CN103882623B - A kind of Prussian blue/polyvinylidene fluoride composite nano fiber film and preparation method thereof - Google Patents
A kind of Prussian blue/polyvinylidene fluoride composite nano fiber film and preparation method thereof Download PDFInfo
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- CN103882623B CN103882623B CN201410064301.0A CN201410064301A CN103882623B CN 103882623 B CN103882623 B CN 103882623B CN 201410064301 A CN201410064301 A CN 201410064301A CN 103882623 B CN103882623 B CN 103882623B
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Abstract
The invention discloses a kind of Prussian blue/polyvinylidene fluoride composite nano fiber film and preparation method thereof, described preparation method includes: Prussian blue, Kynoar are scattered in N, in the mixed solvent of N-dimethyl acetylamide and acetone, configuration obtains spinning liquid, adopts electrostatic spinning to prepare Prussian blue/polyvinylidene fluoride composite nano fiber film.Present invention also offers that described preparation method prepares Prussian blue/polyvinylidene fluoride composite nano fiber film.The present invention is Prussian blue/and the preparation method of polyvinylidene fluoride composite nano fiber film can obtain uniform, stable composite nano-fiber membrane, and improve Prussian blue stability, and preparation method is simply easily controllable.
Description
Technical field
The invention belongs to composite nano fiber technical field, particularly relate to a kind of Prussian blue/polyvinylidene fluoride composite nano fiber film and preparation method thereof.
Background technology
Prussian blue (Prussianblue, PB) is a kind of common hexacyanoferrate, has the advantages such as excellent electrochemical reversibility, the stability of height and cheap, easy preparation, can be made into high sensitivity and the selective sensor of height.But PB modified electrode is unstable in neutral or alkaline solution, soluble and come off.
Development along with nanotechnology, nano material increasingly causes the concern of people in the application of sensor field, nanoparticle and the intrinsic quantum size effect of nanofiber itself, skin effect etc., so as to show the ins and outs not available for many conventional particle or fiber in magnetic, optical, electrical, sensing etc..Utilize specific surface area and activity that nano material is very high, it is possible to significantly increase catalytic efficiency.Therefore, nano material has the advantage of uniqueness in electrochemical reaction as the more conventional material of electron transmission medium.
Electrostatic spinning is prepare various superfine fibre such as macromolecular material, composite, ceramic material etc. to provide a kind of simple and general method.General device as shown in Figure 8, mainly divides three parts: the reception device 3 of high voltage power supply 1, propulsion plant and metal spinning head (capillary tube) 2, ground connection.High voltage power supply is generally direct current, is sized to 10～50KV, and propulsion plant includes syringe 4 and syringe pump, metal spinning nozzle 2 and syringe and connects 4, and syringe is controlled by syringe pump 5, it is possible to constant injection volume.Spinning liquid is limited mainly by three kinds of power, electrostatic repulsion forces, Coulomb attraction and surface tension.After voltage reaches certain value, Coulomb attraction overcomes surface tension to spray, and forms bonded fabric.
The macromolecule organic alreading more than 50 kinds at present can spinning, diameter is typically in tens nanometers between several microns, just because of the nanofiber diameter obtained is little, specific surface area big, in fields such as biomedicine, organizational projects, there is much potential using value.
Existing research at present reports electrostatic spinning and prepares the high polymer composite nanometer fiber film of natural high polymer nano fibrous membrane, 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 uniform, stable composite nano-fiber membrane, improves Prussian blue stability, and preparation method is simply easily controllable.
A kind of Prussian blue/preparation method of polyvinylidene fluoride composite nano fiber film, including:
Being scattered in the mixed solvent of N,N-dimethylacetamide and acetone by Prussian blue, Kynoar, configuration obtains spinning liquid, adopts electrostatic spinning to prepare Prussian blue/polyvinylidene fluoride composite nano fiber film.
Prussian blue addition affects the electric conductivity of spinning liquid, thus affecting the spinnability of spinning liquid and the pattern of the fiber of spinning, it is preferred that mass percent Prussian blue in described spinning liquid is 0.5～2.0%, more preferably 0.5%.
The addition of Kynoar not only affects the stability of composite nano-fiber membrane, also the viscosity of spinning liquid is directly affected, viscosity is too low, then the entanglement of chain is insecure, and jet is unstable, spinning fibre diameter is uniform not, viscosity is too high, and spinning liquid easily blocks medicated pillow, affects spinning, it is preferred that, in described spinning liquid, the mass percent of Kynoar is 8.0～9.5%, more preferably 9.5%.
