CN103882623A - Prussian blue/polyvinylidene fluoride composite nano-fiber membrane and method for manufacturing same - Google Patents
Prussian blue/polyvinylidene fluoride composite nano-fiber membrane and method for manufacturing same Download PDFInfo
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Abstract
The invention discloses a Prussian blue/polyvinylidene fluoride composite nano-fiber membrane and a method for manufacturing the same. The method includes dispersing Prussian blue and polyvinylidene fluoride in N, N-dimethylacetamide and acetone mixed solvents to obtain spinning liquid; manufacturing the Prussian blue/polyvinylidene fluoride composite nano-fiber membrane by means of electrostatic spinning. The Prussian blue/polyvinylidene fluoride composite nano-fiber membrane and the method have the advantages that the uniform and stable composite nano-fiber membrane can be manufactured by the aid of the method, the stability of the Prussian blue can be improved, and the method is simple and is easy to control.
Description
Technical field
The invention belongs to composite nano fiber technical field, relate in particular to a kind of Prussian blue/polyvinylidene fluoride composite nano fiber film and preparation method thereof.
Background technology
Prussian blue (Prussian blue, PB) is a kind of common hexacyanoferrate, has the stability of good electrochemical reversibility, height and cheapness, the easy advantage such as preparation, can be made into the sensor of high sensitivity and high selectivity.But PB modified electrode is unstable in neutral or alkaline solution, soluble and come off.
Along with the development of nanometer technology, nano material more and more causes people's concern in the application of sensor field, intrinsic quantum size effect, the skin effect etc. of nanoparticle and nanofiber itself, makes it to show many conventional particles or the not available ins and outs of fiber at aspects such as magnetic, optical, electrical, sensings.Utilize specific area and activity that nano material is very high, can improve significantly catalytic efficiency.Therefore, nano material is transmitted medium as electronics in electrochemical reaction has unique advantage compared with conventional material.
Electrostatic spinning provides a kind of simple and general method for preparing various superfine fibres such as macromolecular material, composite, ceramic material etc.General device as shown in Figure 8, mainly divides three parts: the receiving system 3 of high voltage source 1, propulsion plant and metal spinning head (capillary) 2, ground connection.High voltage source is generally direct current, and size is 10～50KV, and propulsion plant comprises syringe 4 and syringe pump, and metal spinning nozzle 2 is connected 4 with syringe, and syringe is controlled by syringe pump 5, can constant injection volume.Spinning solution is mainly subject to three kinds of power, electrostatic repulsion forces, Coulomb attraction and surface tension.When voltage reaches after certain value, Coulomb attraction overcomes surface tension ejection, forms bonded fabric.
The macromolecule organic that has exceeded at present 50 kinds can spinning, diameter is generally between tens nanometers are to several microns, just because of the nanofiber diameter obtaining is little, specific area is large, there are a lot of potential using values in fields such as biomedicine, organizational projects.
Studies have reported that at present electrostatic spinning prepares the high polymer composite nanometer fiber film of natural high polymer nano fibrous membrane, artificial synthetic high polymer nano fibrous membrane and inorganic matter or doped with organic matter, but prepare Prussian blue/polyvinylidene fluoride composite nano fiber film in conjunction with electrostatic spinning technique, have not yet to see report.
Summary of the invention
The invention provides a kind of Prussian blue/preparation method of polyvinylidene fluoride composite nano fiber film, the method can obtain even, stable composite nano-fiber membrane, has improved Prussian blue stability, and preparation method is simply easy to control.
A preparation method for Prussian blue/polyvinylidene fluoride composite nano fiber film, comprising:
Prussian blue, Kynoar are scattered in the mixed solvent of DMA and acetone, configuration obtains spinning solution, adopts electrostatic spinning to prepare Prussian blue/polyvinylidene fluoride composite nano fiber film.
Prussian blue addition affects the electric conductivity of spinning solution, thereby affects the pattern of the spinnability of spinning solution and the fiber of spinning, preferred, and in described spinning solution, Prussian blue mass percent is 0.5～2.0%, and more preferably 0.5%.
