CN105903476B - A kind of electrostatic spinning technique preparation FeWO4The preparation method of nanocatalyst - Google Patents
A kind of electrostatic spinning technique preparation FeWO4The preparation method of nanocatalyst Download PDFInfo
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- CN105903476B CN105903476B CN201610287800.5A CN201610287800A CN105903476B CN 105903476 B CN105903476 B CN 105903476B CN 201610287800 A CN201610287800 A CN 201610287800A CN 105903476 B CN105903476 B CN 105903476B
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- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000010041 electrostatic spinning Methods 0.000 title claims abstract description 27
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000009987 spinning Methods 0.000 claims abstract description 31
- 239000007787 solid Substances 0.000 claims abstract description 23
- 239000002121 nanofiber Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 238000013019 agitation Methods 0.000 claims abstract description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 229910005507 FeWO4 Inorganic materials 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 12
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 9
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 7
- 230000003647 oxidation Effects 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 230000003068 static effect Effects 0.000 claims abstract description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 229910001868 water Inorganic materials 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 11
- 239000011964 heteropoly acid Substances 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 abstract description 5
- 238000001914 filtration Methods 0.000 abstract 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 15
- 229940043267 rhodamine b Drugs 0.000 description 15
- 239000000835 fiber Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 230000000593 degrading effect Effects 0.000 description 7
- 239000011941 photocatalyst Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- SSWAPIFTNSBXIS-UHFFFAOYSA-N dioxido(dioxo)tungsten;iron(2+) Chemical compound [Fe+2].[O-][W]([O-])(=O)=O SSWAPIFTNSBXIS-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 238000002242 deionisation method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000008236 heating water Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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Abstract
A kind of electrostatic spinning technique preparation FeWO4The preparation method of nanocatalyst, belongs to technical field of catalytic chemistry, by Na10[Sb2W18Zn3O66(H2O)3]·48H2The aqueous solution of O is stirred with tetra-n-butyl ammonium bromide, is obtained white solid, is dried after filtering, washing, and Zn is obtained3@TBA solid powders；By polyacrylonitrile, Zn3Dimethylformamide is added dropwise after@TBA solid powders and ferric acetyl acetonade mixing, through magnetic agitation, obtains electrostatic spinning liquid, through Static Spinning, obtains nanofiber, then pre-oxidation, high-temperature calcination in air, obtains FeWO4Nanocatalyst.Product of the present invention can overcome heteropoly acid solubility big, the shortcomings that causing catalyst to be difficult to detach with reaction system, product surface bigger, be conducive to improve catalytic performance.
Description
Technical field
The invention belongs to technical field of catalytic chemistry, and in particular to tubulose FeWO4The technology of preparing of nano-fiber material.
Background technology
Although heteropoly acid（Salt）There is good catalytic performance as acid catalyst and oxidation reduction catalyst, some uses
Heteropoly acid（Salt）Process also realized industrialization, but due to heteropoly acid（Salt）Certain deficiencies possessed by itself, such as specific surface
Product is smaller（1~10m2/g）, it is unfavorable for giving full play to for reactivity；Solubility is big in polar solvent and nonpolar solvent,
Cause catalyst to be difficult to detach with reaction system, is unfavorable for industrialized continuous production；Catalyst recycles relatively difficult etc..
Ferrous tungstate（FeWO4）It is a kind of important functional inorganic materials, many is had been achieved in the application of magnetic fields
Achievement, but research also has much room in terms of photocatalysis, a kind of flower-shaped ferrous tungstate material of the hexagonal reported is to RhB
With good photocatalysis effect.
Currently, the synthetic method of ferrous tungstate material includes mainly hydrothermal synthesis method, ultrasonic etc..Prepared
FeWO4Mostly starlike, rodlike, hexagonal flake etc. are micron-sized, and nanoscale is fixed more rare.
Invention content
It is an object of the invention to propose that a kind of method is novel, the simple FeWO of equipment requirement4The preparation of nanocatalyst
Method.
