CN105903476A - Preparation method using electrospinning technology to prepare FeWO4 nano catalyst - Google Patents
Preparation method using electrospinning technology to prepare FeWO4 nano catalyst Download PDFInfo
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- CN105903476A CN105903476A CN201610287800.5A CN201610287800A CN105903476A CN 105903476 A CN105903476 A CN 105903476A CN 201610287800 A CN201610287800 A CN 201610287800A CN 105903476 A CN105903476 A CN 105903476A
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- Prior art keywords
- fewo
- nanocatalyst
- electrostatic spinning
- tba
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- 229910005507 FeWO4 Inorganic materials 0.000 title claims abstract description 25
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000005516 engineering process Methods 0.000 title abstract description 4
- 238000001523 electrospinning Methods 0.000 title abstract 4
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000002121 nanofiber Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 13
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 9
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000009987 spinning Methods 0.000 claims description 29
- 238000010041 electrostatic spinning Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 229910001868 water Inorganic materials 0.000 claims description 19
- 238000013019 agitation Methods 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 4
- 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
- 230000003068 static effect Effects 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims 2
- -1 dimethyl formyl Amine Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 10
- 239000011964 heteropoly acid Substances 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 2
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 238000003760 magnetic stirring Methods 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 238000000967 suction 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 10
- 230000000694 effects Effects 0.000 description 9
- 239000011941 photocatalyst Substances 0.000 description 8
- 230000000593 degrading effect Effects 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
- 230000001699 photocatalysis Effects 0.000 description 5
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000002242 deionisation method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005286 illumination 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
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction 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
- 230000003213 activating effect Effects 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 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
- 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
- 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
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 description 1
- 238000002336 sorption--desorption measurement 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/58—Fabrics or filaments
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
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Abstract
The invention relates to a preparation method using the electrospinning technology to prepare a FeWO4 nano catalyst and belongs to the technical field of catalytic chemistry. The preparation method includes: mixing the aqueous solution of Na10[Sb2W18Zn3O66(H2O)3].48H2O with tetra-n-butyl ammonium bromide to obtain a white solid, performing suction filtration, washing, and drying to obtain Zn3@TBA solid powder; mixing polyacrylonitrile, the Zn3@TBA solid powder and ferric acetylacetonate, dripping dimethyl formamide, performing magnetic stirring to obtain electrospinning liquid, performing electrospinning to obtain nano fibers, pre-oxidizing in air, and performing high-temperature calcination to obtain the FeWO4 nano catalyst. The preparation method has the advantages that by the FeWO4 nano catalyst prepared by the method, the defect that the catalyst is hard to be separated from a reaction system due to the fact that heteropolyacid is high in solubility can be overcome; the prepared FeWO4 nano catalyst is large in surface, and the catalytic performance can be increased favorably.
Description
Technical field
The invention belongs to technical field of catalytic chemistry, be specifically related to tubulose FeWO4The technology of preparing of nano-fiber material.
Background technology
Although heteropoly acid (salt) has good catalytic performance as acid catalyst and oxidation reduction catalyst, some use
The process of heteropoly acid (salt) has realized industrialization the most, but some being had due to heteropoly acid (salt) itself is not enough, such as specific surface
Long-pending less by (1～10m2/ g), it is unfavorable for giving full play to of reactivity；In polar solvent and non-polar solven, dissolubility is big,
Cause catalyst to be difficult to separate with reaction system, be unfavorable for industrialized continuous production；Catalyst recovery is relatively difficult.
Ferrous tungstate (FeWO4) it is a kind of important functional inorganic materials, the application in magnetic fields has been achieved with many
Achievement, but in terms of photocatalysis, research also has much room, and the flower-shaped ferrous tungstate material of a kind of hexagonal of having reported is to RhB
There is good photocatalysis effect.
At present, the synthetic method of ferrous tungstate material mainly includes hydrothermal synthesis method, ultrasonic etc..Prepared
FeWO4There is starlike, bar-shaped, hexagonal flake etc. to be mostly micron-sized, and nanoscale definite proportion is more rare.
