CN106811832A - A kind of pearl-decorated curtain shape BiFeO3The preparation method and products obtained therefrom of micro nanometer fiber - Google Patents
A kind of pearl-decorated curtain shape BiFeO3The preparation method and products obtained therefrom of micro nanometer fiber Download PDFInfo
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- CN106811832A CN106811832A CN201710082287.0A CN201710082287A CN106811832A CN 106811832 A CN106811832 A CN 106811832A CN 201710082287 A CN201710082287 A CN 201710082287A CN 106811832 A CN106811832 A CN 106811832A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
Abstract
The invention discloses a kind of pearl-decorated curtain shape BiFeO3The preparation method and products obtained therefrom of micro nanometer fiber, ferric nitrate, bismuth nitrate, glacial acetic acid, neopentyl glycol are added sequentially in the mixed solvent of water and glycerine, clear solution is obtained, precursor solution is obtained by stirring insulation after solvent thermal reaction treatment, at being placed in 75 85 DEG C；After PVP is dissolved in into the mixed solvent of water and the methylimidazole acetate of 1 ethyl 3, it is slowly added into precursor solution, obtains spinning liquid as precursor, precursor fibre is obtained by method of electrostatic spinning, gained precursor fibre is thermally treated, obtains product.The present invention is prepared for the pearl-decorated curtain shape BiFeO of size adjustable using the mode that solvent-thermal method and method of electrostatic spinning are combined3Micro nanometer fiber, building-up process is easily controllable, and product morphology is unique, reproducible, the pearl-decorated curtain shape BiFeO for obtaining3Micro nanometer fiber has potential application in fields such as photocatalysis, ferroelectric piezoelectric devices.
Description
Technical field
The present invention relates to a kind of pearl-decorated curtain shape BiFeO3The preparation method of micro nanometer fiber, and in particular to a kind of size adjustable
Pearl-decorated curtain shape BiFeO3The preparation method and products obtained therefrom of micro nanometer fiber.
Background technology
Multi-ferroic material has narrower band gap and ferroelectric property, has stronger absorption to visible ray, in photocatalysis
It is big with photovoltaic art application prospect.BiFeO3It is a kind of important room temperature multi-ferroic material, it is excellent with chemical stability higher
Different anti-ferromagnetism and ferromagnetism, Neel transition temperatures higher（640 K）With Curie transition temperatures（1100 K）, band gap
It is 2.0-2.7 eV, it is considered to be third generation visible light responsive photocatalyst material.
BiFeO3The spontaneous polarization of ferroelectric material can strengthen the efficiency of transmission and reactivity of photo-generated carrier, but it is led
With position is relatively low, the defective effect such as specific surface area is small, photo-generated carrier combined efficiency is high BiFeO3Material is in photocatalysis etc.
The extensive use of aspect.Research shows that the optimization of low-dimensional microstructure can be effectively improved BiFeO3Electric transmission, magnetic,
The performances such as ferroelectricity, photocatalysis efficiency.One-dimensional material has specific surface area big, and Debye length is controllable, and interfacial reaction activity is strong
Feature, excellent physicochemical properties are shown at aspects such as lithium battery, photocatalysis, air-sensitives.With nano wire, nanotube, nanometer
Rod is compared, and one dimension fibre structure generally has larger draw ratio, extensively should in fields such as the energy, environment, organizational projects
With.Common BiFeO3The preparation method of fibrous material mainly includes method of electrostatic spinning, hydro-thermal reaction method, microwave process for synthesizing etc.,
The product morphology controllability for obtaining is high, reproducible.It is suitable by selection in particular with the development increasingly of electrostatic spinning technique
Precursor solution system, change electrospinning parameters and subsequent heat treatment system etc., different-diameter can be effectively synthesized
BiFeO3Fibrous material, receives the extensive concern of people.
