CN105056998A - Preparation method of nano zinc oxide/cyclized polyacrylonitrile composite micro-sphere material with zinc oxide nano particles uniformly distributed in polymer - Google Patents
Preparation method of nano zinc oxide/cyclized polyacrylonitrile composite micro-sphere material with zinc oxide nano particles uniformly distributed in polymer Download PDFInfo
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- CN105056998A CN105056998A CN201510555529.4A CN201510555529A CN105056998A CN 105056998 A CN105056998 A CN 105056998A CN 201510555529 A CN201510555529 A CN 201510555529A CN 105056998 A CN105056998 A CN 105056998A
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Abstract
The invention discloses a preparation method of a nano zinc oxide/cyclized polyacrylonitrile composite micro-sphere material with zinc oxide nano particles uniformly distributed in a polymer and belongs to the technical field of a novel material of an environment purification photocatalyst. The preparation method comprises the following steps: firstly, dissolving polyacrylonitrile and zinc nitrate solids into a dimethyl sulfoxide solvent; slowly dripping a mixed solution into a diluted ammonia water solution; condensing polyacrylonitrile into micro-spheres in water and enabling zinc nitrate and hydroxyl ions to react to generate zinc hydroxide in situ to obtain composite micro-spheres with zinc hydroxide nano particles uniformly distributed in polyacrylonitrile; and then separating, washing, drying and baking under inert gas to obtain the nano zinc oxide/cyclized polyacrylonitrile composite micro-sphere material. The preparation method has the advantages that the preparation method is simple, complicated equipment is not needed, used polyacrylonitrile has a cheap price and is easy to obtain and the zinc oxide nano particles are uniformly distributed in the cyclized polyacrylonitrile composite micro-spheres; and the prepared composite micro-sphere material has excellent visible-light catalytic activity.
Description
Technical field
The present invention is specifically related to the preparation method that a kind of zinc oxide nano-particle is uniformly distributed in the nano zine oxide/cyclization polyacrylonitrile composite microsphere material in polymer, belongs to depollution of environment photochemical catalyst new material technology field.
Background technology
Photocatalysis technology based on nano semiconductor material is acknowledged as a kind of elimination environmental contaminants, the green technology that solves energy crisis most with development potentiality and application prospect.In numerous conductor photocatalysis material, the advantage such as photohole oxidability is strong, catalytic activity is high because having, chemical stability is good, cost is low for nano zine oxide, nontoxic, wide material sources and receiving much concern.But zinc oxide is wide bandgap semiconductor, photocatalysis can only be produced by ultraviolet excitation, and its light induced electron/hole-recombination probability is higher, seriously constrains the practical application of zinc oxide as photochemical catalyst.In order to solve the problem, current lot of domestic and foreign researcher by number of ways as nano zine oxide crystal formation, crystal face, pattern, size adjustment, metal ion or nonmetal doping, noble metal loading, semiconductors coupling etc. carry out modification to photocatalyst of zinc oxide, to reach the object improving electrons separative efficiency, widen absorption spectrum ranges.
Research in recent years shows, adopts to have the material with carbon element of conjugated structure and nano zine oxide compound improves the effective way of its visible light catalysis activity.Such as Zhu Yongfa etc. adopt at zinc oxide nano-particle surface recombination football alkene (C60) (EnvironmentalScienceandTechnology, 2008,42:8064 – 8069); FuLi etc. adopt hydro-thermal method to prepare reduced graphene/zinc oxide composite photocatalyst (CeramicsInternational, 2015,41:4007 – 4013); ChenDaimei etc. are by mesoporous carbonitride (mg-C
3n
4) and the ultrasonic disperse of zinc oxide (ZnO) particle in methyl alcohol obtain ZnOmpg-C
3n
4composite photo-catalyst (AppliedCatalysisB:Environmental, 2014,147:554 – 561); LiuPing etc. are by cold plasma treatment technology and chemical deposition polyaniline (the PANI) (JournalofPhysicalChemistryC in zinc oxide nano-particle Surface coating monolayer, 2014,118:9570 – 9577), result shows that these methods all make the photocatalytic activity of gained composite photo-catalyst significantly improve, and photocatalytic activity improves degree and material with carbon element is closely related in the coated degree on zinc oxide particles surface.But in above-mentioned material with carbon element, football alkene (C60) molecule is spherical, Graphene and carbonitride is lamellar structure, strand rigidity is larger, with zinc oxide particles compound tense, be difficult to zinc oxide particles is complete, closely wrap up, and the lamella number of plies of Graphene and carbonitride is difficult to effective control in liquid medium, the thickness of zinc oxide surface Graphene or carbonitride and distribution is caused to be difficult to control.And the shortcoming of polyaniline is water insoluble and common solvent, the more difficult control of uniformity coefficient of its molecular weight and compound, is unsuitable for a large amount of production and application.In addition, when adopting previously prepared good zinc oxide particles to carry out surface recombination, even if carry out ultrasonic disperse be also difficult to thoroughly to solve the agglomeration traits that zinc oxide nano-particle causes because surface energy is high, this will inevitably affect the distributing homogeneity of zinc oxide in compound, and then affects the photocatalysis performance of composite.