Summary of the invention
It is an object of the invention to propose a kind of method novel, the simple FeWO of equipment requirements4The 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 tetra-n-butyl bromine
Change ammonium (TBA) and add Zn3In aqueous solution, magnetic agitation in a heated condition, obtain white solid, sucking filtration, with deionized water and nothing
After water-ethanol washing, through 50 DEG C of drying, obtain Zn3@TBA pressed powder；
2) by polyacrylonitrile (PAN), Zn3@TBA pressed powder and ferric acetyl acetonade (Fe(ACAC)3) it is placed in centrifuge tube mixing, so
Rear dropping dimethylformamide (DMF), through magnetic agitation, obtains electrostatic spinning liquid；
3) by electrostatic spinning liquid through Static Spinning, nanofiber is obtained；
4) nanofiber is pre-oxidized in atmosphere, high-temperature calcination, obtain FeWO4Nanocatalyst.
The feature of present invention process is:
1, the present invention is with Zn3With ferric acetyl acetonade as presoma, synthesize FeWO through method of electrostatic spinning4, there is originality.
2, the nanofiber made has the tubular morphology of high surface area, straight through pre-oxidation and high-temperature calcination fiber pipe
Footpath is hollow FeWO of about 400nm4Nanofiber, structure is the most homogeneous, better crystallinity degree, and there is pore passage structure inside, has
Reasonably heteropolyacid salt density, activity is low, and chemical stability is high.
3, the present invention is the low temperature of a kind of green environment close friend, high activity, high selectivity composite efficient catalyst, more sharp
Carrying out in heterogeneous catalytic reaction；The price comparison of raw material is low simultaneously, can reduce the manufacturing cost of catalyst.
In a word, method of electrostatic spinning of the present invention can obtain the ferrous tungstate material of nanoscale tubulose easily, no
It is dissolved in water, heteropoly acid dissolubility can be overcome big, cause catalyst to be difficult to the shortcoming separated with reaction system；Meanwhile, with tradition
Ferrous tungstate phase specific surface is bigger, is conducive to improving catalytic performance.
Further, in step 1) of the present invention, described Zn3The concentration of aqueous solution is 0.013mol/L.This concentration bar
Part is conducive to quickly completing next step smoothly and carries out cation exchange with tetra-n-butyl ammonium bromide (TBA).
In described step 1), described Zn3Na in aqueous solution10[Sb2W18Zn3O66(H2O)3] and tetra-n-butyl ammonium bromide (TBA)
Mixing mol ratio be 1: 12.The tetra-n-butyl ammonium bromide (TBA) of excess can ensure that replaces Na completely+。
In described step 1), the condition of heating is 80 DEG C, and the speed of magnetic agitation is 800rpm, and mixing time is 1h, first
With deionized water wash 1～3 times, then with absolute ethanol washing 1～3 times.In this temperature and time scope, reactant can be at water
Fully activating under heat condition, reaction is completely；Magnetic stirrer speed is 800rpm；Overcome the stress of conventional agitator not
Uniformly, dispersed with stirring effect is more preferable, reacts more complete；Washing reduces the residual of impurity.
Described step 2) in, described polyacrylonitrile (PAN), Zn3@TBA pressed powder and dimethylformamide (DMF) mixed
Closing mass ratio is 4: 3: 40, Zn3@TBA and ferric acetyl acetonade (Fe(ACAC)3) molar ratio be 3.5～50: 100.This matter
In the range of amount ratio, it is the Key Quality ratio synthesizing nanofiber, the spinning liquid good dispersion degree of preparation.
Described step 2) in, described magnetic agitation speed is 800～1000rpm, and mixing time is 18～24h.At this
Under part, each component can be disperseed fully, and the situation of syringe needle will not occur in spinning process to block.
In described step 3), the spinning speed of Static Spinning is 0.3mm/min；Syringe needle and receive plate distance be 15～
17cm；Spinning voltage is 15～18kv.With this understanding, spinning even thickness, not bonding.
In described step 4), the temperature of described pre-oxidation is 250 DEG C, and preoxidation time is 1h.At this temperature and time model
Enclose, it is possible to remove most carbon.
In described step 4), described calcining heat is 450～550 DEG C, and calcination time is 5h.At this temperature and time model
Enclosing, product form structure is better, and product will not occur morphology change because of calcining.
Accompanying drawing explanation
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 diagram of the three kinds of products using the present invention to prepare.
Fig. 4 is pure Zn3Experiment effect figure as photocatalyst for degrading rhodamine B.
Fig. 5 is the tubular nanometer material FeWO that the present invention makes4Experiment effect as photocatalyst for degrading rhodamine B
Figure.
