CN106811832B - 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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- CN106811832B CN106811832B CN201710082287.0A CN201710082287A CN106811832B CN 106811832 B CN106811832 B CN 106811832B CN 201710082287 A CN201710082287 A CN 201710082287A CN 106811832 B CN106811832 B CN 106811832B
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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
-
- 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 to the in the mixed solvent of water and glycerine, clear solution is obtained, after being handled by solvent thermal reaction, stirring heat preservation at 75-85 DEG C is placed in and obtains precursor solution；It after PVP to be dissolved in the mixed solvent of water and 1- ethyl-3-methylimidazole acetate, 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 by solvent-thermal method and method of electrostatic spinning combine in the way of be prepared for the pearl-decorated curtain shape BiFeO of size adjustable3Micro nanometer fiber, synthesis process is easily controllable, and product morphology is unique, reproducible, obtained pearl-decorated curtain shape BiFeO3Micro 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 technique
Multi-ferroic material has relatively narrow band gap and ferroelectric property, has stronger absorption to visible light, in photocatalysis
It is big with photovoltaic art application prospect.BiFeO3It is a kind of important room temperature multi-ferroic material, chemical stability with higher is excellent
Different anti-ferromagnetism and ferromagnetism, higher Neel transition temperature (640 K) and Curie transition temperature (1100 K), band gap
For 2.0-2.7 eV, it is considered to be third generation visible light responsive photocatalyst material.
BiFeO3The spontaneous polarization of ferroelectric material can enhance the efficiency of transmission and reactivity of photo-generated carrier, but it is led
The defective effects such as, specific surface area small, the combined efficiency height of photo-generated carrier lower with position BiFeO3Material is in photocatalysis etc.
The extensive use of aspect.Studies have shown that the optimization of low-dimensional microstructure can be effectively improved BiFeO3Electron-transport, magnetism,
The performances such as ferroelectricity, photocatalysis efficiency.One-dimensional material has large specific surface area, and Debye length is controllable, and interfacial reaction activity is strong
Feature, lithium battery, photocatalysis, in terms of show excellent physicochemical properties.With nano wire, nanotube, nanometer
Stick is compared, and one dimension fibre structure usually has biggish draw ratio, is answered extensively 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.,
Obtained product morphology controllability is high, reproducible.It is suitable by selecting 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.
Currently, preparing BiFeO using method of electrostatic spinning3The research of fibrous material is at the early-stage, obtained product morphology with
Based on Single Fiber or stub pattern, reaction process be various ions be dissolved in certain solvent with high polymer formed it is transparent molten
Liquid, obtains precursor fibre by electrostatic spinning process, obtains BiFeO using high-temperature burning process3Product structure.It can dash forward
It breaks conventional electrostatic spinning process limitation, introduce different fiber morphology controlled factordisease and fiber Forming Mechanism, be to obtain structure
BiFeO that is special, haveing excellent performance3The important means of fibrous material, and BiFeO is synthesized using electrostatic spinning technique at this stage3It is fine
The most important theories for tieing up material are explored to be innovated with mechanism.
Summary of the invention
The present invention provides a kind of pearl-decorated curtain shape BiFeO for deficiency existing for existing method3The preparation side of micro nanometer fiber
Method, this method have that raw material sources are extensive, synthesis technology is easy, easily operated, product morphology is reproducible, size adjustable etc. is excellent
Gesture.
The present invention also provides use pearl-decorated curtain shape BiFeO obtained by the above method3Micro nanometer fiber product, the product have
Bead chain shape pattern prepares BiFeO for method of electrostatic spinning3Micro nanometer fiber provides new pattern.
Present invention combination solvent-thermal method and electrostatic spinning technique have 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, method includes the following steps:
(1) ferric nitrate, bismuth nitrate, glacial acetic acid and neopentyl glycol are added sequentially to the in the mixed solvent of water and glycerine,
Stir to get clear solution；
(2) clear solution is subjected to solvent thermal reaction, then constant temperature is stirred to react at 75-85 DEG C, obtains precursor solution；
(3) polyvinylpyrrolidone (PVP) is dissolved in water and 1- ethyl-3-methylimidazole acetate ([Emim] Ac)
Then the mixture is slowly added in the precursor solution of step (2) by the mixed solvent, stir to obtain spinning liquid as precursor；
(4) spinning liquid as precursor is formed into precursor fibre by electrostatic spinning, precursor fibre is then subjected to hot place
Reason, obtains 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 BiFeO3Then the finely dispersed aaerosol solution of tiny crystals is stirred by heat preservation
The viscosity for further increasing aaerosol solution, particle dispersion etc. are mixed, precursor solution is formed.Wherein, neopentyl glycol is living for surface
Property agent and dispersing agent, PVP is conducting polymer, and [Emim] Ac is that solvent and dispersing agent contain under their collective effect
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.