Summary of the invention
The present invention, for solving the problems of the prior art, provides a kind of zinc oxide nano-particle to be uniformly distributed in the preparation method of the nano zine oxide/cyclization polyacrylonitrile composite microsphere material in polymer.Namely general polymer polyacrylonitrile is utilized to prepare efficient visible light catalyst for material modification nano zine oxide.
Thinking of the present invention is, dimethyl sulfoxide (DMSO) mixed solution containing polyacrylonitrile and zinc nitrate is slowly instilled in dilute ammonia solution, while polyacrylonitrile is condensed into microballoon in water, in zinc nitrate and the aqueous solution, hydroxide ion reacts in-situ preparation zinc hydroxide nano particle, obtain zinc hydroxide uniform particle and be dispersed in complex microsphere in polyacrylonitrile, then roasting obtains nano zine oxide/cyclization polyacrylonitrile composite microsphere material under inert gas.
Technical scheme of the present invention mainly comprises the steps:.
A. polyacrylonitrile is dissolved in dimethyl sulfoxide solvent, after dissolving completely, is made into the dimethyl sulphoxide solution that polyacrylonitrile mass concentration is 20.0g/L; Separately get zinc nitrate hexahydrate (Zn (NO
3)
26H
2o) solid is dissolved in dimethyl sulfoxide solvent and obtains the dimethyl sulphoxide solution that zinc nitrate concentration is 1.3mol/L ~ 1.4mol/L; Concentrated ammonia solution is made at distillation dilution with water the ammonia spirit that ammonia density is 0.1% ~ 0.4%;
B. get the dimethyl sulphoxide solution 5.0mL of zinc nitrate described in step a, the dimethyl sulphoxide solution 9.0mL ~ 27.0mL of polyacrylonitrile described in removing step a, airtightly to mix, obtain zinc nitrate and polyacrylonitrile dimethyl sulfoxide (DMSO) mixed solution;
C. zinc nitrate described in step b and polyacrylonitrile dimethyl sulfoxide (DMSO) mixed solution are slowly added drop-wise in ammonia spirit described in step a, the volume ratio controlling dimethyl sulfoxide (DMSO) mixed solution and ammonia spirit is 1:10 ~ 1:20, time for adding is 20min ~ 40min, dropwise rear continuation and stir 20min ~ 40min, leave standstill 8h ~ 12h afterwards, product is filtered, washing 3 times, after drying zinc hydroxide nano particle is evenly distributed on nanometer zinc hydroxide/polyacrylonitrile complex microsphere in polyacrylonitrile;
D. by step c gained nanometer zinc hydroxide/polyacrylonitrile complex microsphere in a nitrogen atmosphere in 230 DEG C ~ 260 DEG C roasting 30min ~ 120min, obtain nano zine oxide/cyclization polyacrylonitrile composite microsphere material.
Preferably, in step b, the mass ratio of zinc nitrate and polyacrylonitrile is 2:1 ~ 8:1.
Preferably, in step c, the mol ratio of ammonia and zinc nitrate is 4:1 ~ 5:1.
Preferably, in step c, the volume ratio of dimethyl sulfoxide (DMSO) mixed solution and ammonia spirit is 1:10 ~ 1:15.
Preferably, the nanometer zinc hydroxide described in steps d/polyacrylonitrile complex microsphere sintering temperature is 240 DEG C ~ 250 DEG C, and roasting time is 30min ~ 90min.
Preferably, in nano zine oxide/cyclization polyacrylonitrile composite microsphere material, the mass ratio of polyacrylonitrile and zinc oxide is 1:1 ~ 1:3.
The outstanding advantages that the present invention compared with prior art has is:
(1) with general polymer polyacrylonitrile for conjugated structure polymer prepared by raw material, cheap and easy to get, and polymerization process and polymer molecular weight easily control;
(2) zinc oxide nano-particle can be made to be uniformly distributed in cyclization polyacrylonitrile microballoon, avoid the impact of reunion on photocatalytic activity of zinc oxide nano-particle, described preparation method is simple, does not need complex device, is suitable for suitability for industrialized production;
(3) nano zine oxide prepared by/cyclization polyacrylonitrile composite microsphere material absorbs at visible region and significantly improves, and has excellent visible light catalysis activity.