The present invention adopts N, the mixed liquor of N-dimethyl acetylamide and acetone is as solvent Prussian blue, Kynoar, the spinnability of spinning liquid is better, and both content is also most important in solvent, the too much words of addition such as acetone can increase the evaporation rate of solvent in spinning liquid, affects spinning, N in described spinning liquid, the mass percent of N-dimethyl acetylamide is 35～55%, more preferably 45%.In described spinning liquid, the mass percent of acetone is 35～55%, more preferably 45%.
Described spinning liquid can be prepared via a method which to obtain:
(1) Prussian blue granule, grind into powder are synthesized with amount of substance than for 4:3 by ferric nitrate and potassium ferrocyanide；
(2) prussian blue powder is scattered in N,N-dimethylacetamide and acetone mixed solvent, adds Kynoar, treat that it is completely dissolved, prepare described spinning liquid.
During electrostatic spinning, for obtain uniform and stable Prussian blue/polyvinylidene fluoride composite nano fiber film, spinning parameter should be controlled well, such as electrostatic pressure, receiving range, ejection flow velocity, ambient temperature and humidity etc..
Suitable electrostatic pressure is the essential condition forming continuous-stable fiber, also is able to control suitable fibre diameter simultaneously, and during electrostatic spinning, electrostatic pressure is 10～25KV.
Receiving range is too small, and solvent does not volatilize completely, it is difficult to form fiber, and receiving range is excessive, then tow is difficult to collect on receiving device.Generally, receiving range is 10～20cm, and receiving device can adopt the cylinder ground connection that aluminium foil is coated with to receive.
Ejection flow velocity is the important parameter affecting nanofiber pattern, during electrostatic spinning, controls ejection flow velocity 0.5～2mL/h.
It is furthermore preferred that during electrostatic spinning, ejection flow velocity is 1mL/h, electrostatic pressure is 15KV, and receiving range is 15cm.
The fiber morphology structure of spinning also can be produced certain impact by ambient temperature and humidity, and generally, keeping temperature is 21～26 DEG C, and humidity is 45～55%.
Present invention also offers that described preparation method prepares Prussian blue/polyvinylidene fluoride composite nano fiber film.
Compared with prior art, the invention have the benefit that
(1) present invention is based on electrostatic spinning technique, with Prussian blue, Kynoar for electrospun membrane raw material, due to advantages such as Prussian blue excellent electrochemical reversibility, cheap and easy preparations, but neutral unstable with alkaline solution, and Kynoar has the advantages such as good chemical resistance, heat-resisting quantity, oxidative resistance, the present invention, by both material compounds, has complementary functions, and substantially increases Prussian blue in neutral or weakly alkaline solution stability.
(2) after the present invention carries out electrostatic spinning, can obtaining fiber continuous, uniformly, fibre diameter is at the composite fiber membrane material of nanoscale (250～400nm).This membrane material is because having big specific surface area, bigger hole is had to be beneficial to the transmission of material between fiber and fiber, 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.Additionally the method for electrostatic spinning is fairly simple, it is easy to control and operation.
Accompanying drawing explanation
Fig. 1 is PB nanoparticle and the scanning electron microscope (SEM) photograph of 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；The partial enlarged drawing of (a '), (b '), (c '), (d ') respectively corresponding picture.
Fig. 2 is the X-ray diffraction spectrogram of the PB of preparation.
Fig. 3 be preparation PB((a, c=0.05g/L), (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, adulterate acetone), PB/PVDF composite nano-fiber membrane (d) modified electrode are at 0.001mol/LK4[Fe(CN)6]、0.001mol/LK3[Fe(CN)6] and 0.05mol/LKCl 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 different modifying electrode 20 cycles of cyclic voltammetric at various ph values.(a) PB/PVDF composite nano-fiber membrane modified conducting glass electrode；B () directly electro-deposition is to the PB modified electrode of electro-conductive glass.
The differential pulse voltammetry curve chart that Fig. 7 (A) is PB/PVDF modified electrode, the peak point current that (B) is its correspondence and the concentration relationship curve chart of AA in solution.
Fig. 8 is electrostatic spinning apparatus structural representation.
Detailed description of the invention
Below in conjunction with being embodied as example, the present invention is expanded on further.
In embodiment, agents useful for same is analytical reagent, and experimental water is secondary deionized water.
Embodiment 1
1, Prussian blue preparation
Accurately weigh 15.76gFe (NO3)3·9H2O is dissolved in 30mL water, weighs 12.67gK4[Fe(CN)6]·3H2O is dissolved in 60mL water, while stirring by Fe (NO3)3·9H2O solution is added slowly to K4[Fe(CN)6]·3H2(adding about 10min) in O solution, solution, from the faint yellow blueness that becomes, continuation stirring 5min, stops stirring, is centrifuged, washes 3 times, naturally dry, prepare Prussian blue (PB).