In above-mentioned steps (1), ferric nitrate, bismuth nitrate, neopentyl glycol molar ratio be 1:1:1.5-2, glacial acetic acid, water and third
The volume ratio of triol is 1:3-3.9:1-1.3.
In above-mentioned steps (1), ferric nitrate is 0.3-0.5 mol/L in the concentration of the in the mixed solvent of water and glycerine.
In above-mentioned steps (2), clear solution carries out solvent thermal reaction, reaction time 0.5-8h at 110-130 DEG C.It is molten
Agent thermal response carries out in confined conditions.After solvent thermal reaction, available a large amount of finely dispersed BiFeO3Tiny crystals.
In above-mentioned steps (2), after solvent thermal reaction, solution constant temperature at 75-85 DEG C is stirred to react 1-8 h, further mentions
Viscosity, particle dispersion of high mixed solution etc..
In above-mentioned steps (3), the volume ratio of water and 1- ethyl-3-methylimidazole acetate ([Emim] Ac) is 1:0.1-
0.3.PVP is 1.6-2.3 mol/L in the concentration of in the mixed solvent, and wherein the mole of PVP presses the mole of its polymerized monomer
Meter.
In above-mentioned steps (3), (i.e. PVP is dissolved in water and 1- ethyl-3-methylimidazole vinegar to the solution containing polyvinylpyrrolidone
The mixture that the in the mixed solvent of hydrochlorate is formed) it with the volume ratio of the precursor solution of step (2) is 1:2.1-3.4.
In above-mentioned steps (3), the mixture containing PVP is added in the precursor solution of step (2), stirs 1-8 h
Obtain spinning liquid as precursor.
In above-mentioned steps (4), electrospinning parameters include: positive voltage be 15-20 KV, negative voltage be 0.5 KV, receive away from
From for 14-18 cm, syringe fltting speed is 0.001-0.002 mm/s.
In above-mentioned steps (4), the process that precursor fibre is heat-treated is: by precursor fibre according to 1-3 DEG C/
The heating rate of min rises to 300 DEG C by room temperature, keeps the temperature 1-3 h, then rise to 500-600 DEG C with the heating rate of 5 DEG C/min,
Keep the temperature 1-5 h.Heat treatment process carries out in air atmosphere.
The micro nanometer fiber that the present invention obtains is pearl-decorated curtain shape, by the BeFeO being connected with each other3Particle assembles.The BeFeO3
The pattern of particle be it is spherical, particle size be 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, pattern are special
Very, which is made using method of electrostatic spinning for the first time, and products obtained therefrom of the present invention is also within that scope of the present invention.
The present invention is in state natural sciences fund youth Projects (project approval number: 51402123) and national
Students' Innovation drill program project (project approval number: 201510427002, is completed under subsidy 201610427017)
's.The present invention is prepared for the pearl-decorated curtain shape BiFeO of size adjustable in such a way that solvent thermal reaction and electrostatic spinning technique combine3
Micro nanometer fiber.According to existing conventional method, the continuous fiber of the available different-diameter of electrostatic spinning technique is only directlyed adopt
Shape BiFeO3Micro nano structure, reaction mechanism are mainly that presoma clear solution passes through electrostatic spinning work under the action of PVP
Skill obtains precursor fibre structure, then in follow-up heat treatment process by the control decomposition of organic matter, redox reaction,
Gas evolution speed etc. generates new inorganic compound crystal and grows up, and obtains corresponding continuous fiber product.And it is of the invention
Reaction mechanism and simple method of electrostatic spinning different, the autonomous innovation height that there is essence.It is anti-that the present invention passes through solvent heat first
A large amount of BiFeO should be obtained3The finely dispersed aaerosol solution of tiny crystals, is then further increased 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 at
Core, the processes such as grow up, disperse, fixing carry out Effective Regulation, control BiFeO by heat treatment3Tiny crystals it is mutually reciprocal
It answers, merge, growth process, having finally obtained 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 mentioned along precursor fibre
The template form of confession, which is cascaded, 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 passes through heat treated process control BiFeO under the synergistic effect of suitable surfactant, dispersing agent, solvent etc.3
The fusion of crystal, grow up and one-dimensional square orientation diffusion process.