The present invention comprises the steps of：
1）By Na10[Sb2W18Zn3O66(H2O)3]·48H2O crystal is soluble in water, forms Zn3Aqueous solution, then by four positive fourths
Base ammonium bromide（TBA）Zn is added3In aqueous solution, magnetic agitation, obtains white solid in a heated condition, filters, with deionized water
It after being washed with absolute ethyl alcohol, is dried through 50 DEG C, obtains Zn3@TBA solid powders；
2）By polyacrylonitrile（PAN）、Zn3@TBA solid powders and ferric acetyl acetonade（Fe（ACAC）3）It is mixed to be placed in centrifuge tube
It closes, dimethylformamide is then added dropwise（DMF）, through magnetic agitation, obtain electrostatic spinning liquid；
3）By electrostatic spinning liquid through Static Spinning, nanofiber is obtained；
4）Nanofiber is pre-oxidized in air, high-temperature calcination, obtains FeWO4Nanocatalyst.
The characteristics of present invention process is：
1, the present invention is with Zn3With ferric acetyl acetonade as presoma, synthesize FeWO by method of electrostatic spinning4, there is original creation
Property.
2, manufactured nanofiber has the tubular morphology of high surface area, straight by pre-oxidation and high-temperature calcination fibre pipe
Diameter is the hollow FeWO of 400nm or so4Nanofiber, structure is more uniform, and there is pore passage structure in better crystallinity degree, inside, has
Rational heteropolyacid salt density, activity is low, and chemical stability is high.
3, the present invention is a kind of low temperature of green environment close friend, high activity, highly selective composite efficient catalyst, more sharp
In the progress of heterogeneous catalytic reaction；The price of raw material is relatively low simultaneously, can reduce the manufacturing cost of catalyst.
In short, method of electrostatic spinning of the present invention can easily obtain the ferrous tungstate material of nanoscale tubulose
Material, it is not soluble in water, the shortcomings that heteropoly acid solubility can be overcome big, catalyst is caused to be difficult to detach with reaction system；Meanwhile with
Traditional ferrous tungstate compares surface bigger, is conducive to improve catalytic performance.
Further, step 1 of the present invention）In, the Zn3A concentration of 0.013mol/L of aqueous solution.The concentration item
Part is conducive to smoothly quickly complete next step tetra-n-butyl ammonium bromide（TBA）Carry out cationic exchange.
The step 1）In, the Zn3Na in aqueous solution10[Sb2W18Zn3O66(H2O)3] and tetra-n-butyl ammonium bromide（TBA）
Mixing molar ratio be 1: 12.Excessive tetra-n-butyl ammonium bromide（TBA）It can ensure to replace Na completely+。
The step 1）In, the condition of heating is 80 DEG C, and the rate of magnetic agitation is 800rpm, mixing time 1h, elder generation
It is washed 1~3 time with deionized water, is then washed 1~3 time with absolute ethyl alcohol.In this temperature and time range, reactant can be in water
It is fully activated under heat condition, the reaction was complete；Magnetic stirrer rate is 800rpm；Overcome the stress of conventional agitator not
Uniformly, it is more preferable to be dispersed with stirring effect, reaction is more complete；Washing reduces the residual of impurity.
The step 2）In, the polyacrylonitrile（PAN）、Zn3@TBA solid powders and dimethylformamide（DMF）It is mixed
Conjunction mass ratio is 4: 3: 40, Zn3@TBA and ferric acetyl acetonade（Fe（ACAC）3）Molar ratio be 3.5~50: 100.This matter
It measures than in range, being the Key Quality ratio for synthesizing nanofibers, the spinning solution good dispersion degree of preparation.
The step 2）In, the magnetic agitation speed be 800~1000rpm, mixing time be 18~for 24 hours.At this
Under part, each component can fully disperse, and the situation for blocking syringe needle will not occur in spinning process.
The step 3）In, the spinning rate of Static Spinning is 0.3mm/min；The distance of syringe needle and receiver board be 15~
17cm；Spinning voltage is 15~18kv.With this condition, spinning even thickness does not bond.
The step 4）In, the temperature of the pre-oxidation is 250 DEG C, preoxidation time 1h.In this temperature and time model
It encloses, most carbon can be removed.
The step 4）In, the calcination temperature is 450~550 DEG C, calcination time 5h.In this temperature and time model
It encloses, product form structure is better, and pattern variation will not occur because of calcining for product.
Description of the drawings
Fig. 1 is obtained FeWO4The scanning electron microscope (SEM) photograph of nanofiber.
Fig. 2 is the enlarged drawing of Fig. 1.
Fig. 3 is the X-ray powder diffraction figure using three kinds of products produced by the present invention.