The addition of Kynoar not only affects the stability of composite nano-fiber membrane, also directly affect the viscosity of spinning solution, viscosity is too low, and the entanglement of chain is insecure, jet shakiness, spinning fibre diameter is even not, the too high spinning solution of viscosity easily stops up pillow, affects spinning, preferred, in described spinning solution, the mass percent of Kynoar is 8.0～9.5%, more preferably 9.5%.
The present invention adopts N, the mixed liquor of N-dimethylacetylamide and acetone is as solvent Prussian blue, Kynoar, the spinnability of spinning solution is better, and both content is also most important in solvent, words as too much in the addition of acetone can increase the evaporation rate of solvent in spinning solution, affect spinning, N in described spinning solution, the mass percent of N-dimethylacetylamide is 35～55%, more preferably 45%.In described spinning solution, the mass percent of acetone is 35～55%, more preferably 45%.
Described spinning solution can prepare by the following method:
(1) synthesize Prussian blue particle, grind into powder take amount of substance ratio as 4:3 by ferric nitrate and potassium ferrocyanide;
(2) prussian blue powder is scattered in DMA and acetone mixed solvent, adds Kynoar, treat that it dissolves completely, make described spinning solution.
When electrostatic spinning, for obtain uniform and stable Prussian blue/polyvinylidene fluoride composite nano fiber film, should control spinning parameter well, as electrostatic pressure, receiving range, ejection flow velocity, environment temperature and humidity etc.
Suitable electrostatic pressure is the necessary condition that forms continous-stable fiber, also can control suitable fibre diameter simultaneously, and when electrostatic spinning, electrostatic pressure is 10～25KV.
Receiving range is too small, and solvent is volatilization completely not, be difficult to form fiber, and receiving range is excessive, and tow is difficult to collect on receiving device.Conventionally, receiving range is 10～20cm, and receiving device can adopt the coated cylinder ground connection of aluminium foil to receive.
Ejection flow velocity is an important parameter that affects nanofiber pattern, when electrostatic spinning, controls ejection flow velocity 0.5～2mL/h.
Preferred, when electrostatic spinning, ejection flow velocity is 1mL/h, and electrostatic pressure is 15KV, and receiving range is 15cm.
Environment temperature and humidity also can produce certain impact to the fiber appearance structure of spinning, and conventionally, keeping temperature is 21～26 ℃, and humidity is 45～55%.
The present invention also provides that described preparation method prepares Prussian blue/polyvinylidene fluoride composite nano fiber film.
Compared with prior art, beneficial effect of the present invention is:
(1) the present invention is based on electrostatic spinning technique, take Prussian blue, Kynoar as Electrospun pleurodiaphragmatic in terspace material, due to advantages such as Prussian blue good electrochemical reversibility, cheapness and easy preparations, but unstable in neutral and alkaline solution, and Kynoar has the advantages such as good chemical resistance, heat-resisting quantity, oxidative resistance, the present invention, by compound these two kinds of materials, has complementary functions, and has greatly improved the Prussian blue stability at neutrality or weakly alkaline solution.
(2) the present invention carries out, after electrostatic spinning, can obtaining fiber continuous, and evenly, fibre diameter is at the composite fiber membrane material of nanoscale (250～400nm).This membrane material is because have large specific area, between fiber and fiber, there is larger hole to be beneficial to the transmission of material, the thickness of film is controlled, therefore can significantly widen Prussian blue range of application in electrochemical field, test find the application Prussian blue/polyvinylidene fluoride composite nano fiber film Ascorbic Acid has good chemical property.The method of electrostatic spinning is fairly simple in addition, is easy to control and operation.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of PB nano particle and three kinds of nano fibrous membranes of electrostatic spinning gained.(a) PB; (b) PVDF nano fibrous membrane; (c) PVDF nano fibrous membrane (doping acetone); (d) PB/PVDF composite nano-fiber membrane; (a '), (b '), (c '), (d ') are respectively the partial enlarged drawing of corresponding picture.
Fig. 2 is the X-ray diffraction spectrogram of the PB of preparation.