The method of the present invention is summarized on the basis of a large amount of compound experiments, BiFeO3The microscopic appearance of product and anti-
It answers mechanism novel, prepares BiFeO with the method for electrostatic spinning reported both at home and abroad3There are greatest differences for fiber, and operation controllability is good,
Products collection efficiency is high, with important theory and practical application meaning, obtained pearl-decorated curtain shape BiFeO3Micro nanometer fiber has preferable
Photocatalysis, ferroelectricity, piezoelectric property, photocatalysis, ferroelectric piezoelectric field with good application prospect.
Detailed description of the invention
Fig. 1 is the pearl-decorated curtain shape BiFeO that the embodiment of the present invention 1 synthesizes3The X ray diffracting spectrum (XRD) of fiber.
Fig. 2 is the pearl-decorated curtain shape BiFeO that the embodiment of the present invention 1 synthesizes3Scanning electron microscope (SEM) picture of fiber.
Fig. 3 is the pearl-decorated curtain shape BiFeO that the embodiment of the present invention 1 synthesizes3Transmission electron microscope (TEM) picture of fiber.
Fig. 4 is the BiFeO of comparative example 1 of the present invention synthesis3The SEM picture of fiber.
Specific embodiment
Below by embodiment, the present invention will be further elaborated, and following the description is only for explaining the present invention, not
Its content is defined.
The molecular weight of PVP used in the present invention is greater than 1,000,000, and in following embodiments, 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 (Fe (NO of 3.265 g3)3∙9H2O), the five nitric hydrate bismuth (Bi of 3.920 g
(NO3)3∙5H2O), the glacial acetic acid of 5.0 mL, 1.512 g neopentyl glycol be added sequentially to the deionized water and 5.0 of 15.0 mL
The in the mixed solvent of the glycerine of mL, stirs to get clear solution, which is transferred in reaction kettle, reacts at 120 DEG C
After 4 h, it is placed in and stirs 5 h in 80 DEG C of waters bath with thermostatic control and obtain precursor solution；
1.2 are dissolved in the PVP of 1.376 g the mixed solvent of the deionized water of 5.0 mL and [Emim] Ac of 1.2 mL
Afterwards, it is slowly added into the precursor solution that 1.1 obtain, 6 h of stirring obtain spinning liquid as precursor, are obtained by method of electrostatic spinning
Precursor fibre, spinning parameter are as follows: positive voltage is 18 KV, and negative voltage is 0.5 KV, and receiving distance is 16 cm, and syringe promotes
Speed is 0.001 mm/s.
1.3 are placed in precursor fiber in Muffle furnace, rise to 300 DEG C by room temperature according to the heating rate of 1 DEG C/min, protect
2 h of temperature, then 550 DEG C are risen to the heating rate of 5 DEG C/min, 2 h are kept the temperature, pearl-decorated curtain shape BiFeO is obtained after sample furnace cooling3
Fiber.
The XRD result of product as shown in Figure 1, it can be seen from the figure that all diffraction maximums with standard x RD card (71-
2494) it is consistent, it was demonstrated that products therefrom is the BiFeO of hexagonal phase3Crystal phase；The SEM of product schemes as shown in Fig. 2, the present invention obtains
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, basic structural unit BeFeO3The pattern of particle be it is spherical, particle size be 140-160 nm；Product
TEM figure is as shown in figure 3, by comparison it is found that BiFeO3The microscopic appearance of fiber and the result of SEM are consistent, it was demonstrated that obtained production
Object is pearl-decorated curtain shape BiFeO3Fibre structure.
Embodiment 2
2.1 by the Fe (NO of 2.693 g3)3∙9H2O, the Bi (NO of 3.234 g3)3∙5H2O, the glacial acetic acid of 5.3 mL, 1.042
The neopentyl glycol of g is added sequentially to the in the mixed solvent of the deionized water of 16.0 mL and the glycerine of 5.3 mL, stirs to get
The solution is transferred in reaction kettle by bright solution, 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
To precursor solution；
2.2 are dissolved in the PVP of 1.612 g the mixed solvent of the deionized water of 6.0 mL and [Emim] Ac of 0.6 mL
Afterwards, it is slowly added into the precursor solution that 2.1 obtain, 8 h of stirring obtain spinning liquid as precursor, are obtained by method of electrostatic spinning
Precursor fibre, spinning parameter are as follows: positive voltage is 15 KV, and negative voltage is 0.5 KV, and receiving distance is 14 cm, and syringe promotes
Speed is 0.002 mm/s.