Fig. 4 is pure Zn3Experiment effect figure as photocatalyst for degrading rhodamine B.
Fig. 5 is tubular nanometer material FeWO made of the present invention4Experiment effect as photocatalyst for degrading rhodamine B
Figure.
Fig. 6 is tubular nanometer material FeWO made of the present invention4Pictorial diagram as photocatalyst for degrading rhodamine B.
Specific implementation mode
One, in order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments to this hair
It is bright to be described in detail.
Embodiment 1
（1）Prepare Zn3@TBA solids：
Antimony wolframic acid crystal is synthesized according to the method for Michael Bosing et al., then using it as raw material, with reference to Ulrich
The method of Kortz et al. synthesizes Na10[Sb2W18Zn3O66(H2O)3]·48H2O crystal, hereinafter referred to as Zn3。
Weigh the Zn that 0.8g is synthesized in advance3It is dissolved in 10mL water, forms Zn3Aqueous solution, then Zn is added in 0.52gTBA3Water
In solution, 80 DEG C of heating water baths are filtered with the rate magnetic agitation 1h of 800rpm to get white solid, and deionization is washed 3 times,
Absolute ethyl alcohol is washed 1 time, and product Zn is collected in 50 DEG C of drying3@TBA solid powders.
（2）Prepare heteropoly acid nanofiber：
0.8gPAN, 0.6gZn are weighed respectively3@TBA and 0.6gFe (ACAC)3It is put into centrifuge tube mixing, then weighs 8gDMF
It is added dropwise in centrifuge tube by liquid dropwise, continues with the rate magnetic agitation of 1000rpm for 24 hours, its mixing to be made to be uniformly dispersed,
10mL electrostatic spinning liquids are obtained, setting electrostatic spinning machine spinning rate is 0.3mm/min, and spinning syringe needle and receiver board distance are
15cm, spinning voltage 17kv, spinning 6h obtain nanofiber, fiber are pre-oxidized 1h for 250 DEG C in Muffle furnace, in 450 DEG C of height
Temperature calcining 5h, finally obtains tubular fiber product.
Embodiment 2
（1）Prepare Zn3@TBA solids：
Weigh the Zn that 0.8g is synthesized in advance3It is dissolved in 10mL water, forms Zn3Aqueous solution, then Zn is added in 0.52gTBA3Water
In solution, 80 DEG C of heating water baths are filtered with the rate magnetic agitation 1h of 800rpm to get white solid, and deionization is washed 3 times,
Absolute ethyl alcohol is washed 1 time, and product Zn is collected in 50 DEG C of drying3@TBA solid powders.
（2）Prepare heteropoly acid nanofiber：
0.8gPAN, 0.6gZn are weighed respectively3@TBA and 0.2gFe (ACAC)3It is put into centrifuge tube mixing, then weighs 8gDMF
It is added dropwise in centrifuge tube by liquid dropwise, continues with the rate magnetic agitation of 1000rpm for 24 hours, its mixing to be made to be uniformly dispersed,
10mL electrostatic spinning liquids are obtained, setting electrostatic spinning machine spinning rate is 0.3mm/min, and spinning syringe needle and receiver board distance are
16cm, spinning voltage 17.6kv, spinning 6h obtain nanofiber, fiber are pre-oxidized 1h for 250 DEG C in Muffle furnace, at 500 DEG C
High-temperature calcination 5h finally obtains tubular fiber product.
Embodiment 3
（1）Prepare Zn3@TBA solids：
Weigh the Zn that 0.8g is synthesized in advance3It is dissolved in 10mL water, forms Zn3Aqueous solution, then Zn is added in 0.52gTBA3Water
In solution, 80 DEG C of heating water baths are filtered with the rate magnetic agitation 1h of 800rpm to get white solid, and deionization is washed 3 times,
Absolute ethyl alcohol is washed 1 time, and product Zn is collected in 50 DEG C of drying3@TBA solid powders.