At present, BiFeO is prepared using method of electrostatic spinning3The research of fibrous material is at the early-stage, the product morphology for obtaining with
Based on Single Fiber or stub pattern, course of reaction forms transparent molten for various ions are dissolved in certain solvent with high polymer
Liquid, obtains precursor fibre, then obtain BiFeO by high-temperature burning process by electrostatic spinning process3Product structure.Can dash forward
Break conventional electrostatic spinning process limitation, introduce different fiber morphology controlled factordiseases and fiber Forming Mechanism, be to obtain structure
Special, excellent performance BiFeO3The important means of fibrous material, is also to synthesize BiFeO using electrostatic spinning technique at this stage3It is fine
The most important theories for tieing up material are explored and mechanism innovation.
The content of the invention
A kind of deficiency that the present invention exists for existing method, there is provided pearl-decorated curtain shape BiFeO3The preparation side of micro nanometer fiber
Method, the method has that raw material sources are extensive, synthesis technique is easy, the reproducible, size adjustable of easily operated, product morphology etc. is excellent
Gesture.
Present invention also offers the pearl-decorated curtain shape BiFeO obtained using the above method3Micro nanometer fiber product, the product has
Bead chain shape pattern, is that method of electrostatic spinning prepares BiFeO3Micro nanometer fiber provides new pattern.
The present invention combines solvent-thermal method and electrostatic spinning technique has obtained pearl-decorated curtain shape BiFeO3Micro nanometer fiber, particular technique
Scheme is as follows：
A kind of pearl-decorated curtain shape BiFeO3The preparation method of micro nanometer fiber, the method is comprised the following steps：
（1）Ferric nitrate, bismuth nitrate, glacial acetic acid and neopentyl glycol are added sequentially in the mixed solvent of water and glycerine, are stirred
Obtain clear solution；
（2）Clear solution is carried out into solvent thermal reaction, then the constant temperature stirring reaction at 75-85 DEG C, obtains precursor solution；
（3）By polyvinylpyrrolidone（PVP）It is dissolved in water and 1- ethyl-3-methylimidazole acetate（[ Emim]Ac）Mixing
In solvent, the mixture is then slowly added to step（2）Precursor solution in, stir to obtain spinning liquid as precursor；
（4）Spinning liquid as precursor is formed into precursor fibre by electrostatic spinning, then precursor fibre is heat-treated, obtained
To pearl-decorated curtain shape BiFeO3Micro nanometer fiber.
The present invention prepares pearl-decorated curtain shape BiFeO by the combination of solvent-thermal method and method of electrostatic spinning3Micro nanometer fiber, first will be saturating
Bright solution carries out solvent thermal reaction, obtains a large amount of BiFeO3The finely dispersed aaerosol solution of tiny crystals, is then stirred by insulation
Mix and further improve viscosity, particle dispersion of aaerosol solution etc., form precursor solution.Wherein, neopentyl glycol is surface work
Property agent and dispersant, PVP is conducting polymer, and [Emim] Ac is solvent and dispersant, under their collective effect, is contained
BiFeO3The precursor solution of tiny crystals easily can form fiber by electrostatic spinning process, and through Overheating Treatment
Also it is readily formed pearl-decorated curtain shape BiFeO3Micro nanometer fiber.
Above-mentioned steps（1）In, ferric nitrate, bismuth nitrate, the mol ratio of neopentyl glycol are 1：1：1.5-2, glacial acetic acid, water and third
The volume ratio of triol is 1：3-3.9：1-1.3.
Above-mentioned steps（1）In, concentration of the ferric nitrate in the mixed solvent of water and glycerine is 0.3-0.5 mol/L.
Above-mentioned steps（2）In, clear solution carries out solvent thermal reaction at 110-130 DEG C, and the reaction time is 0.5-8h.It is molten
Agent thermal response is carried out in confined conditions.After solvent thermal reaction, a large amount of finely dispersed BiFeO can be obtained3Tiny crystals.
Above-mentioned steps（2）In, after solvent thermal reaction, solution constant temperature stirring reaction 1-8 h at 75-85 DEG C are further carried
Viscosity, particle dispersion of mixed solution high etc..
