CN105420854A - BiVO4 full mesoporous fiber material and preparation method thereof - Google Patents

BiVO4 full mesoporous fiber material and preparation method thereof Download PDF

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Publication number
CN105420854A
CN105420854A CN201510946577.6A CN201510946577A CN105420854A CN 105420854 A CN105420854 A CN 105420854A CN 201510946577 A CN201510946577 A CN 201510946577A CN 105420854 A CN105420854 A CN 105420854A
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China
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bivo
fiber material
preparation
full
fiber
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杨为佑
刘华兵
侯慧林
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Ningbo University of Technology
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Ningbo University of Technology
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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
    • 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
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties

Abstract

The invention discloses a BiVO4 full mesoporous fiber material and a preparation method thereof. The fiber material comprises three elements including Bi, V and O; the surface of the fiber material adopts a porous structure; the fiber material comprises monoclinic BiVO4 crystals. According to a scheme, the BiVO4 fiber material with higher structured crystallinity is provided and further has excellent micropore distribution and good fine controllability of a microporous structure.

Description

A kind of BiVO 4full mesoporous fiber material and preparation method thereof
Technical field
The present invention relates to a kind of porous fibrous material and preparation method thereof, particularly full mesoporous fiber material of a kind of BiVO4 and preparation method thereof.
Background technology
Pucherite (BiVO 4) monodimension nanometer material takes on important role because it has nontoxic, the good and specific geometric shape of chemistry steady some property constructing nano electron device field.The BiVO of full meso-hole structure 4nanofiber, while inheriting tradition monodimension nanometer material advantage, possesses again unique high-ratio surface sum large pore volume character, in fields such as catalysis, the energy, sensing, medical treatment, has using value more widely.
Since the use of solar energy clean energy resource obtains extensive concern, the development of visible light catalyst is just more and more paid attention to.Therefore, find and a kind ofly there is more highlight catalytic active and the photochemical catalyst can in daily life with larger use value becomes an important directions of photochemical catalyst development in the world today.At present, titanium dioxide optical catalyst is considered to a kind of photochemical catalyst with good photocatalysis performance, and it has obtained good application at photodissociation organic pollution and area of solar cell.But only under UV light region, just can have photocatalytic activity due to it, therefore add the limitation of its application.Pucherite is a kind of novel visible light catalyst, and it not only has photocatalytic activity well in UV light region, and light-catalyzed reaction can occur under visible light.But it also has shortcomings, because the conduction band of pucherite is lower, it can not meet H in visible ray hydrolysis +reduction potential because pucherite electronics and hole association rate in light-catalyzed reaction is fast, electric transmission speed is comparatively slow, thus have impact on the photocatalytic activity of pucherite.
But, consider from practical application and business-like angle, the BiVO of full meso-hole structure 4nanofiber still needs to be optimized regulation and control, in the hope of being obtained the BiVO that performance is strengthened by conveniently technology 4material.Recent research report shows, the BiVO of the full meso-hole structure of one dimension 4nano material has the novel characteristics such as low-density and larger specific area, if thus can effectively at the complete mesoporous BiVO of preparation 4while fiber, realize regulation and control prepared by complete mesoporous one dimension fibre material, will work in coordination with and improve BiVO 4the permeability of material and adsorptivity, as catalyst as the fields such as photochemical catalyst have very tempting application prospect.
One of the important foundation that the research of nano material can agree with to practical application is the easy controlledly synthesis realizing its material.Based on the BiVO of above-mentioned regulatable full meso-hole structure 4the potential researching value of nanofiber, more existing research work both at home and abroad report the BiVO of meso-hole structure 4nanofiber, mainly adopts method of electrostatic spinning, auxiliary with different Technologies for Heating Processing etc.But the method can only obtain the mesoporous material under different temperatures, be difficult to realize the finely regulating to its structure.Therefore, the BiVO of full meso-hole structure is realized 4the easy controlled synthesis of nanofiber, is still faced with difficulty and challenge.
Summary of the invention
For solving the problem, the invention discloses full mesoporous fiber material of a kind of BiVO4 and preparation method thereof, providing one and there is higher regular crystalline BiVO 4fibrous material, has good micropore distributivity simultaneously, has the meticulous controllability of good microcellular structure simultaneously.And it is good that its processing method has security, cost controllability is good, good to the processing controllability of product, regulates can realize finely regulating to the distribution of micropore and size.
BiVO disclosed by the invention 4full mesoporous fiber material, its component of fibrous material comprises Bi, V, O tri-kinds of elements, and dimension material surface has loose structure, and fibrous material comprises monocline BiVO 4crystal.