Fig. 6 is the tubular nanometer material FeWO that the present invention makes4Pictorial diagram as photocatalyst for degrading rhodamine B.
Detailed description of the invention
One, in order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment to this
Bright it is described in detail.
Embodiment 1
(1) Zn is prepared3@TBA solid:
Method synthesis antimony wolframic acid crystal according to Michael Bosing et al., then using it as raw material, with reference to Ulrich
The method synthesis Na of Kortz et al.10[Sb2W18Zn3O66(H2O)3]·48H2O crystal, hereinafter referred to as Zn3。
Weigh the Zn that 0.8g synthesizes in advance3It is dissolved in 10mL water, forms Zn3Aqueous solution, then 0.52gTBA is added Zn3Water
In solution, 80 DEG C of heating in water bath, with speed magnetic agitation 1h of 800rpm, obtain white solid, sucking filtration, deionization is washed 3 times,
Dehydrated alcohol is washed 1 time, 50 DEG C of drying, collects product Zn3@TBA pressed powder.
(2) heteropoly acid nanofiber is prepared:
Weigh 0.8gPAN, 0.6gZn respectively3@TBA and 0.6gFe (ACAC)3Put into centrifuge tube mixing, then weigh 8gDMF liquid
Body, is dropwise added dropwise to it in centrifuge tube, continues speed magnetic agitation 24h with 1000rpm so that it is mixing is uniformly dispersed, and takes
Obtaining 10mL electrostatic spinning liquid, arranging electrostatic spinning machine spinning speed is 0.3mm/min, and spinning syringe needle and reception plate distance are
15cm, spinning voltage is 17kv, and spinning 6h obtains nanofiber, by fiber 250 DEG C of pre-oxidation 1h in Muffle furnace, high at 450 DEG C
Temperature calcining 5h, finally gives tubular fiber product.
Embodiment 2
(1) Zn is prepared3@TBA solid:
Weigh the Zn that 0.8g synthesizes in advance3It is dissolved in 10mL water, forms Zn3Aqueous solution, then 0.52gTBA is added Zn3Aqueous solution
In, 80 DEG C of heating in water bath, with speed magnetic agitation 1h of 800rpm, obtain white solid, sucking filtration, deionization is washed 3 times, anhydrous
Ethanol is washed 1 time, 50 DEG C of drying, collects product Zn3@TBA pressed powder.
(2) heteropoly acid nanofiber is prepared:
Weigh 0.8gPAN, 0.6gZn respectively3@TBA and 0.2gFe (ACAC)3Put into centrifuge tube mixing, then weigh 8gDMF liquid
Body, is dropwise added dropwise to it in centrifuge tube, continues speed magnetic agitation 24h with 1000rpm so that it is mixing is uniformly dispersed, and takes
Obtaining 10mL electrostatic spinning liquid, arranging electrostatic spinning machine spinning speed is 0.3mm/min, and spinning syringe needle and reception plate distance are
16cm, spinning voltage is 17.6kv, and spinning 6h obtains nanofiber, by fiber 250 DEG C of pre-oxidation 1h in Muffle furnace, at 500 DEG C
High-temperature calcination 5h, finally gives tubular fiber product.
Embodiment 3
(1) Zn is prepared3@TBA solid:
Weigh the Zn that 0.8g synthesizes in advance3It is dissolved in 10mL water, forms Zn3Aqueous solution, then 0.52gTBA is added Zn3Aqueous solution
In, 80 DEG C of heating in water bath, with speed magnetic agitation 1h of 800rpm, obtain white solid, sucking filtration, deionization is washed 3 times, anhydrous
Ethanol is washed 1 time, 50 DEG C of drying, collects product Zn3@TBA pressed powder.
(2) heteropoly acid nanofiber is prepared:
Weigh 0.8gPAN, 0.6gZn respectively3@TBA and 0.07gFe (ACAC)3Put into centrifuge tube mixing, then weigh 8gDMF liquid
Body, is dropwise added dropwise to it in centrifuge tube, continues speed magnetic agitation 18h with 1000rpm so that it is mixing is uniformly dispersed, and takes
Obtaining 10mL electrostatic spinning liquid, arranging electrostatic spinning machine spinning speed is 0.3mm/min, and spinning syringe needle and reception plate distance are
16cm, spinning voltage is 18.2kv, and spinning 6h obtains nanofiber, by fiber 250 DEG C of pre-oxidation 1h in Muffle furnace, at 550 DEG C
High-temperature calcination 5h, finally gives tubular fiber product.