Above-mentioned steps（3）In, water and 1- ethyl-3-methylimidazole acetate（[Emim]Ac）Volume ratio be 1：0.1-
0.3.Concentration of the PVP in mixed solvent is 1.6-2.3 mol/L, and the wherein mole of PVP presses the mole of its polymerized monomer
Meter.
Above-mentioned steps（3）In, the solution containing polyvinylpyrrolidone（That is PVP is dissolved in water and 1- ethyl-3-methylimidazole vinegar
The mixture formed in the mixed solvent of hydrochlorate）With step（2）Precursor solution volume ratio be 1:2.1-3.4.
Above-mentioned steps（3）In, the mixture containing PVP is added to step（2）Precursor solution in, stir 1-8 h
Obtain spinning liquid as precursor.
Above-mentioned steps（4）In, electrospinning parameters include：Positive voltage be 15-20 KV, negative voltage be 0.5 KV, receive away from
From being 14-18 cm, syringe fltting speed is 0.001-0.002 mm/s.
Above-mentioned steps（4）In, it is by the process that precursor fibre is heat-treated：By precursor fibre according to 1-3 DEG C/
The programming rate of min rises to 300 DEG C by room temperature, is incubated 1-3 h, then rises to 500-600 DEG C with the programming rate of 5 DEG C/min,
Insulation 1-5 h.Heat treatment process is carried out in air atmosphere.
The micro nanometer fiber that the present invention is obtained is pearl-decorated curtain shape, by the BeFeO being connected with each other3Particle assembles.The BeFeO3
The pattern of particle is spherical, and grain size is 50-500 nm, pearl-decorated curtain shape BiFeO3The average diameter of micro nanometer fiber is also
50-500 nm。
The present invention has obtained pearl-decorated curtain shape BiFeO by solvent-thermal method and method of electrostatic spinning3Micro nanometer fiber, its pattern is special
Very, the pattern is obtained using method of electrostatic spinning first, and products obtained therefrom of the present invention is also within the scope of the present invention.
The present invention is in state natural sciences fund youth's Projects（Project approval number：51402123）And country
Students' Innovation drill program project（Project approval number：201510427002、201610427017）Subsidy under completed
's.The present invention is prepared for the pearl-decorated curtain shape BiFeO of size adjustable by way of solvent thermal reaction and electrostatic spinning technique are combined3
Micro nanometer fiber.According to existing conventional method, the continuous fiber of different-diameter only can be directly obtained using electrostatic spinning technique
Shape BiFeO3Micro nano structure, its reaction mechanism is mainly presoma clear solution and passes through electrostatic spinning work in the presence of PVP
Skill obtains precursor fibre structure, then in follow-up heat treatment process by control the decomposition of organic matter, redox reaction,
Gas effusion speed etc. makes new inorganic compound crystal produce and grow up, and obtains corresponding continuous fiber product.And it is of the invention
Reaction mechanism have that essence is different from simple method of electrostatic spinning, autonomous innovation is high.The present invention is anti-by solvent heat first
A large amount of BiFeO should have been obtained3The finely dispersed aaerosol solution of tiny crystals, is then further improved by way of stirring in water bath
The viscosity of mixed solution, particle dispersion etc.；The electricity of precursor solution is effectively enhanced by the introducing of PVP, [Emim] Ac
The parameters such as conductance, viscosity, not only contribute to the forming process of precursor fibre, are also beneficial to heat treatment stages control pearl-decorated curtain shape
BiFeO3The forming process of micro nanometer fiber.In the present invention, by solvent thermal reaction and stirring in water bath to BiFeO3Crystal into
Core, the process such as grow up, disperse, fixing carry out Effective Regulation, and BiFeO is controlled by heat treatment3Tiny crystals it is mutually reciprocal
Should, fusion, growth process, finally given various sizes of pearl-decorated curtain shape BiFeO3Micro nanometer fiber, pearl-decorated curtain shape BiFeO3It is micro-nano
The basic component units of fiber are spherical BiFeO3Micro-nano granules, BiFeO3Micro-nano granules are carried along precursor fibre
The template form of confession is cascaded and forms pearl-decorated curtain shape BiFeO3Micro nanometer fiber.That is, the BiFeO in the present invention3It is brilliant
The nucleation process of body mostlys come from solvent thermal reaction process, and pearl-decorated curtain shape BiFeO3The formation mechenism of micro nanometer fiber is mainly
BiFeO3Crystal is under the synergy of suitable surfactant, dispersant, solvent etc. by heat treated process control BiFeO3
The fusion of crystal, grow up and one-dimensional square orientation diffusion process.