（2）Prepare heteropoly acid nanofiber：
0.8gPAN, 0.6gZn are weighed respectively3@TBA and 0.07gFe (ACAC)3It is put into centrifuge tube mixing, is then weighed
It is added dropwise in centrifuge tube by 8gDMF liquid dropwise, continues the rate magnetic agitation 18h with 1000rpm, makes its mixing dispersion
Uniformly, obtain 10mL electrostatic spinning liquids, setting electrostatic spinning machine spinning rate be 0.3mm/min, spinning syringe needle and receiver board away from
Nanofiber is obtained from for 16cm, spinning voltage 18.2kv, spinning 6h, fiber is pre-oxidized into 1h for 250 DEG C in Muffle furnace,
550 DEG C of high-temperature calcination 5h, finally obtain tubular fiber product.
Embodiment 4
（1）Prepare Zn3@TBA solids：
Weigh the Zn that 0.8g is synthesized in advance3It is dissolved in 10mL water, forms Zn3Aqueous solution, then Zn is added in 0.52gTBA3Water
In solution, 80 DEG C of heating water baths are filtered with the rate magnetic agitation 1h of 800rpm to get white solid, and deionization is washed 3 times,
Absolute ethyl alcohol is washed 1 time, and product Zn is collected in 50 DEG C of drying3@TBA solid powders.
（2）Prepare heteropoly acid nanofiber：
0.8gPAN, 0.6gZn are weighed respectively3@TBA and 0.042gFe (ACAC)3It is put into centrifuge tube mixing, is then weighed
It is added dropwise in centrifuge tube by 8gDMF liquid dropwise, continues the rate magnetic agitation 18h with 1000rpm, makes its mixing dispersion
Uniformly, obtain 10mL electrostatic spinning liquids, setting electrostatic spinning machine spinning rate be 0.3mm/min, spinning syringe needle and receiver board away from
Nanofiber is obtained from for 17cm, spinning voltage 18.3kv, spinning 6h, fiber is pre-oxidized into 1h for 250 DEG C in Muffle furnace,
500 DEG C of high-temperature calcination 5h, finally obtain tubular fiber product.
Two, product property：
As shown in Fig. 1,2, for the scanning electron microscope under the different amplification of the tubular fiber product acquired by above each example
Figure.It can be seen that：Gained FeWO4Nanofiber is tubular fiber, and caliber is 400nm or so.
As shown in figure 3, being pure Zn3Spinning fibre after@TBA, 250 DEG C of pre-oxidation and the spinning after 500 DEG C of high-temperature calcinations
The XRD diagram of silk fiber.It can be seen that：Pure Zn3The peak of@TBA is apparent；After the spinning fibre pre-oxidation for mixing ferric acetyl acetonade, only see
See the peak of C；After 500 DEG C of high-temperature calcination 5h, product FeWO is generated4（JCPDC 27-0256）.It is wherein underlying
Vertical line is the characteristic diffraction peak position in standard spectrogram.
Fig. 4 is pure Zn3As the experiment effect figure of photocatalyst for degrading rhodamine B, wherein curve A, B, C, D, E, F, G divides
Pure Zn Biao Shi not used3The experiment passed through respectively 0,5,15,25,35,55,65 minute as photocatalyst for degrading rhodamine B is imitated
Fruit curve.
Fig. 5 is tubular nanometer material FeWO made of the present invention4Experiment effect as photocatalyst for degrading rhodamine B
Figure, wherein curve A, B, C, D, E, F, G are indicated respectively using tubular nanometer material FeWO made of the present invention4As photochemical catalyst
Rhodamine B degradation passes through 0,5,15,25,35,55,65 minute experiment effect curve respectively.
Comparison diagram 4,5, it is seen that：Tubulose FeWO4Nanofiber and pure Zn3It compares, in same time to the photocatalytic of RhB
It can be more preferable.
As shown in fig. 6, being tubular nanometer material FeWO4Pictorial diagram as photocatalyst for degrading rhodamine B.Wherein in figure
A be that RhB solution is added catalyst and stirs 30 minutes up to the reference after adsorption equilibrium, B~G is to be respectively separated 5 points after illumination
Clock, 10 minutes, 15 minutes, 25 minutes, 35 minutes, 55 minutes, sampling in 65 minutes, the color from A to G in bottle is gradually thin out,
It is essentially colourless in especially G bottles, it can be seen that rhodamine B is by degradation quickly.