Fig. 3 is PB((a, the c=0.05g/L of preparation), (b, c=0.1g/L), (c, c=0.2g/L), (d, c=0.3g/L)) uv-visible absorption spectra figure.
Fig. 4 is that electro-conductive glass (ITO) bare electrode (a), PVDF nano fibrous membrane (b), PVDF nano fibrous membrane (c, doping acetone), PB/PVDF composite nano-fiber membrane (d) modified electrode are at 0.001mol/LK
4[Fe (CN)
6], 0.001mol/LK
3[Fe (CN)
6] and 0.05mol/L KCl solution in the AC impedance figure of gained.
Fig. 5 is ITO bare electrode (a), PVDF nano fibrous membrane (b), PB/PVDF composite nano-fiber membrane (c) the modified electrode cyclic voltammogram of (0.1M, pH5.0) in phosphate buffered solution.
Fig. 6 is the retention of peak current after 20 cycles of the cyclic voltammetric of different modifying electrode under different pH values.(a) PB/PVDF composite nano-fiber membrane modified conducting glass electrode; (b) direct electro-deposition is to the PB modified electrode of electro-conductive glass.
Fig. 7 (A) is the differential pulse voltammetry curve map of PB/PVDF modified electrode, is (B) the concentration relationship curve map of AA in its corresponding peak point current and solution.
Fig. 8 is electrostatic spinning apparatus structural representation.
The specific embodiment
Below in conjunction with concrete embodiment, further set forth the present invention.
In embodiment, agents useful for same is AR, and experimental water is secondary deionized water.
1, Prussian blue preparation
Accurately take 15.76g Fe (NO
3)
39H
2o is dissolved in 30mL water, takes 12.67g K
4[Fe (CN)
6] 3H
2o is dissolved in 60mL water, while stirring by Fe (NO
3)
39H
2o solution is slowly added to K
4[Fe (CN)
6] 3H
2in O solution, (add about 10min), solution is from the faint yellow blueness that becomes, and continues to stir 5min, stops stirring, and centrifugal, washing 3 times, dries naturally, prepares Prussian blue (PB).
2, the preparation of Electrospun liquid
Accurately take 0.1g PB powder and be dissolved in 9.0g DMA and 9.0g acetone mixed solvent, stir 2h, treat that PB dissolves completely, add 1.9g PVDF(Kynoar) powder, stirs 12h, treat that PVDF dissolves completely, obtain blue opaque stickiness Electrospun solution.
3, electrostatic spinning is prepared PB/PVDF composite nano-fiber membrane
With syringe, (specification of syringe is 10mL, syringe needle internal diameter is 0.6～0.8mm) extraction PB/PVDF spinning solution, be fixed on electrostatic spinning apparatus, control ejection flow velocity 1.0mL/h, electrostatic pressure 15.00KV, receiver sheet adopts the coated cylinder ground connection of aluminium foil to receive, and the distance of syringe needle and dash receiver is 15cm, indoor temperature and humidity are respectively 21～26 ℃ and 45～55%, and spinning obtains PB/PVDF composite nano-fiber membrane.
4, the preparation of modified electrode
(1) accurately intercept 4cm × 2cm electro-conductive glass (China Nanbo Group Co), with acetone, absolute ethyl alcohol, the ultrasonic 10min washing of deionized water, dry stand-by successively;
(2) the PB/PVDF composite nano-fiber membrane preparing is taken off with the card punch that aperture is 19mm, stand-by;
(3) 50 μ L shitosan (0.5wt%) solution are added drop-wise to the one side that the electro-conductive glass in step (1) conducts electricity, coating evenly, is covered with the PB/PVDF composite nano-fiber membrane in step (2), naturally dry, be immersed in PBS(0.1M, PH5.0) middle 12h, prepare modified electrode.
With reference to the method for embodiment 1, change the composition of spinning solution, other conditions are constant, carry out electrostatic spinning, and nano fibrous membrane spinning being obtained by ESEM is observed.