BiVO disclosed by the invention 4the one of full mesoporous fiber material is improved, and fibrous material is monocline BiVO 4material.
BiVO disclosed by the invention 4the one of full mesoporous fiber material is improved, and fibrous material has so the mesoporous loose structure that is of hole.
BiVO disclosed by the invention 4the preparation method of full mesoporous fiber material, comprises the steps, 1), precursor spinning solution preparation; 2), precursor fiber preparation; 3), full mesoporous fiber material is prepared in pyrolysis;
Wherein, step 3) to prepare full mesoporous fiber material be by step 2 in pyrolysis) obtained precursor fiber calcines under air ambient.This programme is in order to improve BiVO 4the degree of crystallinity of material, thus select and carry out calcination processing in air atmosphere.
BiVO disclosed by the invention 4the one of the preparation method of full mesoporous fiber material is improved, step 1) in precursor spinning solution be prepared as raw material (to account for the mass percent metering of mixed solvent total amount) 8-12% polyvinylpyrrolidone, 15-18% five nitric hydrate bismuth, 8-10% vanadyl acetylacetonate, diisopropyl azodiformate be dissolved in N-N dimethyl formamide, absolute ethyl alcohol and glacial acetic acid mixed solvent and form mixed solution, wherein blowing agent diisopropyl azodiformate content in mixed solution is 0-20wt%.In this programme, PVP regulates and controls the viscosity of spinning solution and volatilizees decomposing in the process of calcination processing completely; Bi (NO 3) 35H 2o provides Bi source; VO (acac) 2v source is provided; DIPA is blowing agent, discharges a large amount of object of gas realization to fibrous matrix pore-creating in the process of calcination processing; DMF act as the solvent of vanadyl acetylacetonate; Ethanol act as the solvent of five nitric hydrate bismuths; Glacial acetic acid is jointly as while solvent, also for electrostatic spinning solution provides acetate ion to improve spinning property, thus in the process of spinning, because the effect blowing agent (DIPA) of electrostatic force is distributed in presoma inside equably, after calcination processing, decompose the formation of volatilization for full meso-hole structure; Along with the difference of foaming agents content, the final BiVO forming different internal structure 4full meso-porous nano fibrous material.Blowing agent adds very few, although fiber has meso-hole structure, pattern and structure are not very good, and not easily obtain full mesoporous fiber, and blowing agent adds excessive, then easily cause fiber ruptures, be difficult to keep good fibre structure.
BiVO disclosed by the invention 4the one of the preparation method of full mesoporous fiber material is improved, step 1) in precursor spinning solution be prepared as and material polyethylene pyrrolidones, five nitric hydrate bismuths, vanadyl acetylacetonate, diisopropyl azodiformate be dissolved in absolute ethyl alcohol and glacial acetic acid mixed solvent and after stirring at normal temperature 4-8 hour, then add diisopropyl azodiformate mixing.
BiVO disclosed by the invention 4the one of the preparation method of full mesoporous fiber material is improved, step 2) in precursor fiber be prepared as precursor spinning solution obtained fiber constant temperature drying again through electrostatic spinning, the temperature of constant temperature drying is 70-100 DEG C.The conductive cathode that negative electrode is tinfoil paper negative electrode or other material is received during electrostatic spinning.Temperature during electrostatic spinning is 20-55 DEG C, and humidity is 15-60%.
BiVO disclosed by the invention 4the one of the preparation method of full mesoporous fiber material is improved, step 2) in the preparation of precursor fiber during electrostatic spinning the field intensity of electrostatic field be 0.5-1KV/cm.
Compared with prior art, the invention has the advantages that:
1. present invention achieves BiVO 4the regulation and control of full meso-porous nano fibrous material meso-hole structure;
2. select blowing agent in view of in experimental program, be easily evenly distributed in presoma inner in the effect of electrostatic force, thus can realize the good BiVO of Stability Analysis of Structures pattern 4effective synthesis of full meso-porous nano fiber;
3. select blowing agent in the present invention program, along with the content of blowing agent increases, the viscosity of spinning solution also can decrease, and then needs to regulate and control spinning temperature and humidity, thus reaches the object of mesoporous form on precise hard_drawn tuhes fiber.The impact of solution temperature on electrostatic spinning process shows: the environment temperature raising electrostatic spinning can accelerate the motion of jet Middle molecule chain, improves the electrical conductivity of solution; Secondly, the environment temperature raising electrostatic spinning reduces viscosity and the surface tension of solution, makes blowing agent addition at room temperature can not the polymer solution of electrostatic spinning at more than 5-10wt%, can carry out electrostatic spinning after rising environment temperature.In electrostatic spinning process, the taylor cone surface of jet is formed, and is rapidly to the motion of reception pole plate, and solvent volatilizees rapidly within the extremely short time, and jet is solidified into polymer fiber.Under general electrostatic spinning environment, the medium of Around Jet is air, and in jet, the exchange of solvent and surrounding medium is a double diffusion process.The solvent evaporates of jet surface, its internal solvent center diffuses to the surface, and the competitive relation between the evaporation rate of jet surface solvent and diffusion inside speed can affect the form of fiber.Therefore, ambient humidity having a great impact the fibre diameter of electrostatic spinning and pattern.In the present invention, along with the increase of foaming agents content, the viscosity of solution constantly reduces, and in electrostatic spinning process, if solvent can not volatilize timely, so can cause the change of electrostatic spinning pattern (as caking, spherical etc.).So along with the continuous interpolation of blowing agent in electrostatic spinning liquid, the environment temperature in spinning process and the requirement of ambient humidity will improve constantly.