Embodiment 4
(1) Zn is prepared3@TBA solid:
Weigh the Zn that 0.8g synthesizes in advance3It is dissolved in 10mL water, forms Zn3Aqueous solution, then 0.52gTBA is added Zn3Aqueous solution
In, 80 DEG C of heating in water bath, with speed magnetic agitation 1h of 800rpm, obtain white solid, sucking filtration, deionization is washed 3 times, anhydrous
Ethanol is washed 1 time, 50 DEG C of drying, collects product Zn3@TBA pressed powder.
(2) heteropoly acid nanofiber is prepared:
Weigh 0.8gPAN, 0.6gZn respectively3@TBA and 0.042gFe (ACAC)3Put into centrifuge tube mixing, then weigh 8gDMF
Liquid, is dropwise added dropwise to it in centrifuge tube, continues speed magnetic agitation 18h with 1000rpm so that it is mixing is uniformly dispersed,
Obtaining 10mL electrostatic spinning liquid, arranging electrostatic spinning machine spinning speed is 0.3mm/min, and spinning syringe needle and reception plate distance are
17cm, spinning voltage is 18.3kv, and spinning 6h obtains nanofiber, by fiber 250 DEG C of pre-oxidation 1h in Muffle furnace, at 500 DEG C
High-temperature calcination 5h, finally gives tubular fiber product.
Two, product property:
Such as Fig. 1, shown in 2, the scanning electron microscope (SEM) photograph under the different amplification of the tubular fiber product acquired by above each example.
Visible: gained FeWO4Nanofiber is tubular fiber, and caliber is about 400nm.
As shown in Fig. 3, for pure Zn3@TBA, 250 DEG C pre-oxidation after spinning fibre and 500 DEG C of high-temperature calcinations after spin
The XRD figure of silk fiber.Visible: pure Zn3The peak of@TBA is obvious；After the spinning fibre pre-oxidation of mixing ferric acetyl acetonade, only see
See the peak of C；After 500 DEG C of high-temperature calcination 5h, generate product FeWO4(JCPDC 27-0256).Wherein it is positioned at lower section
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
Biao Shi not use pure Zn3Imitate respectively through the experiment of 0,5,15,25,35,55,65 minutes as photocatalyst for degrading rhodamine B
Really curve.
Fig. 5 is the tubular nanometer material FeWO that the present invention makes4Experiment effect as photocatalyst for degrading rhodamine B
Figure, wherein curve A, B, C, D, E, F, G represents the tubular nanometer material FeWO using the present invention to make respectively4As photocatalyst
Rhodamine B degradation was respectively through the experiment effect curve of 0,5,15,25,35,55,65 minutes.
Comparison diagram 4,5, it is seen that: tubulose FeWO4Nanofiber and pure Zn3Compare, the photocatalytic to RhB in the identical time
Can be more preferably.
As shown in Figure 6, for tubular nanometer material FeWO4Pictorial diagram as photocatalyst for degrading rhodamine B.Wherein in figure
A be that RhB solution adds catalyst stirring and within 30 minutes, reaches 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, the sampling of 65 minutes, the color from A to G bottle is the most thin out,
In particularly G bottle the most colourless, it can be seen that rhodamine B is by degraded quickly.
Three, application tubulose FeWO4Nanofiber catalytic degradation rhodamine B:
Carry out photocatalytic activity evaluation with rhodamine B aqueous solution for simulating pollution thing, catalyst of the present invention for 0.07g is added to equipped with
In the glass reactor of 100mL rhodamine B solution (10mg/L), dark adsorption 30min makes catalyst surface reach adsorption-desorption
Balance, with xenon lamp for light source 300W, uses optical filter to ensure that incident illumination is visible ray, and logical condensed water keeps that reaction temperature is constant is
25 DEG C, after reaction starts, separated in time samples, and sample, through 10000r/min high speed centrifugation 2min, uses spectrophotometer
Measure the absorbance of rhodamine B at wavelength 553nm and detect the concentration change of rhodamine B.
Experimental result shows: the hollow pipe nanometer ferrous tungstate material obtained by the present invention can fully drop after 65min
Solving rhodamine B, in front 5min, degradation rate is the fastest, and degradation rate has reached 61%, only remains 39%, has significant photocatalysis performance.