2, the preparation of Electrospun liquid
Accurately weigh 0.1gPB powder and be dissolved in 9.0gN, N-dimethyl acetylamide and 9.0g acetone mixed solvent, stir 2h, treat that PB is completely dissolved, add 1.9gPVDF(Kynoar) powder, stirs 12h, treat that PVDF is completely dissolved, obtain blue opaque stickiness Electrospun solution.
3, electrostatic spinning prepares PB/PVDF composite nano-fiber membrane
With syringe, (specification of syringe is 10mL, syringe needle internal diameter is 0.6～0.8mm) extract PB/PVDF spinning liquid, it is fixed on electrostatic spinning apparatus, control ejection flow velocity 1.0mL/h, electrostatic pressure 15.00KV, receiver sheet adopts the cylinder ground connection of aluminium foil cladding to receive, and syringe needle and the distance receiving plate are 15cm, indoor temperature and humidity respectively 21～26 DEG C and 45～55%, 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), successively with acetone, dehydrated alcohol, the ultrasonic 10min washing of deionized water, dry stand-by；
(2) card punch that PB/PVDF composite nano-fiber membrane aperture is 19mm prepared is taken off, stand-by；
(3) one side of the electro-conductive glass conduction 50 μ L chitosan (0.5wt%) solution being added drop-wise in step (1), coating uniformly, is covered with the PB/PVDF composite nano-fiber membrane in step (2), naturally dry, be immersed in PBS(0.1M, PH5.0) in 12h, prepare modified electrode.
Embodiment 2
With reference to the method for embodiment 1, changing the composition of spinning liquid, other conditions are constant, carry out electrostatic spinning, and nano fibrous membrane spinning obtained by scanning electron microscope is observed.
Fig. 1 is scanning electron microscope (SEM) photograph, the PB nanoparticle that (a) is prepared for embodiment 1；B () PVDF nano fibrous membrane (being not added with acetone), its spinning liquid consists of: PVDF mass percent in spinning liquid is 14%, and the mass percent of N,N-dimethylacetamide is 86%；C () PVDF nano fibrous membrane (interpolation acetone), its spinning liquid consists of: PVDF mass percent in spinning liquid is 10%, and the mass percent of N,N-dimethylacetamide and acetone is 45%；(d) PB/PVDF composite nano-fiber membrane, its spinning liquid consists of: Prussian blue mass percent in spinning liquid is 0.5%, the mass percent of PVDF is 9.5%, the mass percent of N,N-dimethylacetamide and acetone is 45%, and spinning voltage is 15.00KV, accept distance for 15cm, injection flow velocity is 1.0mL/h, and ambient temperature is 21～26 DEG C, and ambient humidity is 45%～55%(and the condition of embodiment 1).Wherein (b) compares with (c) it can be seen that add acetone when preparing spinning liquid, forms loose structure on nanofiber, and this is beneficial to the transmission of medium；D can be seen that in () that the fiber of the PB/PVDF composite nano-fiber membrane that the application obtains is continuous, uniformly, smooth surface, the diameter of fiber seldom has adhesion between 250～400nm, fiber.
Fig. 2 is Prussian blue x-ray diffraction pattern, and Prussian blue diffraction maximum is consistent completely with theoretical value.
Fig. 3 is Prussian blue uv-visible absorption spectra figure, and Prussian blue concentration respectively 0.05g/L, 0.1g/L, 0.2g/L, the 0.3g/L that curve a, b, c, d are corresponding, its maximum absorption band is at about 700nm.
By Fig. 2, Fig. 3 it can be seen that the method for the embodiment of the present invention 1 has successfully prepared Prussian blue.
Embodiment 3
Electrochemical impedance collection of illustrative plates can accurately reflect the impedance variation of electrode surface in building sensor process.The electrochemical impedance of different modifying electrode is 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/LK4[Fe(CN)6]、0.001mol/LK3[Fe(CN)6] and 0.05mol/LKCl solution in carry out AC impedance experiment, amplitude is 5mV, and frequency range is 0.1-100000Hz.