2.3 are placed in precursor fiber in Muffle furnace, rise to 300 DEG C by room temperature according to the heating rate of 2 DEG C/min, protect
1 h of temperature, then 500 DEG C are risen to the heating rate of 5 DEG C/min, 5 h are kept the temperature, 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∙9H2O, the Bi (NO of 5.439 g3)3∙5H2O, the glacial acetic acid of 5.0 mL, 2.330
The neopentyl glycol of g is added sequentially to the in the mixed solvent of the deionized water of 17.0 mL and the glycerine of 5.7 mL, stirs to get
The solution is transferred in reaction kettle by bright solution, 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
To precursor solution；
3.2 are dissolved in the PVP of 1.227 g the mixed solvent of the deionized water of 5.5 mL and [Emim] Ac of 1.0 mL
Afterwards, it is slowly added into the precursor solution that 3.1 obtain, 4 h of stirring obtain spinning liquid as precursor, are obtained by method of electrostatic spinning
Precursor fibre, spinning parameter are as follows: positive voltage is 16 KV, and negative voltage is 0.5 KV, and receiving distance is 15 cm, and syringe promotes
Speed is 0.002 mm/s.
3.3 are placed in precursor fiber in Muffle furnace, rise to 300 DEG C by room temperature according to the heating rate of 3 DEG C/min, protect
3 h of temperature, then 600 DEG C are risen to the heating rate of 5 DEG C/min, 1 h is kept the temperature, 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∙9H2O, the Bi (NO of 3.185 g3)3∙5H2O, the glacial acetic acid of 4.5 mL, 1.162
The neopentyl glycol of g is added sequentially to the in the mixed solvent of the deionized water of 14.0 mL and the glycerine of 4.7 mL, stirs to get
The solution is transferred in reaction kettle by bright solution, 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
To precursor solution；
4.2 are dissolved in the PVP of 1.608 g the mixed solvent of the deionized water of 5.8 mL and [Emim] Ac of 1.1 mL
Afterwards, it is slowly added into the precursor solution that 4.1 obtain, 6 h of stirring obtain spinning liquid as precursor, are obtained by method of electrostatic spinning
Precursor fibre, spinning parameter are as follows: positive voltage is 18 KV, and negative voltage is 0.5 KV, and receiving distance is 17 cm, and syringe promotes
Speed is 0.001 mm/s.
4.3 are placed in precursor fiber in Muffle furnace, rise to 300 DEG C by room temperature according to the heating rate of 2 DEG C/min, protect
2 h of temperature, then 550 DEG C are risen to the heating rate of 5 DEG C/min, 3 h are kept the temperature, 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∙9H2O, the Bi (NO of 4.704 g3)3∙5H2O, the glacial acetic acid of 4.8 mL, 1.919
The neopentyl glycol of g is added sequentially to the in the mixed solvent of the deionized water of 16.0 mL and the glycerine of 5.3 mL, stirs to get
The solution is transferred in reaction kettle by bright solution, 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
To precursor solution；
5.2 are dissolved in the PVP of 1.399 g the mixed solvent of the deionized water of 5.4 mL and [Emim] Ac of 1.6 mL
Afterwards, it is slowly added into the precursor solution that 5.1 obtain, 7 h of stirring obtain spinning liquid as precursor, are obtained by method of electrostatic spinning
Precursor fibre, spinning parameter are as follows: positive voltage is 20 KV, and negative voltage is 0.5 KV, and receiving distance is 14 cm, and syringe promotes
Speed is 0.001 mm/s.
