine) dioctyl phthalate
Three-electrode system are as follows: using glass-carbon electrode as working electrode, platinum filament to be to the calomel electrode of electrode, saturation be reference electricity
Pole, 0.4mol/L sodium dihydrogen phosphate-sodium radio-phosphate,P-32 solution and 6mmol/L (2,6- pyridine) dioctyl phthalate mixed solution as polymer fluid,
Speed is swept as under the conditions of 35mV/s, 8 scannings of circulating polymerization are all in -0.1V~+1.7V potential range using cyclic voltammetry
Phase；In the polymerizable layers of polymer film of glassy carbon electrode surface.
(4) preparation of tri compound film modified electrode
The Fe that 0.5mg step (2) are obtained3O4Nanoparticle-short carbon nanometer tube is dispersed in 1mL secondary distilled water, is pipetted
The 5 μ L dispersion liquids, drop coating are dried in poly- (2,6- pyridine) dioctyl phthalate membrane electrode surface prepared by step (2), room temperature, obtain whole production
Product, i.e. Fe3O4Nanoparticle-short carbon nanometer tube/poly- (2,6- pyridine) dioctyl phthalate compound.
Embodiment 5
(1) cutting and functionalization of carbon nanotube skeleton: the carbon nanotube that 75mg is newly bought is distributed in the dense nitration mixture of 50mL,
In dense HNO3(68wt.%): dense H2SO4(98wt.%) is mixed with the volume ratio of 1:3, then ultrasound 4 hours under 80 DEG C of water-baths,
Then, the short carbon nanometer tube distilled water of acidification is diluted, is then centrifuged for, and is washed, then be centrifuged, and washing is repeatedly until neutrality, vacuum
It is dry at 90 DEG C in drying box.
(2)Fe3O4Nanoparticle-short carbon nanometer tube compound preparation: the 40ml configured with 0.1mol/L hydrochloric acid
FeCl3·6H2O 5.0mmol/L) and FeCl2·4H2O 2.5mmol/L) mixed liquor be sufficiently stirred under nitrogen protection
Then 40mg short carbon nanometer tube is added in mixed liquor, after coming into full contact with 60min, passes through electrostatic to iron metal ion by 50min
Gravitation is sufficiently adsorbed in the surface of short carbon pipe.Mixed liquor is heated to 70 DEG C, ammonium hydroxide, adjusting pH value to 6, isothermal reaction is added
After 100min, then 90 DEG C are warming up to mixed liquor, rear isothermal reaction 100min.Finally, cooling, repeatedly centrifugation and washing, in 60
At DEG C, 20h is dried in vacuo to get required compound.
(3) electropolymerization (2,6- pyridine) dioctyl phthalate
Three-electrode system are as follows: using glass-carbon electrode as working electrode, platinum filament to be to the calomel electrode of electrode, saturation be reference electricity
Pole, 0.5 mol/L sodium nitrate solution and 7mmol/L (2,6- pyridine) dioctyl phthalate mixed solution are lied prostrate as polymer fluid using circulation
An Fa is swept under the conditions of speed is 40mV/s, 15 scan periods of circulating polymerization in -0.1V~+1.7V potential range；In glass carbon
The polymerizable layers of polymer film of electrode surface.
(4) preparation of tri compound film modified electrode
The Fe that 3.0mg step (2) are obtained3O4Nanoparticle-short carbon nanometer tube is dispersed in 1mL secondary distilled water, is pipetted
The 5 μ L dispersion liquids, drop coating are dried in poly- (2,6- pyridine) dioctyl phthalate membrane electrode surface prepared by step (2), room temperature, obtain whole production
Product, i.e. Fe3O4Nanoparticle-short carbon nanometer tube/poly- (2,6- pyridine) dioctyl phthalate compound.
Embodiment 6
(1) cutting and functionalization of carbon nanotube skeleton: the carbon nanotube that 150mg is newly bought is distributed in the dense nitration mixture of 50mL,
Wherein dense HNO3(68wt.%): dense H2SO4(98wt.%) is mixed with the volume ratio of 1:3, and then ultrasound 3 is small under 65 DEG C of water-baths
When, then, the short carbon nanometer tube distilled water dilution of acidification is then centrifuged for, and is washed, then be centrifuged, washing is repeatedly up to neutral, very
It is dry at 60 DEG C in empty drying box.