4. the present invention is by the content of regulation and control blowing agent, effectively can realize the regulation and control of full meso-porous nano fiber;
5. this technique is simply controlled, has good repeatability, and it is convenient to implement, and security is good, and easy to operate, and environment friendly is good.
Accompanying drawing explanation
ESEM (SEM) figure of the solid-state organic precursor nanofiber of Fig. 1 obtained by the embodiment of the present invention one;
The BiVO of Fig. 2 obtained by the embodiment of the present invention one 4low power ESEM (SEM) figure of nanofiber;
The BiVO of Fig. 3 obtained by the embodiment of the present invention one 4high power ESEM (SEM) figure of nanofiber; ;
The BiVO of Fig. 4 obtained by the embodiment of the present invention one 4the X-ray diffraction spectrogram of nanofiber;
The BiVO of Fig. 5 obtained by the embodiment of the present invention one 4the Raman figure of nanofiber
The BiVO of Fig. 6 obtained by the embodiment of the present invention two 4low power ESEM (SEM) figure of full mesoporous fiber material;
The BiVO of Fig. 7 obtained by the embodiment of the present invention two 4high power ESEM (SEM) figure of full mesoporous fiber material;
The BiVO of Fig. 8 obtained by the embodiment of the present invention three 4low power ESEM (SEM) figure of full mesoporous fiber material;
The BiVO of Fig. 9 obtained by the embodiment of the present invention three 4high power ESEM (SEM) figure of full mesoporous fiber material;
The BiVO of Figure 10 obtained by the embodiment of the present invention three 4transmission electron microscope (TEM) figure of full mesoporous fiber material;
The BiVO of Figure 11 obtained by the embodiment of the present invention three 4high-resolution-ration transmission electric-lens (HRTEM) figure of full mesoporous fiber material;
The BiVO of Figure 12 obtained by the embodiment of the present invention four 4low power ESEM (SEM) figure of full mesoporous fiber material;
The BiVO of Figure 13 obtained by the embodiment of the present invention four 4low power ESEM (SEM) figure of full mesoporous fiber material;
The BiVO of Figure 14 obtained by the embodiment of the present invention five 4low power ESEM (SEM) figure of full mesoporous fiber material;
The BiVO of Figure 15 obtained by the embodiment of the present invention five 4low power ESEM (SEM) figure of full mesoporous fiber material.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, illustrate the present invention further, following detailed description of the invention should be understood and be only not used in for illustration of the present invention and limit the scope of the invention.It should be noted that, the word "front", "rear" of use is described below, "left", "right", "up" and "down" refer to direction in accompanying drawing, word " interior " and " outward " refer to the direction towards or away from particular elements geometric center respectively.
Embodiment 1
Take polyvinylpyrrolidone (PVP) 0.7g (10%), five nitric hydrate bismuth (Bi (NO 3) 35H 2o) 1.21g (17.3%) and vanadyl acetylacetonate (VO (acac) 2) 0.662g (9.5%) is dissolved in the mixed liquor of 2.5g absolute ethyl alcohol, N-N dimethyl formamide (DMF) 2.5g and 2g glacial acetic acid, is at room temperature uniformly mixed 6 hours with magneton and obtains bottle green clear solution.To measure after the solution left standstill spun in 6ml injected plastic needle tubing, and be placed on micro-injection pump, arranging injection speed is 0.2mm/min.Metal needle makes Electrospun anode, the negative electrode receiving material is made with the cylinder that aluminium foil is coated, distance between anode and negative electrode is 20cm, under 12kV high pressure, carrying out electrostatic spinning, (during spinning, environment is room temperature (20-30 DEG C), humidity: 50-60%), prepare organic precursor fibrous material.Then organic precursor fibrous material is placed in 80 DEG C of constant temp. drying boxes, the organic precursor fiber (Fig. 1) of acquisition.Finally SOLID ORGANIC presoma is placed in quartz boat, within 1 hour, carries out calcination processing in 500 DEG C of insulations in air atmosphere, then cool with stove.Prepared BiVO 4the typical scan Electronic Speculum (SEM) of nano-fiber material under different amplification as shown in Figures 2 and 3, shows that prepared material is not entirely mesoporous nanofiber; Fig. 4 is its corresponding X-ray diffraction spectrogram (XRD), shows that prepared nanofiber is typical monoclinic crystal structure in pucherite three kinds of crystal structures; Fig. 5 is Raman (Raman) figure of single nanofiber, further demonstrate that synthesized material is monoclinic crystal structure.