The inventive method is summarized on the basis of a large amount of compound experiments and gone out, BiFeO3The microscopic appearance of product with it is anti-
Answer mechanism novel, the method for electrostatic spinning with domestic and international report prepares BiFeO3There are greatest differences in fiber, and operation controllability is good,
Products collection efficiency is high, with important theoretical and practical application meaning, the pearl-decorated curtain shape BiFeO for obtaining3Micro nanometer fiber has preferable
Photocatalysis, ferroelectricity, piezoelectric property, there is preferable application prospect in photocatalysis, ferroelectric piezoelectric field.
Brief description of the drawings
Fig. 1 is the pearl-decorated curtain shape BiFeO of the synthesis of the embodiment of the present invention 13The X ray diffracting spectrum of fiber（XRD）.
Fig. 2 is the pearl-decorated curtain shape BiFeO of the synthesis of the embodiment of the present invention 13The ESEM of fiber（SEM）Picture.
Fig. 3 is the pearl-decorated curtain shape BiFeO of the synthesis of the embodiment of the present invention 13The transmission electron microscope of fiber（TEM）Picture.
Fig. 4 is the BiFeO of the synthesis of comparative example of the present invention 13The SEM pictures of fiber.
Specific embodiment
Below by embodiment, the present invention will be further elaborated, and the description below is of the invention only for explaining, not
Its content is defined.
The molecular weight of PVP used of the invention is more than 1,000,000, in following embodiments, and the molecular weight of PVP used is 1300000,
The molal quantity of PVP presses monomer calculating, and monomer molal weight is 111.
Embodiment 1
1.1 by the Fe(NO3)39H2O of 3.265 g（Fe(NO3)3∙9H2O）, 3.920 g five nitric hydrate bismuths（Bi(NO3)3∙
5H2O）, the glacial acetic acid of 5.0 mL, the neopentyl glycol of 1.512 g be added sequentially to 15.0 mL deionized water and 5.0 mL third
In the mixed solvent of triol, stirring obtains clear solution, and the solution is transferred in reactor, after 4 h are reacted at 120 DEG C,
It is placed in and stirs 5 h in 80 DEG C of waters bath with thermostatic control and obtain precursor solution；
After the PVP of 1.376 g is dissolved in the mixed solvent of [Emim] Ac of the deionized water of 5.0 mL and 1.2 mL by 1.2, delay
Slowly it is added in 1.1 precursor solutions for obtaining, 6 h of stirring obtain spinning liquid as precursor, and forerunner is obtained by method of electrostatic spinning
Body fiber, spinning parameter is：Positive voltage is 18 KV, and negative voltage is 0.5 KV, and it is 16 cm, syringe fltting speed to receive distance
It is 0.001 mm/s.
1.3 are placed in Muffle furnace precursor fiber, and 300 DEG C are risen to by room temperature according to the programming rate of 1 DEG C/min, protect
2 h of temperature, then 550 DEG C are risen to the programming rate of 5 DEG C/min, 2 h are incubated, pearl-decorated curtain shape BiFeO is obtained after sample furnace cooling3
Fiber.