5.3 are placed in precursor fiber in Muffle furnace, rise to 300 DEG C by room temperature according to the heating rate of 1 DEG C/min, protect
1 h of temperature, then 600 DEG C are risen to the heating rate of 5 DEG C/min, 4 h are kept the temperature, 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∙9H2O, the Bi (NO of 3.136 g3)3∙5H2O, the glacial acetic acid of 4.5 mL, 1.145
The neopentyl glycol of g is added sequentially to the in the mixed solvent of the deionized water of 15.0 mL and the glycerine of 5.0 mL, stirs to get
The solution is transferred in reaction kettle by bright solution, 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
To precursor solution；
6.2 are dissolved in the PVP of 1.562 g the mixed solvent of the deionized water of 5.3 mL and [Emim] Ac of 1.4 mL
Afterwards, it is slowly added into the precursor solution that 6.1 obtain, 3 h of stirring obtain spinning liquid as precursor, are obtained by method of electrostatic spinning
Precursor fibre, spinning parameter are as follows: positive voltage is 16 KV, and negative voltage is 0.5 KV, and receiving distance is 15 cm, and syringe promotes
Speed is 0.002 mm/s.
6.3 are placed in precursor fiber in Muffle furnace, rise to 300 DEG C by room temperature according to the heating rate of 2 DEG C/min, protect
2 h of temperature, then 550 DEG C are risen to the heating rate of 5 DEG C/min, 3 h are kept the temperature, 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∙9H2O, the Bi (NO of 3.920 g3)3∙5H2O, the glacial acetic acid of 5.0 mL,
The neopentyl glycol of 1.512 g is added sequentially to the in the mixed solvent of the deionized water of 15.0 mL and the glycerine of 5.0 mL, stirring
Obtain clear solution；
1.2 with embodiment 1.
1.3 the same as embodiment 1.
The SEM of products therefrom schemes as shown in figure 4, it can be seen from the figure that products therefrom is size distributing inhomogeneity, reunites
The apparent BiFeO of phenomenon3Continuous fiber pattern, distribution of fiber diameters range is big, bad dispersibility.The product no longer has pearl-decorated curtain shape
BiFeO3Fibre structure.It can thus be seen that the introducing of solvent thermal reaction has important shadow to the generation of the microscopic appearance of product
It rings.
Comparative example 2
2.1 by the Fe (NO of 3.265 g3)3∙9H2O, the Bi (NO of 3.920 g3)3∙5H2O, the glacial acetic acid of 5.0 mL, 0.421
The neopentyl glycol of g is added sequentially to the in the mixed solvent of the deionized water of 15.0 mL and the ethylene glycol of 5.0 mL, stirs to get
The solution is transferred in reaction kettle by bright solution, 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
To precursor solution；
2.2 the same as embodiment 1.
2.3 the same as embodiment 1.
It obtains that size is inhomogenous after products therefrom furnace cooling and distribution is big, reunite serious BiFeO3Spherical
Grain no longer has BiFeO3Fibre structure.It can thus be seen that the setting of clear solution composition and solvent thermal reaction condition is to production
Object pattern has great influence, 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 (Fe (NO of 3.265 g3)3∙9H2O), the five nitric hydrate bismuth (Bi of 3.920 g
(NO3)3∙5H2O), the glacial acetic acid of 5.0 mL, be added sequentially to the mixing of the deionized water of 15.0 mL and the glycerine of 5.0 mL
In solvent, clear solution is stirred to get, which is transferred in reaction kettle, after 4 h are reacted at 120 DEG C, is placed in 80 DEG C of perseverances
5 h are stirred in tepidarium obtains precursor solution.
3.2 are dissolved in the PVP of 1.376 g in the deionized water of 5.0 mL, and it is molten to be slowly added into the presoma that 3.1 obtain
In liquid, 6 h of stirring obtain spinning liquid as precursor, obtain precursor fibre, spinning parameter by method of electrostatic spinning are as follows: positive voltage is
18 KV, negative voltage are 0.5 KV, and receiving distance is 16 cm, and syringe fltting speed is 0.001 mm/s.
3.3 the same as embodiment 1.
It is obtained after products therefrom furnace cooling by distributing inhomogeneity of taking measurements greatly, the blocky-shaped particle collection combinate form without fixed pattern
At BiFeO3Fiber, distribution of fiber diameters range is big, and particle agglomeration phenomenon is serious, no longer has pearl-decorated curtain shape structure.Thus may be used
To find out, the addition of neopentyl glycol and [Emim] Ac are to pearl-decorated curtain shape BiFeO3The formation of fibre structure has great influence.
Comparative example 4
4.1 the same as embodiment 1.