(2)Fe3O4Nanoparticle-short carbon nanometer tube compound preparation: the 40ml configured with 0.2mol/L hydrochloric acid
FeCl3·6H2O 0.5mmol/L) and FeCl2·4H2O 0.1mmol/L) mixed liquor be sufficiently stirred under nitrogen protection
Then 40 mg short carbon nanometer tubes are added in mixed liquor, after coming into full contact with 100min, pass through electrostatic to iron metal ion by 30min
Gravitation is sufficiently adsorbed in the surface of short carbon pipe.Mixed liquor is heated to 80 DEG C, ammonium hydroxide, adjusting pH value to 9, isothermal reaction is added
After 150min, then 100 DEG C are warming up to mixed liquor, rear isothermal reaction 120min.Finally, cooling, repeatedly centrifugation and washing, in 60
At DEG C, 20h is dried in vacuo to get required compound.
(3) electropolymerization (2,6- pyridine) dioctyl phthalate
Three-electrode system are as follows: using glass-carbon electrode as working electrode, platinum filament to be to the calomel electrode of electrode, saturation be reference electricity
Pole, 0.05mol/L potassium nitrate solution and 8mmol/L (2,6- pyridine) dioctyl phthalate mixed solution are lied prostrate as polymer fluid using circulation
An Fa is swept under the conditions of speed is 50mV/s, 3 scan periods of circulating polymerization in -0.1V~+1.7V potential range；In glass carbon electricity
The polymerizable layers of polymer film of pole surface.
(4) preparation of tri compound film modified electrode
The Fe that 0.8mg step (2) are obtained3O4Nanoparticle-short carbon nanometer tube is dispersed in 1mL secondary distilled water, is pipetted
The 5 μ L dispersion liquids, drop coating are dried in poly- (2,6- pyridine) dioctyl phthalate membrane electrode surface prepared by step (2), room temperature, obtain whole production
Product, i.e. Fe3O4Nanoparticle-short carbon nanometer tube/poly- (2,6- pyridine) dioctyl phthalate compound.
Claims (10)
1. a kind of Fe3O4Nanoparticle-short carbon nanometer tube/poly- (2,6- pyridine) dioctyl phthalate compound, which is characterized in that it is poly- (2,
6- pyridine) dioctyl phthalate electropolymerization film surface, Fe of the stable bond using short carbon nanometer tube as support matrix3O4Nanocomposite；
The short carbon nanometer tube is obtained by cutting with functionalization, that is, is taken carbon nanotube-sample after purification, be added to dense HNO3
With dense H2S04Nitration mixture in, be placed in supersonic generator, under water bath condition carry out ultrasound, be then centrifuged for isolated.
2. Fe according to claim 13O4Nanoparticle-short carbon nanometer tube/poly- (2,6- pyridine) dioctyl phthalate compound,
It is characterized in that, is combined between short carbon nanometer tube and poly- (2,6- pyridine) dioctyl phthalate by pi-pi accumulation effect；Fe3O4Nanoparticle is logical
It crosses co sendimentation in situ and is attached to short carbon nanometer tube surface.
3. Fe of any of claims 1 or 23O4The system of nanoparticle-short carbon nanometer tube/poly- (2,6- pyridine) dioctyl phthalate compound
Preparation Method, which comprises the following steps:
(1) cutting and functionalization of carbon nanotube skeleton: carbon nanotube-sample after purification is taken, dense HNO is added to3With dense H2S04
Nitration mixture in, be placed in supersonic generator, under water bath condition carry out ultrasound, be then centrifuged for separating, obtain carbon nanotube skeleton；
(2) Fe3O4Nanoparticle-short carbon nanometer tube compound preparation: by FeCl3•6H2O and FeCl2•4H2O is under protective gas
It is thoroughly mixed and is configured to mixed liquor, then short carbon nanometer tube is added in mixed liquor and obtains short carbon nanometer tube dispersion liquid, sufficiently
Contact makes metal ion sufficiently be adsorbed in the surface of short carbon nanometer tube by electrostatic attraction；Ammonium hydroxide is added, adjusts pH value, then
10 ~ 300 min are reacted under the conditions of 30 ~ 90 DEG C, then 10 ~ 150 min are reacted under the conditions of 40 ~ 100 DEG C；Finally, it is cooling, point
It dries from after washing to get Fe3O4Nanoparticle-short carbon nanometer tube compound；
(3) preparation of the tri compound film based on poly- (2,6- pyridine) dioctyl phthalate: with 2,6- pyridinedicarboxylic acid for polymer fluid, benefit
Fe then is added dropwise in poly- (2,6- pyridine) dioctyl phthalate film surface in glassy carbon electrode surface polymerization film formation with cyclic voltammetry3O4It receives
Rice corpuscles-short carbon nanometer tube compound dispersion liquid, being dried to obtain the tri compound film based on poly- (2,6- pyridine) dioctyl phthalate is
Fe3O4Nanoparticle-short carbon nanometer tube/poly- (2,6- pyridine) dioctyl phthalate compound.