The XRD results of product as shown in figure 1, it can be seen that all of diffraction maximum with standard x RD cards（71-
2494）It is consistent, it was demonstrated that products therefrom is the BiFeO of hexagonal phase3Crystalline phase；The SEM figures of product are as shown in Fig. 2 of the invention obtain
To fiber be by BeFeO3The one-dimensional pearl-decorated curtain shape pattern that particle is assembled into, the pearl-decorated curtain shape BiFeO3The average diameter of fiber is
140-160 nm, its basic structural unit BeFeO3The pattern of particle is spherical, and grain size is 140-160 nm；Product
TEM is schemed as shown in figure 3, by contrast, BiFeO3The microscopic appearance of fiber is consistent with the result of SEM, it was demonstrated that the product for obtaining
Thing is pearl-decorated curtain shape BiFeO3Fibre structure.
Embodiment 2
2.1 by the Fe (NO of 2.693 g3)3∙9H2Bi (the NO of O, 3.234 g3)3∙5H2O, the glacial acetic acid of 5.3 mL, 1.042 g
Neopentyl glycol is added sequentially in the mixed solvent of the glycerine of the deionized water of 16.0 mL and 5.3 mL, and stirring obtains transparent
Solution, the solution is transferred in reactor, after 7 h are reacted at 110 DEG C, is placed in and is stirred 8 h in 80 DEG C of waters bath with thermostatic control and obtain
Precursor solution；
After the PVP of 1.612 g is dissolved in the mixed solvent of [Emim] Ac of the deionized water of 6.0 mL and 0.6 mL by 2.2, delay
Slowly it is added in 2.1 precursor solutions for obtaining, 8 h of stirring obtain spinning liquid as precursor, and forerunner is obtained by method of electrostatic spinning
Body fiber, spinning parameter is：Positive voltage is 15 KV, and negative voltage is 0.5 KV, and it is 14 cm, syringe fltting speed to receive distance
It is 0.002 mm/s.
2.3 are placed in Muffle furnace precursor fiber, and 300 DEG C are risen to by room temperature according to the programming rate of 2 DEG C/min, protect
1 h of temperature, then 500 DEG C are risen to the programming rate of 5 DEG C/min, 5 h are incubated, obtaining average diameter after sample furnace cooling is
The pearl-decorated curtain shape BiFeO of 70-90 nm3Fibre structure.
Embodiment 3
3.1 by the Fe (NO of 4.530 g3)3∙9H2Bi (the NO of O, 5.439 g3)3∙5H2O, the glacial acetic acid of 5.0 mL, 2.330 g
Neopentyl glycol is added sequentially in the mixed solvent of the glycerine of the deionized water of 17.0 mL and 5.7 mL, and stirring obtains transparent
Solution, the solution is transferred in reactor, after 1 h is reacted at 130 DEG C, is placed in and is stirred 4 h in 80 DEG C of waters bath with thermostatic control and obtain
Precursor solution；
After the PVP of 1.227 g is dissolved in the mixed solvent of [Emim] Ac of the deionized water of 5.5 mL and 1.0 mL by 3.2, delay
Slowly it is added in 3.1 precursor solutions for obtaining, 4 h of stirring obtain spinning liquid as precursor, and forerunner is obtained by method of electrostatic spinning
Body fiber, spinning parameter is：Positive voltage is 16 KV, and negative voltage is 0.5 KV, and it is 15 cm, syringe fltting speed to receive distance
It is 0.002 mm/s.
3.3 are placed in Muffle furnace precursor fiber, and 300 DEG C are risen to by room temperature according to the programming rate of 3 DEG C/min, protect
3 h of temperature, then 600 DEG C are risen to the programming rate of 5 DEG C/min, 1 h is incubated, obtaining average diameter after sample furnace cooling is
The pearl-decorated curtain shape BiFeO of 230-260 nm3Fibre structure.
Embodiment 4
4.1 by the Fe (NO of 2.653 g3)3∙9H2Bi (the NO of O, 3.185 g3)3∙5H2O, the glacial acetic acid of 4.5 mL, 1.162 g
Neopentyl glycol is added sequentially in the mixed solvent of the glycerine of the deionized water of 14.0 mL and 4.7 mL, and stirring obtains transparent
Solution, the solution is transferred in reactor, after 2 h are reacted at 120 DEG C, is placed in and is stirred 3 h in 80 DEG C of waters bath with thermostatic control and obtain
Precursor solution；
After the PVP of 1.608 g is dissolved in the mixed solvent of [Emim] Ac of the deionized water of 5.8 mL and 1.1 mL by 4.2, delay
Slowly it is added in 4.1 precursor solutions for obtaining, 6 h of stirring obtain spinning liquid as precursor, and forerunner is obtained by method of electrostatic spinning
Body fiber, spinning parameter is：Positive voltage is 18 KV, and negative voltage is 0.5 KV, and it is 17 cm, syringe fltting speed to receive distance
It is 0.001 mm/s.