Doping PB(refer to the Prussian blue of embodiment 1) afterwards the impedance of the electron transfer of static spinning membrane be obviously reduced, show the Prussian blue electrical conductance path constructing high speed between electrode and electrolyte, improve the iron cyanide simultaneously and arrive the rate of dispersion of electrode surface；The PVDF nano fibrous membrane interface impedance that PB electrostatic spinning obtains if undoping significantly increases a lot, but prepare spinning liquid adds acetone after the PVDF nano fibrous membrane interface impedance that obtains of electrostatic spinning than spinning time be added without the PVDF nano fibrous membrane of acetone and be slightly reduced, when this is owing to electrostatic spinning, the addition of acetone adds the formation of nanofiber porous.
Embodiment 4
With reference to the method for embodiment 1, changing the composition of spinning liquid, other conditions are constant, prepare modified electrode after carrying out electrostatic spinning, adopt cyclic voltammetry to test each modified electrode；Wherein, (a), ITO bare electrode；B (), PVDF nanofiber film modified electrode, spinning liquid consists of: PVDF mass percent in spinning liquid is 10%, and the mass percent of N,N-dimethylacetamide and acetone is 45%；C (), PB/PVDF composite nano-fiber membrane modified electrode, spinning liquid consists of: Prussian blue mass percent in spinning liquid is 0.5%, and the mass percent of PVDF is 9.5%, and the mass percent of N,N-dimethylacetamide 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/LPBS(pH5.0) solution, electric potential scanning ranges for-0.3～0.7V, and scanning speed is 0.05V/s.
Modified electrode is at 0.1mol/LPBS(pH5.0) solution carries out, test by cyclic voltammetry, as shown in Figure 5, the electrode that PB/PVDF modifies has very strong a pair oxidoreduction peak at about 0.25V, and PVDF modified electrode and electro-conductive glass bare electrode in this position all without peak occurs, illustrate PB/PVDF composite nano-fiber membrane is implicitly present in Prussian blue and electron exchange transfer can be carried out in PBS solution.
Embodiment 5
Method with reference to embodiment 4, adopt cyclic voltammetry test PB/PVDF modified electrode 20 cycles of circulation under different pH value (pH5.0～9.0), the ratio utilizing the oxidation peak current value in the 20th cycle and the oxidation peak current value in the 1st cycle is vertical coordinate, different pH value 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, make comparisons.
The peak point current of result PB/PVDF modified electrode just occurs significantly decaying at pH7.0, and finally also can reach about 60% in the environment of pH9.0；But, adopt direct electro-deposition PB bigger to peak current pad value in equivalent environment of the modified electrode of electro-conductive glass, and at more than pH8.0, peak point current has been reduced to very low (about 20%), illustrate that PB/PVDF nano fibrous membrane can improve the character of PB, improve PB in neutral and in weakly alkaline environment stability.
Embodiment 6
Method with reference to embodiment 1, adopt the PB/PVDF modified electrode of differential pulse voltammetry testing example 1 preparation at 0.1mol/LPBS(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 it is shown in fig. 7, the differential pulse voltammetry curve chart that (A) is PB/PVDF modified electrode, the peak point current that (B) is its correspondence and the concentration relationship curve chart of AA in solution.
Result is along with the increase of AA concentration in solution, and peak current also increases therewith, and its linearly dependent coefficient is 0.9973, illustrates that AA is had good response by PB/PVDF, and PB/PVDF modified electrode has good stability.
Claims (2)
1. the preparation method of Prussian blue/polyvinylidene fluoride composite nano fiber film, it is characterised in that including:
Being scattered in the mixed solvent of N,N-dimethylacetamide and acetone by Prussian blue, Kynoar, configuration obtains spinning liquid, adopts electrostatic spinning to prepare Prussian blue/polyvinylidene fluoride composite nano fiber film；
Mass percent Prussian blue in described spinning liquid is 0.5～2.0%；The mass percent of Kynoar is 8.0～9.5%；The mass percent of DMAC N,N' dimethyl acetamide is 35～55%；The mass percent of acetone is 35～55%；
During electrostatic spinning, ejection flow velocity is 0.5～2mL/h, and electrostatic pressure is 10～25KV, and receiving range is 10～20cm；The temperature keeping environment is 21～26 DEG C, and humidity is 45～55%.
2. as claimed in claim 1 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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| CN110760144B (en) * | 2019-11-06 | 2021-07-23 | 裘天政 | Polyvinylidene fluoride composite piezoelectric film and preparation method and application thereof |
| CN112342694A (en) * | 2020-10-30 | 2021-02-09 | 江苏省农业科学院 | FeZn Prussian blue/polyacrylonitrile composite nanofiber membrane as well as preparation method and application thereof |
| CN112430898B (en) * | 2020-11-11 | 2022-06-07 | 山东大学 | Thermal or solvent dual-stimulus color-change response nanofiber membrane and preparation method and application thereof |
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