Embodiment 2
Take polyvinylpyrrolidone (PVP) 0.7g, five nitric hydrate bismuth (Bi (NO 3) 35H 2o) 1.21g and vanadyl acetylacetonate (VO (acac) 2) 0.662g is dissolved in the mixed liquor of 2.5g absolute ethyl alcohol, N-N dimethyl formamide (DMF) 2.5g and 2g glacial acetic acid, stirred at ambient temperature adds 0.5g diisopropyl azodiformate (blowing agent, DIPA) and continues to stir the clear solution obtaining shallow breen after mixing 6 hours.Measure after the microemulsion spun leaves standstill in 6ml injected plastic needle tubing, and be placed on micro-injection pump, the setting speed of injecting is 0.2mm/min.Metal needle makes Electrospun anode, the negative electrode receiving material made by wire netting, and the distance between anode and negative electrode is 20cm, and under 12kV high pressure, carrying out electrostatic spinning, (during spinning, environment is 30 DEG C, humidity: 50-60%), prepare organic precursor fibrous material.Then organic precursor fibrous material is placed in 80 DEG C of constant temp. drying boxes, obtains the organic precursor fiber that core is solid-state.Finally SOLID ORGANIC presoma is placed in quartz boat, within 1 hour, carries out calcination processing in 500 DEG C of insulations in air atmosphere, then cool with stove.Prepared BiVO 4the typical scan Electronic Speculum (SEM) of nano-fiber material under different amplification as shown in Figure 6 and Figure 7, shows that prepared material is meso-porous nano fiber; The result of comparative example 1 is known, in initial feed time the amount of blowing agent less (5wt%), is meso-hole structure finally by the material prepared by calcining, illustrates that adding a small amount of blowing agent can obtain mesoporous nanofiber.
Embodiment 3
Take polyvinylpyrrolidone (PVP) 0.7g, five nitric hydrate bismuth (Bi (NO 3) 35H 2o) 1.21g and vanadyl acetylacetonate (VO (acac) 2) 0.662g is dissolved in the mixed liquor of 2.5g absolute ethyl alcohol, N-N dimethyl formamide (DMF) 2.5g and 2g glacial acetic acid, stirred at ambient temperature adds 1.06g diisopropyl azodiformate (blowing agent, DIPA) and continues to stir the clear solution obtaining shallow breen after mixing 6 hours.Measure after the microemulsion spun leaves standstill in 6ml injected plastic needle tubing, and be placed on micro-injection pump, the setting speed of injecting is 0.2mm/min.Metal needle makes Electrospun anode, the negative electrode receiving material made by wire netting, and the distance between anode and negative electrode is 20cm, and under 12kV high pressure, carrying out electrostatic spinning, (during spinning, environment is 40 DEG C, humidity: 30-40%), prepare organic precursor fibrous material.Then organic precursor fibrous material is placed in 80 DEG C of constant temp. drying boxes, obtains the organic precursor fiber that core is solid-state.Finally SOLID ORGANIC presoma is placed in quartz boat, within 1 hour, carries out calcination processing in 500 DEG C of insulations in air atmosphere, then cool with stove.Prepared BiVO 4the typical scan Electronic Speculum (SEM) of nano-fiber material under different amplification as shown in Figure 8 and Figure 9, shows that prepared material is meso-porous nano fiber; Figure 10 is transmission electron microscope (TEM) figure of single nanofiber, show further synthesized material and has typical full meso-hole structure.Figure 11 is the corresponding high-resolution-ration transmission electric-lens of institute's crystal (HRTEM), confirms that prepared fibrous material is monoclinic crystal phase.The result of comparative example 1,2 is known, when in initial feed, the addition of blowing agent reaches (10wt%), be meso-hole structure finally by the material prepared by calcining, illustrate when foaming agents content reaches 10%wt, the good meso-porous nano fiber entirely of pattern and structure can be obtained.