4.3 are placed in Muffle furnace precursor fiber, and 300 DEG C are risen to by room temperature according to the programming rate of 2 DEG C/min, protect
2 h of temperature, then 550 DEG C are risen to the programming rate of 5 DEG C/min, 3 h are incubated, obtaining average diameter after sample furnace cooling is
The pearl-decorated curtain shape BiFeO of 190-220 nm3Fibre structure.
Embodiment 5
5.1 by the Fe (NO of 3.918 g3)3∙9H2Bi (the NO of O, 4.704 g3)3∙5H2O, the glacial acetic acid of 4.8 mL, 1.919 g
Neopentyl glycol is added sequentially in the mixed solvent of the glycerine of the deionized water of 16.0 mL and 5.3 mL, and stirring obtains transparent
Solution, the solution is transferred in reactor, after 1 h is reacted at 130 DEG C, is placed in and is stirred 7 h in 80 DEG C of waters bath with thermostatic control and obtain
Precursor solution；
After the PVP of 1.399 g is dissolved in the mixed solvent of [Emim] Ac of the deionized water of 5.4 mL and 1.6 mL by 5.2, delay
Slowly it is added in 5.1 precursor solutions for obtaining, 7 h of stirring obtain spinning liquid as precursor, and forerunner is obtained by method of electrostatic spinning
Body fiber, spinning parameter is：Positive voltage is 20 KV, and negative voltage is 0.5 KV, and it is 14 cm, syringe fltting speed to receive distance
It is 0.001 mm/s.
5.3 are placed in Muffle furnace precursor fiber, and 300 DEG C are risen to by room temperature according to the programming rate of 1 DEG C/min, protect
1 h of temperature, then 600 DEG C are risen to the programming rate of 5 DEG C/min, 4 h are incubated, obtaining average diameter after sample furnace cooling is
The pearl-decorated curtain shape BiFeO of 420-470 nm3Fibre structure.
Embodiment 6
6.1 by the Fe (NO of 2.586 g3)3∙9H2Bi (the NO of O, 3.136 g3)3∙5H2O, the glacial acetic acid of 4.5 mL, 1.145 g
Neopentyl glycol is added sequentially in the mixed solvent of the glycerine of the deionized water of 15.0 mL and 5.0 mL, and stirring obtains transparent
Solution, the solution is transferred in reactor, after 4 h are reacted at 110 DEG C, is placed in and is stirred 5 h in 80 DEG C of waters bath with thermostatic control and obtain
Precursor solution；
After the PVP of 1.562 g is dissolved in the mixed solvent of [Emim] Ac of the deionized water of 5.3 mL and 1.4 mL by 6.2, delay
Slowly it is added in 6.1 precursor solutions for obtaining, 3 h of stirring obtain spinning liquid as precursor, and forerunner is obtained by method of electrostatic spinning
Body fiber, spinning parameter is：Positive voltage is 16 KV, and negative voltage is 0.5 KV, and it is 15 cm, syringe fltting speed to receive distance
It is 0.002 mm/s.
6.3 are placed in Muffle furnace precursor fiber, and 300 DEG C are risen to by room temperature according to the programming rate of 2 DEG C/min, protect
2 h of temperature, then 550 DEG C are risen to the programming rate of 5 DEG C/min, 3 h are incubated, obtaining average diameter after sample furnace cooling is
The pearl-decorated curtain shape BiFeO of 280-320 nm3Fibre structure.