Three, apply --- tubulose FeWO4Nanofiber catalytic degradation rhodamine B：
Photocatalytic activity evaluation is carried out by simulating pollution object of rhodamine B aqueous solution, 0.07g catalyst of the present invention is added to
Dark adsorption 30min makes catalyst surface reach absorption-in glass reactor equipped with 100mL rhodamine B solutions (10mg/L)
Desorption equilibrium ensures that incident light is visible light using optical filter, leads to condensed water and keep reaction temperature permanent using xenon lamp as light source 300W
It is set to 25 DEG C, after reaction starts, separated in time sampling, sample is through 10000r/min high speed centrifugation 2min, using light splitting light
The absorbance of rhodamine B changes to detect the concentration of rhodamine B at the long 553nm of degree measurement standing wave.
Experimental result is shown：Hollow tube nanometer ferrous tungstate material obtained by the present invention can fully drop after 65min
Rhodamine B is solved, degradation rate is most fast in preceding 5min, and degradation rate has reached 61%, only residue 39%, there is significant photocatalysis performance.
Claims (9)
1. a kind of electrostatic spinning technique prepares FeWO4The method of nanocatalyst, it is characterised in that comprise the steps of：
1）By Na10[Sb2W18Zn3O66(H2O)3]·48H2O crystal is soluble in water, forms Zn3Aqueous solution, then by tetra-n-butyl bromine
Change ammonium and Zn is added3In aqueous solution, magnetic agitation, obtains white solid in a heated condition, filters, with deionized water and absolute ethyl alcohol
It after washing, is dried through 50 DEG C, obtains Zn3@TBA solid powders；
2）By polyacrylonitrile, Zn3@TBA solid powders and ferric acetyl acetonade are placed in centrifuge tube mixing, and dimethyl formyl is then added dropwise
Amine obtains electrostatic spinning liquid through magnetic agitation；
3）By electrostatic spinning liquid through Static Spinning, nanofiber is obtained；
4）Nanofiber is pre-oxidized in air, high-temperature calcination, obtains FeWO4Nanocatalyst.
2. electrostatic spinning technique prepares FeWO according to claim 14The method of nanocatalyst, it is characterised in that：The step
Rapid 1）In, the Zn3A concentration of 0.013mol/L of aqueous solution.
3. electrostatic spinning technique prepares FeWO according to claim 14The method of nanocatalyst, it is characterised in that：The step
Rapid 1）In, the Zn3Na in aqueous solution10[Sb2W18Zn3O66(H2O)3] with the mixing molar ratio of tetra-n-butyl ammonium bromide it is 1: 12.
4. electrostatic spinning technique prepares FeWO according to claim 14The method of nanocatalyst, it is characterised in that：The step
Rapid 1）In, the condition of heating is 80 DEG C, and the rate of magnetic agitation is 800rpm, mixing time 1h, first washs 1 with deionized water
It~3 times, is then washed 1~3 time with absolute ethyl alcohol.
5. electrostatic spinning technique prepares FeWO according to claim 14The method of nanocatalyst, it is characterised in that：The step
Rapid 2）In, the polyacrylonitrile, Zn3The mixing quality of@TBA solid powders and dimethylformamide ratio is 4: 3: 40；The Zn3@
The molar ratio of TBA and ferric acetyl acetonade is 3.5~50: 100.
6. electrostatic spinning technique prepares FeWO according to claim 14The method of nanocatalyst, it is characterised in that：The step
Rapid 2）In, the magnetic agitation speed be 800~1000rpm, mixing time be 18~for 24 hours.
7. electrostatic spinning technique prepares FeWO according to claim 14The method of nanocatalyst, it is characterised in that：The step
Rapid 3）In, the spinning rate of Static Spinning is 0.3mm/min；The distance of syringe needle and receiver board is 15~17cm；Spinning voltage is 15
~18kv.
8. electrostatic spinning technique prepares FeWO according to claim 14The method of nanocatalyst, it is characterised in that：The step
Rapid 4）In, the temperature of the pre-oxidation is 250 DEG C, preoxidation time 1h.
9. electrostatic spinning technique prepares FeWO according to claim 14The method of nanocatalyst, it is characterised in that：The step
Rapid 4）In, the calcination temperature is 450~550 DEG C, calcination time 5h.
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| CN102923784A (en) * | 2012-11-14 | 2013-02-13 | 陕西科技大学 | Preparation method of FeWO4 nanowire |
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| One-dimensional CaWO4 and CaWO4 ：Tb3+ nanowires and nanotubes electrospinning preparation and luminescent properties;Zhiyao Hou等;《J. Mater. Chem.》;20090303;第19卷;第2节 * |
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