Claims (9)
1. an 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 add Zn3In aqueous solution, magnetic agitation in a heated condition, obtain white solid, sucking filtration, with deionized water and dehydrated alcohol
After washing, through 50 DEG C of drying, obtain Zn3@TBA pressed powder；
2) by polyacrylonitrile, Zn3@TBA pressed powder and ferric acetyl acetonade are placed in centrifuge tube mixing, then dropping dimethyl formyl
Amine, through magnetic agitation, obtains electrostatic spinning liquid；
3) by electrostatic spinning liquid through Static Spinning, nanofiber is obtained；
4) nanofiber is pre-oxidized in atmosphere, high-temperature calcination, obtain FeWO4Nanocatalyst.
The most according to claim 1, electrostatic spinning technique prepares FeWO4The method of nanocatalyst, it is characterised in that: described step
Rapid 1) in, described Zn3The concentration of aqueous solution is 0.013mol/L.
The most according to claim 1, electrostatic spinning technique prepares FeWO4The method of nanocatalyst, it is characterised in that: described step
Rapid 1) in, described Zn3Na in aqueous solution10[Sb2W18Zn3O66(H2O)3] it is 1: 12 with the mixing mol ratio of tetra-n-butyl ammonium bromide.
The most according to claim 1, electrostatic spinning technique prepares FeWO4The method of nanocatalyst, it is characterised in that: described step
Rapid 1) in, the condition of heating is 80 DEG C, and the speed of magnetic agitation is 800rpm, and mixing time is 1h, first with deionized water wash 1
～3 times, then with absolute ethanol washing 1～3 times.
The most according to claim 1, electrostatic spinning technique prepares FeWO4The method of nanocatalyst, it is characterised in that: described step
Rapid 2) in, described polyacrylonitrile, Zn3The mixing quality ratio of@TBA pressed powder and dimethylformamide is 4: 3: 40；Described Zn3@
The molar ratio of TBA and ferric acetyl acetonade is 3.5～50: 100.
The most according to claim 1, electrostatic spinning technique prepares FeWO4The method of nanocatalyst, it is characterised in that: described step
Rapid 2) in, described magnetic agitation speed is 800～1000rpm, and mixing time is 18～24h.
The most according to claim 1, electrostatic spinning technique prepares FeWO4The method of nanocatalyst, it is characterised in that: described step
Rapid 3), in, the spinning speed of Static Spinning is 0.3mm/min；Syringe needle and the distance receiving plate are 15～17cm；Spinning voltage is 15
～18kv.
The most according to claim 1, electrostatic spinning technique prepares FeWO4The method of nanocatalyst, it is characterised in that: described step
Rapid 4) in, the temperature of described pre-oxidation is 250 DEG C, and preoxidation time is 1h.
The most according to claim 1, electrostatic spinning technique prepares FeWO4The method of nanocatalyst, it is characterised in that: described step
Rapid 4) in, described calcining heat is 450～550 DEG C, and calcination time is 5h.
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| CN112517068A (en) * | 2020-12-11 | 2021-03-19 | 扬州大学 | Visible light catalyst for treating hexavalent chromium wastewater and synthesis method thereof |
| CN113893878A (en) * | 2021-10-15 | 2022-01-07 | 海南师范大学 | Preparation method and application of nanofiber-supported heteropolyacid salt catalyst |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106830092A (en) * | 2017-01-23 | 2017-06-13 | 重庆市畜牧科学院 | A kind of preparation method of iron molybdate/iron tungstate with 1-dimention nano fibre structure and product and application |
| CN106830092B (en) * | 2017-01-23 | 2019-03-08 | 重庆市畜牧科学院 | It is a kind of with the iron molybdate/iron tungstate preparation method and product of 1-dimention nano fibre structure and application |
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| CN109292954B (en) * | 2018-11-20 | 2020-07-31 | 湖北省工程咨询股份有限公司 | FeWO4Method for degrading pollutants in water by nanosheet |
| CN112517068A (en) * | 2020-12-11 | 2021-03-19 | 扬州大学 | Visible light catalyst for treating hexavalent chromium wastewater and synthesis method thereof |
| CN113893878A (en) * | 2021-10-15 | 2022-01-07 | 海南师范大学 | Preparation method and application of nanofiber-supported heteropolyacid salt catalyst |
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