Fig. 1 is scanning electron microscope (SEM) photograph, the PB nano particle of (a) preparing for embodiment 1; (b) PVDF nano fibrous membrane (not adding acetone), its spinning solution consists of: the mass percent of PVDF in spinning solution is 14%, and the mass percent of DMA is 86%; (c) PVDF nano fibrous membrane (interpolation acetone), its spinning solution consists of: the mass percent of PVDF in spinning solution is 10%, and the mass percent of DMA and acetone is 45%; (d) PB/PVDF composite nano-fiber membrane, its spinning solution consists of: Prussian blue mass percent in spinning solution is 0.5%, the mass percent of PVDF is 9.5%, the mass percent of DMA and acetone is 45%, and spinning voltage is 15.00KV, accepting distance is 15cm, injection flow velocity is 1.0mL/h, and environment temperature is 21～26 ℃, and ambient humidity is that 45%～55%(is the condition of embodiment 1).Wherein (b) with (c) relatively can find out, add acetone in preparation when spinning solution, on nanofiber, form loose structure, this will be conducive to the transmission of medium; (d) fiber that can find out the PB/PVDF composite nano-fiber membrane that the application obtains in is continuous, evenly, smooth surface, the diameter of fiber, at 250～400nm, seldom has adhesion between fiber.
Fig. 2 is Prussian blue x-ray diffraction pattern, and Prussian blue diffraction maximum conforms to completely with theoretical value.
Fig. 3 is Prussian blue uv-visible absorption spectra figure, curve a, and b, c, the Prussian blue concentration that d is corresponding is respectively 0.05g/L, 0.1g/L, 0.2g/L, 0.3g/L, its maximum absorption band is in 700nm left and right.
From Fig. 2, Fig. 3, the method for the embodiment of the present invention 1 has successfully prepared Prussian blue.
Electrochemical impedance collection of illustrative plates can accurately be reflected in the impedance variations that builds electrode surface in sensor process.The electrochemical impedance of different modifying electrode as shown in Figure 4.By electro-conductive glass (ITO) bare electrode (a), PVDF nano fibrous membrane (b), PVDF nano fibrous membrane (c, doping acetone), PB/PVDF composite nano-fiber membrane (d) modified electrode is respectively as working electrode, saturated calomel electrode is as reference electrode, and platinum filament is as to electrode.At 0.001mol/L K
4[Fe (CN)
6], 0.001mol/L K
3[Fe (CN)
6] and 0.05mol/L KCl solution in carry out AC impedance experiment, amplitude is 5mV, frequency range is 0.1-100000Hz.
In doping, PB(refers to that embodiment's 1 is Prussian blue) after the impedance shifted of the electronics of static spinning membrane obviously reduce, show the Prussian blue electrical conductance path at a high speed that built between electrode and electrolyte, improved the rate of dispersion of iron cyanide arrival electrode surface simultaneously; The PVDF nano fibrous membrane interface impedance that PB electrostatic spinning obtains if undope obviously increases a lot, but the PVDF nano fibrous membrane interface impedance that electrostatic spinning obtains after preparation adds acetone in spinning solution does not add the PVDF nano fibrous membrane of acetone slightly to reduce during than spinning, this during owing to electrostatic spinning acetone add the formation that has increased nanofiber porous.
With reference to the method for embodiment 1, change the composition of spinning solution, other conditions are constant, carry out preparing modified electrode after electrostatic spinning, adopt cyclic voltammetry to test each modified electrode; Wherein, (a), ITO bare electrode; (b), PVDF nano fibrous membrane modified electrode, spinning solution consists of: the mass percent of PVDF in spinning solution is 10%, and the mass percent of DMA and acetone is 45%; (c), PB/PVDF composite nano-fiber membrane modified electrode, spinning solution consists of: the mass percent that Prussian blue mass percent in spinning solution is 0.5%, PVDF is 9.5%, and the mass percent of DMA and acetone is 45%.
Experiment adopts three-electrode system, and reference electrode is saturated calomel electrode, and auxiliary electrode is platinum filament, and electrolyte is 0.1mol/L PBS(pH5.0) solution, electric potential scanning scope is-0.3～0.7V, sweep speed is 0.05V/s.