4. Fe according to claim 33O4The system of nanoparticle-short carbon nanometer tube/poly- (2,6- pyridine) dioctyl phthalate compound
Preparation Method, which is characterized in that in step (1), dense HNO3With dense H2S04Volume ratio be 1:3；Bath temperature is 60 ~ 90 DEG C, is surpassed
The sound time is 2 ~ 6 hours.
5. Fe according to claim 33O4The system of nanoparticle-short carbon nanometer tube/poly- (2,6- pyridine) dioctyl phthalate compound
Preparation Method, which is characterized in that the mixed liquor of step (2) is prepared using hydrochloric acid solution, and the concentration of hydrochloric acid solution is 0.1 ~ 0.3mol/
L；In short carbon nanometer tube dispersion liquid, the concentration of short carbon nanometer tube is 0.1 ~ 3.0 mg/mL, FeCl3Concentration be 0.1 ~ 6.0
MmoL/mL, FeCl2Concentration be 0.1 ~ 6.0 mmoL/mL；FeCl3•6H2O and FeCl2•4H2O mole dosage ratio is 1 ~ 6.
6. Fe according to claim 33O4The system of nanoparticle-short carbon nanometer tube/poly- (2,6- pyridine) dioctyl phthalate compound
Preparation Method, which is characterized in that in step (2), the incorporation time for preparing mixed liquor is 10 ~ 300 min；Time of contact is 10 ~ 300
min；Ammonium hydroxide is concentrated ammonia liquor, and it is 6 ~ 12 that pH value, which adjusts control,；The separation of step (2), separation number are 3 ~ 5 times, and separation method is
Filtering is filtered, is centrifuged or settled, and disengaging time is 5 ~ 60 min.
7. Fe according to claim 33O4The system of nanoparticle-short carbon nanometer tube/poly- (2,6- pyridine) dioctyl phthalate compound
Preparation Method, which is characterized in that Fe3O4In nanoparticle-short carbon nanometer tube compound dispersion liquid, decentralized medium is water, Fe3O4
Nanoparticle-short carbon nanometer tube compound concentration is 0.1-3.0 mg/mL.
8. Fe according to claim 33O4The system of nanoparticle-short carbon nanometer tube/poly- (2,6- pyridine) dioctyl phthalate compound
Preparation Method, which is characterized in that the cyclic voltammetry of step (3), specifically:
It is to the calomel electrode of electrode, saturation for reference electrode by working electrode, platinum filament of glass-carbon electrode, with 2,6- pyridine two
Formic acid is polymer fluid, in the electrolytic solution, using cyclic voltammetry, -0.8~+2.5 V potential range, to sweep speed be 5-50
Under the conditions of mV/s, the 2-20 scan period of circulating polymerization obtains poly- (2,6- pyridine) diformazan in glassy carbon electrode surface polymerization film formation
Sorrel.
9. Fe according to claim 83O4The system of nanoparticle-short carbon nanometer tube/poly- (2,6- pyridine) dioctyl phthalate compound
Preparation Method, which is characterized in that the electrolyte is Klorvess Liquid, sodium chloride solution, potassium phosphate-phosphoric acid hydrogen potassium solution, phosphorus
One or more of acid dihydride sodium-sodium radio-phosphate,P-32 solution, sodium nitrate solution, potassium nitrate solution, the concentration of electrolyte are
0.01-0.5 mol/L；The concentration of 2,6- pyridinedicarboxylic acid is 0.5-10 mmol/L.
10. Fe described in claim 13O4Nanoparticle-short carbon nanometer tube/poly- (2,6- pyridine) dioctyl phthalate compound is measuring
Application in Omeprazole.
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| CN101329296A (en) * | 2007-12-20 | 2008-12-24 | 复旦大学 | Glucolase electrode based on magnetic carbon nano-tube and preparation method thereof |
| CN102040212A (en) * | 2009-10-23 | 2011-05-04 | 清华大学 | Carbon nano tube composite structure |
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| CN101329296A (en) * | 2007-12-20 | 2008-12-24 | 复旦大学 | Glucolase electrode based on magnetic carbon nano-tube and preparation method thereof |
| CN102040212A (en) * | 2009-10-23 | 2011-05-04 | 清华大学 | Carbon nano tube composite structure |
| CN102583315A (en) * | 2012-02-15 | 2012-07-18 | 西北工业大学 | Method for preparing ferroferric oxide/ carbon nano tube composite material |
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