Embodiment 4
Take polyvinylpyrrolidone (PVP) 0.7g, five nitric hydrate bismuth (Bi (NO 3) 35H 2o) 1.21g and vanadyl acetylacetonate (VO (acac) 2) 0.662g is dissolved in the mixed liquor of 2.5g absolute ethyl alcohol, N-N dimethyl formamide (DMF) 2.5g and 2g glacial acetic acid, stirred at ambient temperature adds 1.69g diisopropyl azodiformate (blowing agent, DIPA) and continues to stir the clear solution obtaining shallow breen after mixing 6 hours.Measure after the microemulsion spun leaves standstill in 6ml injected plastic needle tubing, and be placed on micro-injection pump, the setting speed of injecting is 0.2mm/min.Metal needle makes Electrospun anode, the negative electrode receiving material made by wire netting, and the distance between anode and negative electrode is 20cm, and under 12kV high pressure, carrying out electrostatic spinning, (during spinning, environment is 50 DEG C, humidity: 28-32%), prepare organic precursor fibrous material.Then organic precursor fibrous material is placed in 80 DEG C of constant temp. drying boxes, obtains the organic precursor fiber that core is solid-state.Finally SOLID ORGANIC presoma is placed in quartz boat, within 1 hour, carries out calcination processing in 500 DEG C of insulations in air atmosphere, then cool with stove.Prepared BiVO 4the typical scan Electronic Speculum (SEM) of nano-fiber material under different amplification as shown in Figure 12 and Figure 13, shows that prepared material is meso-porous nano fiber; The result of comparative example 1,2 and 3 is known, when in initial feed, the amount of blowing agent is increased to 15wt% further, the blowing agent being meso-hole structure explanation interpolation 15%wt finally by the material prepared by calcining still can obtain entirely mesoporous nanofiber, and hole content and size increase all to some extent.
Embodiment 5
Take polyvinylpyrrolidone (PVP) 0.7g, five nitric hydrate bismuth (Bi (NO 3) 35H 2o) 1.21g and vanadyl acetylacetonate (VO (acac) 2) 0.662g is dissolved in the mixed liquor of 2.5g absolute ethyl alcohol, N-N dimethyl formamide (DMF) 2.5g and 2g glacial acetic acid, stirred at ambient temperature adds 2.39g diisopropyl azodiformate (blowing agent, DIPA) and continues to stir the clear solution obtaining shallow breen after mixing 6 hours.Measure after the microemulsion spun leaves standstill in 6ml injected plastic needle tubing, and be placed on micro-injection pump, the setting speed of injecting is 0.2mm/min.Metal needle makes Electrospun anode, and wire netting is done to receive the negative electrode of material, and the distance between anode and negative electrode is 20cm, carries out electrostatic spinning (during spinning 55 DEG C, humidity: 15-20%), prepare organic precursor fibrous material under 12kV high pressure.Then organic precursor fibrous material is placed in 80 DEG C of constant temp. drying boxes, obtains the organic precursor fiber that core is solid-state.Finally SOLID ORGANIC presoma is placed in quartz boat, within 1 hour, carries out calcination processing in 500 DEG C of insulations in air atmosphere, then cool with stove.Prepared BiVO 4the typical scan Electronic Speculum (SEM) of nano-fiber material under different amplification as shown in Figure 14 and Figure 15, shows that prepared material is meso-porous nano fiber; The result of comparative example 1,2,3 and 3 is known, in initial feed time the amount of blowing agent more (20wt%), finally by calcining prepared by material be meso-hole structure, but because foaming agents content is too much, when high-temperature calcination process, blowing agent is decomposed into gas, few fibers is caused to break, there is the nanofiber that part is banded simultaneously, illustrate that adding few blowing agent that excessively adds can obtain mesoporous nanofiber, but few fibers can not keep good fibre structure.
In view of the present invention program's embodiment is numerous, each embodiment experimental data is huge numerous, be not suitable for particularize explanation herein, but the content of the required checking of each embodiment is all close with the final conclusion obtained, so do not illustrate one by one the checking content of each embodiment, only with embodiment 1 to 5, the excellent part of the present patent application is representatively described herein.