Comparative example 1
1.1 by the Fe (NO of 3.265 g3)3∙9H2Bi (the NO of O, 3.920 g3)3∙5H2O, the glacial acetic acid of 5.0 mL, 1.512 g
Neopentyl glycol be added sequentially in the mixed solvent of the glycerine of the deionized water of 15.0 mL and 5.0 mL, stirring obtain
Bright solution；
1.2 with embodiment 1.
1.3 with embodiment 1.
The SEM figures of products therefrom are as shown in figure 4, it can be seen that products therefrom is Size Distribution heterogeneity, reunites
The obvious BiFeO of phenomenon3Continuous fiber pattern, distribution of fiber diameters scope is big, bad dispersibility.The product no longer has pearl-decorated curtain shape
BiFeO3Fibre structure.It can thus be seen that generation of the introducing of solvent thermal reaction to the microscopic appearance of product has important shadow
Ring.
Comparative example 2
2.1 by the Fe (NO of 3.265 g3)3∙9H2Bi (the NO of O, 3.920 g3)3∙5H2O, the glacial acetic acid of 5.0 mL, 0.421 g
Neopentyl glycol is added sequentially in the mixed solvent of the ethylene glycol of the deionized water of 15.0 mL and 5.0 mL, and stirring obtains transparent
Solution, the solution is transferred in reactor, after 5 h are reacted at 150 DEG C, is placed in and is stirred 5 h in 80 DEG C of waters bath with thermostatic control and obtain
Precursor solution；
2.2 with embodiment 1.
2.3 with embodiment 1.
Size heterogeneity is obtained after products therefrom furnace cooling and distribution is big, reunite serious BiFeO3Spherical
Grain, no longer with BiFeO3Fibre structure.It can thus be seen that the setting of clear solution composition and solvent thermal reaction condition is to producing
Thing pattern has material impact, and the setting of solvent thermal reaction condition is improper to be will be unable to obtain pearl-decorated curtain shape BiFeO3Fiber.
Comparative example 3
3.1 by the Fe(NO3)39H2O of 3.265 g（Fe(NO3)3∙9H2O）, 3.920 g five nitric hydrate bismuths（Bi(NO3)3∙
5H2O）, 5.0 mL glacial acetic acid, be added sequentially in the mixed solvent of the glycerine of the deionized water of 15.0 mL and 5.0 mL,
Stirring obtains clear solution, and the solution is transferred in reactor, after 4 h are reacted at 120 DEG C, is placed in 80 DEG C of waters bath with thermostatic control
5 h of middle stirring obtain precursor solution.
3.2 are dissolved in the deionized water of 5.0 mL the PVP of 1.376 g, are slowly added into 3.1 presomas for obtaining molten
In liquid, 6 h of stirring obtain spinning liquid as precursor, and precursor fibre is obtained by method of electrostatic spinning, and spinning parameter is：Positive voltage is
18 KV, negative voltage is 0.5 KV, and it is 16 cm to receive distance, and syringe fltting speed is 0.001 mm/s.
3.3 with embodiment 1.
Obtained after products therefrom furnace cooling by a large amount of Size Distribution heterogeneities, the blocky-shaped particle collection combinate form without fixed pattern
Into BiFeO3Fiber, distribution of fiber diameters scope is big, and particle agglomeration phenomenon is serious, no longer with pearl-decorated curtain shape structure.Thus may be used
To find out, the addition of neopentyl glycol and [Emim] Ac is to pearl-decorated curtain shape BiFeO3The formation of fibre structure has material impact.
Comparative example 4
4.1 with embodiment 1.
4.2 mixed solvents that the PVP of 1.376 g is dissolved in the deionized water of 5.0 mL and [Emim] Ac of 1.2 mL
Afterwards, it is slowly added into 1.1 precursor solutions for obtaining, 6 h of stirring obtain spinning liquid as precursor, are obtained by method of electrostatic spinning
Precursor fibre, spinning parameter is：Positive voltage is 25 KV, and negative voltage is 0.5 KV, and it is 23 cm, syringe propulsion to receive distance
Speed is 0.004 mm/s.