Modified electrode is at 0.1mol/L PBS(pH5.0) carry out in solution, test by cyclic voltammetry, as shown in Figure 5, the electrode that PB/PVDF modifies has a pair of very strong redox peak in 0.25V left and right, and peak does not all appear in PVDF modified electrode and electro-conductive glass bare electrode in this position, illustrate and in PB/PVDF composite nano-fiber membrane, really exist Prussian blue and can in PBS solution, carry out electron exchange transfer.
With reference to the method for embodiment 4, adopt cyclic voltammetry test PB/PVDF modified electrode in different pH values (pH5.0～9.0) 20 cycles of lower circulation, utilizing the oxidation peak current value in the 20th cycle and the ratio of the oxidation peak current value in the 1st cycle is ordinate, different pH values are abscissa mapping, as shown in Figure 6.
Adopt direct electro-deposition PB to electro-conductive glass modified electrode, the same said method of other step, makes comparisons.
Just there is significantly decay at pH7.0 in the peak point current of result PB/PVDF modified electrode, and in the environment of pH9.0, finally also can reach 60% left and right; But, the peak current pad value in equivalent environment is larger to the modified electrode of electro-conductive glass to adopt direct electro-deposition PB, and more than pH8.0, peak point current has dropped to very low (approximately 20%), illustrate that PB/PVDF nano fibrous membrane can improve the character of PB, improve the stability of PB in neutral and weakly alkaline environment.
With reference to the method for embodiment 1, adopt PB/PVDF modified electrode prepared by differential pulse voltammetry test implementation example 1 at 0.1mol/L PBS(pH5.0) response relation of Ascorbic Acid (AA) in solution, in solution, the concentration of AA is 0mM, 0.1mM, 0.2mM, 0.3mM, 0.4mM, 0.5mM, 0.6mM, 0.7mM, 0.8mM, 0.9mM.As shown in Figure 7, (A) being the differential pulse voltammetry curve map of PB/PVDF modified electrode, is (B) the concentration relationship curve map of AA in its corresponding peak point current and solution.
Result is along with the increase of AA concentration in solution, and peak current also increases thereupon, and its linearly dependent coefficient is 0.9973, illustrate that PB/PVDF has good response to AA, and PB/PVDF modified electrode has good stability.
Claims (8)
1. a preparation method for Prussian blue/polyvinylidene fluoride composite nano fiber film, is characterized in that, comprising:
Prussian blue, Kynoar are scattered in the mixed solvent of DMA and acetone, configuration obtains spinning solution, adopts electrostatic spinning to prepare Prussian blue/polyvinylidene fluoride composite nano fiber film.
2. preparation method as claimed in claim 1, is characterized in that, in described spinning solution, Prussian blue mass percent is 0.5～2.0%.
3. preparation method as claimed in claim 1, is characterized in that, in described spinning solution, the mass percent of Kynoar is 8.0～9.5%.
4. preparation method as claimed in claim 1, is characterized in that, in described spinning solution, the mass percent of DMA is 35～55%.
5. preparation method as claimed in claim 1, is characterized in that, in described spinning solution, the mass percent of acetone is 35～55%.
6. preparation method as claimed in claim 1, is characterized in that, when electrostatic spinning, ejection flow velocity is 0.5～2mL/h, and electrostatic pressure is 10～25KV, and receiving range is 10～20cm.
7. preparation method as claimed in claim 1, is characterized in that, when electrostatic spinning, keeping the temperature of environment is 21～26 ℃, and humidity is 45～55%.
As claim 1～7 any one preparation method prepare Prussian blue/polyvinylidene fluoride composite nano fiber film.
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| CN104695129A (en) * | 2015-03-03 | 2015-06-10 | 四川大学 | Polyvinylidene fluoride directionally arranged piezoelectric fiber membrane and preparation method thereof |
| CN109252293A (en) * | 2018-09-03 | 2019-01-22 | 内蒙古农业大学 | A kind of nano polymer fibers film and preparation method thereof and purposes |
| CN109576903A (en) * | 2018-10-29 | 2019-04-05 | 南京理工大学 | FeCo is Prussian blue/preparation method of polyacrylonitrile film |
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