Embodiment 6
Take polyvinylpyrrolidone (PVP) 0.56g (8%), five nitric hydrate bismuth (Bi (NO 3) 35H 2o) 1.049g (15%) and vanadyl acetylacetonate (VO (acac) 2) 0.676g (9.7%) is dissolved in the mixed liquor of 2.5g absolute ethyl alcohol, N-N dimethyl formamide (DMF) 2.5g and 2g glacial acetic acid, stirred at ambient temperature adds 0.31g (3.2wt%) diisopropyl azodiformate (blowing agent, DIPA) and continues to stir the clear solution obtaining shallow breen after mixing 6 hours.Measure after the microemulsion spun leaves standstill in 6ml injected plastic needle tubing, and be placed on micro-injection pump, the setting speed of injecting is 0.2mm/min.Metal needle makes Electrospun anode, and the negative electrode receiving material made by wire netting, and the distance between anode and negative electrode is 20cm, under 12kV high pressure, carry out electrostatic spinning, prepares organic precursor fibrous material.Then organic precursor fibrous material is placed in 80 DEG C of constant temp. drying boxes, obtains the organic precursor fiber that core is solid-state.Finally SOLID ORGANIC presoma is placed in quartz boat, within 1 hour, carries out calcination processing in 500 DEG C of insulations in air atmosphere, then cool with stove.
Embodiment 7
Take polyvinylpyrrolidone (PVP) 0.84g (12%), five nitric hydrate bismuth (Bi (NO 3) 35H 2o) 1.12g (16%) and vanadyl acetylacetonate (VO (acac) 2) 0.697g (10%) is dissolved in the mixed liquor of 2.5g absolute ethyl alcohol, N-N dimethyl formamide (DMF) 2.5g and 2g glacial acetic acid, stirred at ambient temperature adds 0.71g (6.85wt%) diisopropyl azodiformate (blowing agent, DIPA) and continues to stir the clear solution obtaining shallow breen after mixing 6 hours.Measure after the microemulsion spun leaves standstill in 6ml injected plastic needle tubing, and be placed on micro-injection pump, the setting speed of injecting is 0.2mm/min.Metal needle makes Electrospun anode, and the negative electrode receiving material made by wire netting, and the distance between anode and negative electrode is 20cm, under 12kV high pressure, carry out electrostatic spinning, prepares organic precursor fibrous material.Then organic precursor fibrous material is placed in 80 DEG C of constant temp. drying boxes, obtains the organic precursor fiber that core is solid-state.Finally SOLID ORGANIC presoma is placed in quartz boat, within 1 hour, carries out calcination processing in 500 DEG C of insulations in air atmosphere, then cool with stove.
Embodiment 8
Take polyvinylpyrrolidone (PVP) 0.77g (11%), five nitric hydrate bismuth (Bi (NO 3) 35H 2o) 1.19g (17%) and vanadyl acetylacetonate (VO (acac) 2) 0.627g (9%) is dissolved in the mixed liquor of 2.5g absolute ethyl alcohol, N-N dimethyl formamide (DMF) 2.5g and 2g glacial acetic acid, stirred at ambient temperature adds 1.12g (10.46wt%) diisopropyl azodiformate (blowing agent, DIPA) and continues to stir the clear solution obtaining shallow breen after mixing 6 hours.Measure after the microemulsion spun leaves standstill in 6ml injected plastic needle tubing, and be placed on micro-injection pump, the setting speed of injecting is 0.2mm/min.Metal needle makes Electrospun anode, and the negative electrode receiving material made by wire netting, and the distance between anode and negative electrode is 20cm, under 12kV high pressure, carry out electrostatic spinning, prepares organic precursor fibrous material.Then organic precursor fibrous material is placed in 80 DEG C of constant temp. drying boxes, obtains the organic precursor fiber that core is solid-state.Finally SOLID ORGANIC presoma is placed in quartz boat, within 1 hour, carries out calcination processing in 500 DEG C of insulations in air atmosphere, then cool with stove.
Embodiment 9
Take polyvinylpyrrolidone (PVP) 0.63g (9%), five nitric hydrate bismuth (Bi (NO 3) 35H 2o) 1.26g (18%) and vanadyl acetylacetonate (VO (acac) 2) 0.592g (8.5%) is dissolved in the mixed liquor of 2.5g absolute ethyl alcohol, N-N dimethyl formamide (DMF) 2.5g and 2g glacial acetic acid, stirred at ambient temperature adds 1.63g (14.67wt%) diisopropyl azodiformate (blowing agent, DIPA) and continues to stir the clear solution obtaining shallow breen after mixing 6 hours.Measure after the microemulsion spun leaves standstill in 6ml injected plastic needle tubing, and be placed on micro-injection pump, the setting speed of injecting is 0.2mm/min.Metal needle makes Electrospun anode, and the negative electrode receiving material made by wire netting, and the distance between anode and negative electrode is 20cm, under 12kV high pressure, carry out electrostatic spinning, prepares organic precursor fibrous material.Then organic precursor fibrous material is placed in 80 DEG C of constant temp. drying boxes, obtains the organic precursor fiber that core is solid-state.Finally SOLID ORGANIC presoma is placed in quartz boat, within 1 hour, carries out calcination processing in 500 DEG C of insulations in air atmosphere, then cool with stove.