4.3 are placed in Muffle furnace precursor fiber, and 550 DEG C are risen to by room temperature according to the programming rate of 5 DEG C/min, protect
2 h of temperature, product is obtained after sample furnace cooling.
Products therefrom is that the blocky-shaped particle by a large amount of Size Distribution heterogeneities, agglomeration seriously, without fixed pattern gathers
The BiFeO of formation3Laminated structure, it can thus be seen that the setting of electrostatic spinning and heat treatment parameter is to pearl-decorated curtain shape BiFeO3Fiber
The formation of structure has material impact.
Claims (10)
1. a kind of pearl-decorated curtain shape BiFeO3The preparation method of micro nanometer fiber, it is characterized in that comprising the following steps：
（1）Ferric nitrate, bismuth nitrate, glacial acetic acid and neopentyl glycol are added sequentially in the mixed solvent of water and glycerine, are stirred
Obtain clear solution；
（2）Clear solution is carried out into solvent thermal reaction, then the constant temperature stirring reaction at 75-85 DEG C, obtains precursor solution；
（3）Polyvinylpyrrolidone is dissolved in the mixed solvent of water and 1- ethyl-3-methylimidazole acetate, then this is mixed
Compound is slowly added to step（2）Precursor solution in, stir to obtain spinning liquid as precursor；
（4）Spinning liquid as precursor is formed into precursor fibre by electrostatic spinning, then precursor fibre is heat-treated, obtained
To pearl-decorated curtain shape BiFeO3Micro nanometer fiber.
2. preparation method according to claim 1, it is characterized in that：Step（1）In, ferric nitrate, bismuth nitrate, neopentyl glycol
Mol ratio is 1：1：1.5-2, the volume ratio of glacial acetic acid, water and glycerine is 1：3-3.9：1-1.3；Step（3）In, water and 1- second
The volume ratio of base -3- methylimidazole acetate is 1：0.1-0.3.
3. preparation method according to claim 1 and 2, it is characterized in that：Step（1）In, ferric nitrate is in water and glycerine
Concentration in mixed solvent is 0.3-0.5 mol/L；Step（3）In, concentration of the PVP in mixed solvent is 1.6-2.3 mol/
The mole of L, wherein PVP presses the molar amount of its polymerized monomer.
4. the preparation method according to claim 1,2 or 3, it is characterized in that：Step（3）In, containing polyvinylpyrrolidone
Mixture is 1 with the volume ratio of precursor solution:2.1-3.4.
5. the preparation method according to any one of claim 1-4, it is characterized in that：Step（2）In, clear solution is in 110-
Solvent thermal reaction is carried out at 130 DEG C, the reaction time is 0.5-8 h；After solvent thermal reaction, solution constant temperature stirring at 75-85 DEG C
Reaction 1-8 h.
6. preparation method according to claim 1 or 5, it is characterized in that：Solvent thermal reaction is carried out in confined conditions.
7. preparation method according to claim 1, it is characterized in that：Step（4）In, during electrostatic spinning, positive voltage is 15-20
KV, negative voltage is 0.5 KV, and it is 14-18 cm to receive distance, and syringe fltting speed is 0.001-0.002 mm/s.
8. the preparation method according to any one of claim 1-7, it is characterized in that：Step（4）In, heat treatment process is：
Precursor fibre is risen to 300 DEG C according to the programming rate of 1-3 DEG C/min by room temperature, 1-3 h are incubated, then with 5 DEG C/min's
Programming rate rises to 500-600 DEG C, insulation 1-5 h.
9. the preparation method according to any one of claim 1-8, it is characterized in that：Gained BiFeO3Micro nanometer fiber is pearl
Curtain shape, by the BeFeO being connected with each other3Particle assembles, BeFeO3The pattern of particle is spherical, and grain size is 50-500
nm。
10. according to the pearl-decorated curtain shape BiFeO any one of claim 1-93Pearl-decorated curtain obtained in the preparation method of micro nanometer fiber
Shape BiFeO3Micro nanometer fiber.
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