4.2 are dissolved in the PVP of 1.376 g the mixed solvent of the deionized water of 5.0 mL and [Emim] Ac of 1.2 mL
Afterwards, it is slowly added into the precursor solution that 1.1 obtain, 6 h of stirring obtain spinning liquid as precursor, are obtained by method of electrostatic spinning
Precursor fibre, spinning parameter are as follows: positive voltage is 25 KV, and negative voltage is 0.5 KV, and receiving distance is 23 cm, and syringe promotes
Speed is 0.004 mm/s.
4.3 are placed in precursor fiber in Muffle furnace, rise to 550 DEG C by room temperature according to the heating rate of 5 DEG C/min, protect
2 h of temperature, obtain product after sample furnace cooling.
Products therefrom is that the blocky-shaped particle by distributing inhomogeneity of taking measurements greatly, 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 great influence.
Claims (7)
1. a kind of pearl-decorated curtain shape BiFeO3The preparation method of micro nanometer fiber, it is characterized in that the following steps are included:
(1) ferric nitrate, bismuth nitrate, glacial acetic acid and neopentyl glycol are added sequentially to the in the mixed solvent of water and glycerine, stirred
Obtain clear solution；
(2) clear solution is subjected to solvent thermal reaction, then constant temperature is stirred to react at 75-85 DEG C, obtains precursor solution；
(3) polyvinylpyrrolidone is dissolved in the in the mixed solvent of water and 1- ethyl-3-methylimidazole acetate, then mixes this
It closes object to be slowly added in the precursor solution of step (2), stirs 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, is obtained
To pearl-decorated curtain shape BiFeO3Micro nanometer fiber；
In step (1), ferric nitrate, bismuth nitrate, neopentyl glycol molar ratio be 1:1:1.5-2, the body of glacial acetic acid, water and glycerine
Product is than being 1:3-3.9:1-1.3；In step (3), the volume ratio of water and 1- ethyl-3-methylimidazole acetate is 1:0.1-0.3；
In step (2), clear solution carries out solvent thermal reaction at 110-130 DEG C, and the reaction time is 0.5-8 h；Solvent heat is anti-
Ying Hou, solution constant temperature at 75-85 DEG C are stirred to react 1-8 h；
In step (4), heat treatment process is: precursor fibre is risen to 300 by room temperature according to the heating rate of 1-3 DEG C/min
DEG C, 1-3 h is kept the temperature, then rise to 500-600 DEG C with the heating rate of 5 DEG C/min, keeps the temperature 1-5 h.
2. preparation method according to claim 1, it is characterized in that: in step (1), mixing of the ferric nitrate in water and glycerine
Concentration in solvent is 0.3-0.5 mol/L；In step (3), PVP is 1.6-2.3 mol/L in the concentration of in the mixed solvent,
The mole of middle PVP presses the molar amount of its polymerized monomer.
3. preparation method according to claim 1 or 2, it is characterized in that: in step (3), it is mixed containing polyvinylpyrrolidone
The volume ratio for closing object and precursor solution is 1:2.1-3.4.
4. preparation method according to claim 1, it is characterized in that: solvent thermal reaction carries out in confined conditions.
5. preparation method according to claim 1, it is characterized in that: in step (4), when electrostatic spinning, positive voltage 15-20
KV, negative voltage are 0.5 KV, and receiving distance is 14-18 cm, and syringe fltting speed is 0.001-0.002 mm/s.
6. preparation method according to claim 1, it is characterized in that: gained BiFeO3Micro nanometer fiber is pearl-decorated curtain shape, by each other
Connected BeFeO3Particle assembles, BeFeO3The pattern of particle be it is spherical, particle size be 50-500 nm.
7. according to pearl-decorated curtain shape BiFeO of any of claims 1-63Pearl-decorated curtain made from the preparation method of micro nanometer fiber
Shape BiFeO3Micro nanometer fiber.
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| CN111554523B (en) * | 2020-05-18 | 2021-11-30 | 江苏理工学院 | BiFeO3-MoO2Composite material and preparation method and application thereof |
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| CN112569955B (en) * | 2020-12-09 | 2022-05-17 | 江南大学 | CeO for degrading organic dye wastewater2/BiFeO3Nano fiber photocatalyst and preparation method thereof |
| CN112661159B (en) * | 2021-01-13 | 2022-11-04 | 中南大学 | Chain bead-shaped silicon carbide nano material, preparation method and application thereof |
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| CN113617359A (en) * | 2021-08-16 | 2021-11-09 | 大连工业大学 | Preparation method and application of bismuth ferrite fibrous pyroelectric catalyst |
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