Embodiment 10
Take polyvinylpyrrolidone (PVP) 0.595g (8.5%), five nitric hydrate bismuth (Bi (NO 3) 35H 2o) 1.14g (16.3%) and vanadyl acetylacetonate (VO (acac) 2) 0.557g (8%) is dissolved in the mixed liquor of 2.5g absolute ethyl alcohol, N-N dimethyl formamide (DMF) 2.5g and 2g glacial acetic acid, stirred at ambient temperature adds 1.81g (16.30wt%) diisopropyl azodiformate (blowing agent, DIPA) and continues to stir the clear solution obtaining shallow breen after mixing 6 hours.Measure after the microemulsion spun leaves standstill in 6ml injected plastic needle tubing, and be placed on micro-injection pump, the setting speed of injecting is 0.2mm/min.Metal needle makes Electrospun anode, and the negative electrode receiving material made by wire netting, and the distance between anode and negative electrode is 20cm, under 12kV high pressure, carry out electrostatic spinning, prepares organic precursor fibrous material.Then organic precursor fibrous material is placed in 80 DEG C of constant temp. drying boxes, obtains the organic precursor fiber that core is solid-state.Finally SOLID ORGANIC presoma is placed in quartz boat, within 1 hour, carries out calcination processing in 500 DEG C of insulations in air atmosphere, then cool with stove.
The technical scope midrange non-limit part that this place embodiment is protected application claims and in embodiment technical scheme to the new technical scheme that the equal replacement of single or multiple technical characteristic is formed, equally all in the scope of protection of present invention; Simultaneously in all embodiments enumerated or do not enumerate of the present invention program, parameters in the same embodiment only represents an example (i.e. a kind of feasible scheme) of its technical scheme, and between parameters, there is not strict cooperation and qualified relation, wherein each parameter can be replaced, except special declaration mutually when stating ask without prejudice to axiom and the present invention.
Technological means disclosed in the present invention program is not limited only to the technological means disclosed in above-mentioned technological means, also comprises the technical scheme be made up of above technical characteristic.The above is the specific embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.

Claims (8)

1. a BiVO 4full mesoporous fiber material, is characterized in that: its component of described fibrous material comprises Bi, V, O tri-kinds of elements, and described fibrous material surface has loose structure, and described fibrous material comprises monocline BiVO 4crystal.
2. BiVO according to claim 1 4full mesoporous fiber material, is characterized in that: described fibrous material is monocline BiVO 4material.
3. BiVO according to claim 1 and 2 4full mesoporous fiber material, is characterized in that: described fibrous material has so the mesoporous loose structure that is of hole.
4. a BiVO 4the preparation method of full mesoporous fiber material, is characterized in that: comprise the steps, 1), precursor spinning solution preparation; 2), precursor fiber preparation; 3), full mesoporous fiber material is prepared in pyrolysis;
Wherein, step 3) to prepare full mesoporous fiber material be by step 2 in pyrolysis) obtained precursor fiber calcines under air ambient.
5. BiVO according to claim 4 4the preparation method of full mesoporous fiber material, it is characterized in that: described step 1) in precursor spinning solution be prepared as raw material (to account for the mass percent metering of mixed solvent total amount) that 8-12% polyvinylpyrrolidone, 15-18% five nitric hydrate bismuth, 8-10% vanadyl acetylacetonate and diisopropyl azodiformate be dissolved in N-N dimethyl formamide, absolute ethyl alcohol and glacial acetic acid mixed solvent and form mixed solution, wherein diisopropyl azodiformate content in mixed solution is 0-20wt%.
6. BiVO according to claim 5 4the preparation method of full mesoporous fiber material, it is characterized in that: described step 1) in precursor spinning solution be prepared as and material polyethylene pyrrolidones, five nitric hydrate bismuths, vanadyl acetylacetonate, diisopropyl azodiformate be dissolved in absolute ethyl alcohol and glacial acetic acid mixed solvent and after stirring at normal temperature 4-8 hour, then add diisopropyl azodiformate mixing.
7. BiVO according to claim 4 4the preparation method of full mesoporous fiber material, is characterized in that: described step 2) in precursor fiber be prepared as precursor spinning solution obtained fiber constant temperature drying again through electrostatic spinning, the temperature of constant temperature drying is 70-100 DEG C.
8. BiVO according to claim 7 4the preparation method of full mesoporous fiber material, is characterized in that: described step 2) in precursor fiber preparation in electrostatic spinning time electrostatic field field intensity be 0.5-1KV/cm.
CN201510946577.6A 2015-12-17 2015-12-17 BiVO4 full mesoporous fiber material and preparation method thereof Pending CN105420854A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106082334A (en) * 2016-06-20 2016-11-09 宁波工程学院 A kind of BiVO4the preparation method of nanobelt material
CN106082333A (en) * 2016-06-20 2016-11-09 宁波工程学院 A kind of regulation and control BiVO4the method of full meso-porous nano carrying material
CN106380970A (en) * 2016-11-17 2017-02-08 重庆文理学院 Preparation method of antibacterial formaldehyde buster aqueous nano latex paint
CN106433356A (en) * 2016-11-17 2017-02-22 重庆文理学院 Inner wall nano-paint for purifying formaldehyde by visible light catalysis
CN106675250A (en) * 2016-11-17 2017-05-17 重庆文理学院 Preparation method of interior wall nano-paint capable of removing formaldehyde by means of visible light
CN107446435A (en) * 2016-11-17 2017-12-08 重庆文理学院 A kind of preparation method of high stability exterior wall nano paint
CN110747536A (en) * 2019-02-28 2020-02-04 安徽科技学院 Preparation method of nanofiber with wide visible light absorption range

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101362649A (en) * 2008-07-01 2009-02-11 北京师范大学 Method for preparing electro spinning mesoporous zircite fiber film
CN103074704A (en) * 2013-01-22 2013-05-01 陕西科技大学 Electrospinning preparation method of BiVO4 (bismuth vanadium oxide) fibers
CN104178822A (en) * 2014-07-30 2014-12-03 东华大学 Flexible inorganic fiber material and preparation method thereof
CN104404653A (en) * 2014-11-25 2015-03-11 宁波工程学院 General preparation method of full-mesopore nano-fiber material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101362649A (en) * 2008-07-01 2009-02-11 北京师范大学 Method for preparing electro spinning mesoporous zircite fiber film
CN103074704A (en) * 2013-01-22 2013-05-01 陕西科技大学 Electrospinning preparation method of BiVO4 (bismuth vanadium oxide) fibers
CN104178822A (en) * 2014-07-30 2014-12-03 东华大学 Flexible inorganic fiber material and preparation method thereof
CN104404653A (en) * 2014-11-25 2015-03-11 宁波工程学院 General preparation method of full-mesopore nano-fiber material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
YONGLIANG CHENG ETAL: "Preparation of porous BiVO4 fibers by electrospinning and their photocatalytic performance under visible light", 《RSC ADVANCES》 *
张大省: "《超细纤维生产技术及应用》", 31 January 2007, 中国纺织出版社 *

Cited By (12)

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CN106082334A (en) * 2016-06-20 2016-11-09 宁波工程学院 A kind of BiVO4the preparation method of nanobelt material
CN106082333A (en) * 2016-06-20 2016-11-09 宁波工程学院 A kind of regulation and control BiVO4the method of full meso-porous nano carrying material
CN106082334B (en) * 2016-06-20 2018-11-27 宁波工程学院 A kind of BiVO4The preparation method of nanobelt material
CN106380970A (en) * 2016-11-17 2017-02-08 重庆文理学院 Preparation method of antibacterial formaldehyde buster aqueous nano latex paint
CN106433356A (en) * 2016-11-17 2017-02-22 重庆文理学院 Inner wall nano-paint for purifying formaldehyde by visible light catalysis
CN106675250A (en) * 2016-11-17 2017-05-17 重庆文理学院 Preparation method of interior wall nano-paint capable of removing formaldehyde by means of visible light
CN107446435A (en) * 2016-11-17 2017-12-08 重庆文理学院 A kind of preparation method of high stability exterior wall nano paint
CN106675250B (en) * 2016-11-17 2019-07-30 重庆文理学院 A kind of preparation method of the interior wall nano paint of the net aldehyde of visible light
CN106380970B (en) * 2016-11-17 2019-08-09 重庆文理学院 A kind of preparation method of the net aldehyde water nano emulsion paint of antibacterial
CN107446435B (en) * 2016-11-17 2020-04-28 重庆文理学院 Preparation method of high-stability exterior wall nano coating
CN110747536A (en) * 2019-02-28 2020-02-04 安徽科技学院 Preparation method of nanofiber with wide visible light absorption range
CN110747536B (en) * 2019-02-28 2022-04-05 安徽科技学院 Preparation method of nanofiber with wide visible light absorption range

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