Accompanying drawing explanation
Fig. 1 nano zine oxide prepared by embodiment 1/cyclization polyacrylonitrile complex microsphere X ray diffracting spectrum and zinc oxide standard X-ray diffraction collection of illustrative plates;
The polyacrylonitrile of Fig. 2 prepared by embodiment 1 and nano zine oxide/cyclization polyacrylonitrile composite microsphere material Fourier transform infrared spectrogram;
The nano zine oxide of Fig. 3 prepared by embodiment 1/cyclization polyacrylonitrile composite microsphere material scanning electron microscope (SEM) photograph;
Fig. 4 is Zn-ef ficiency distribution map in nano zine oxide/cyclization polyacrylonitrile complex microsphere grain material;
Fig. 5 is oxygen element distribution map in nano zine oxide/cyclization polyacrylonitrile complex microsphere grain material;
Fig. 6 is carbon distribution map in nano zine oxide/cyclization polyacrylonitrile complex microsphere grain material;
Fig. 7 is nitrogen distribution diagram of element in nano zine oxide/cyclization polyacrylonitrile complex microsphere grain material;
The UV-Vis DRS of the zinc oxide prepared under Fig. 8 nano zine oxide prepared by embodiment 1/cyclization polyacrylonitrile composite microsphere material and the same terms absorbs spectrogram;
The zinc oxide visible light photocatalytic degradation methyl orange situation prepared under Fig. 9 nano zine oxide prepared by embodiment 1/cyclization polyacrylonitrile composite microsphere material and the same terms.
Detailed description of the invention
Embodiment 1
Take polyacrylonitrile solid 1.00g to be dissolved in completely in dimethyl sulfoxide (DMSO), be made into the polyacrylonitrile dimethyl sulphoxide solution of 50mL, separately getting zinc nitrate hexahydrate solid 2.00g is dissolved in 5.0mL dimethyl sulfoxide (DMSO), then pipette above-mentioned polyacrylonitrile dimethyl sulphoxide solution 27.0mL to mix with zinc nitrate dimethyl sulphoxide solution, obtain the dimethyl sulfoxide (DMSO) mixed solution of zinc nitrate and polyacrylonitrile.By ammonia density be again 25% ammonia spirit 2.20g distill dilution with water at 320mL, be made into the dilute ammonia solution that mass concentration is 0.17%.Then under rapid mixing conditions, the dimethyl sulfoxide (DMSO) mixed solution of described zinc nitrate and polyacrylonitrile is slowly added drop-wise in described dilute ammonia solution, time for adding is 30min, dropwise and continue to stir 30min, leave standstill 12h afterwards, product is filtered, washing 3 times, obtain zinc hydroxide nano particle at 60 DEG C after drying and be dispersed in zinc hydroxide/polyacrylonitrile complex microsphere in polyacrylonitrile.Finally by gained nanometer zinc hydroxide/polyacrylonitrile complex microsphere 250 DEG C of roasting 60min in a nitrogen atmosphere, obtain nano zine oxide/cyclization polyacrylonitrile composite microsphere material.
The X ray diffracting spectrum of nano zine oxide prepared by the present embodiment/cyclization polyacrylonitrile composite microsphere material is as shown in spectral line (a) in Fig. 1, can find out, diffraction maximum is there is in nano zine oxide prepared by this method/cyclization polyacrylonitrile composite microsphere material at the places such as 31.78 °, 34.43 °, 36.27 °, 47.54 °, completely corresponding with the type of hexagonal wurtzite spectral line (b) Suo Shi zinc oxide standard X-ray diffraction collection of illustrative plates (PDF#01-089-0510), illustrate that prepared nano zine oxide is hexagonal wurtzite type.Fig. 2 is the Fourier transform infrared spectrogram of polyacrylonitrile and prepared nano zine oxide/cyclization polyacrylonitrile composite microsphere material, in figure, spectral line a is polyacrylonitrile Fourier transform infrared spectrogram, and spectral line b is nano zine oxide/cyclization polyacrylonitrile composite microsphere material Fourier transform infrared spectrogram.In spectral line b, wave number is at 400cm
-1~ 500cm
-1between absworption peak be zinc oxide signature peaks, by spectral line b and polyacrylonitrile infrared spectrum, (spectral line a) contrasts and can find, spectral line b is at 2245cm
-1place itrile group (– C ≡ N) vibration peak obviously weakens, and at wave number 1580cm
-1, 1610cm
-1place occurs belonging to carbon-to-nitrogen double bon (– C=N –), carbon-carbon double bond (– C=C –) stronger absworption peak, and 1455cm
-1locate hydrocarbon (C – H) flexural vibrations peak to move to lower wave number, show that in composite microsphere material, polyacrylonitrile after heat treatment forms the cyclization polyacrylonitrile of Ju You – C=C – C=N – conjugated structure.Nano zine oxide prepared by embodiment 1/cyclization polyacrylonitrile composite microsphere material ESEM is illustrated in Fig. 3, can finds out, prepared nano zine oxide/cyclization polyacrylonitrile complex microsphere domain size distribution is comparatively even, is about 30nm ~ 50nm.Fig. 4 is Zn-ef ficiency distribution map in nano zine oxide/cyclization polyacrylonitrile complex microsphere grain material, Fig. 5 is oxygen element distribution map in nano zine oxide/cyclization polyacrylonitrile complex microsphere grain material, Fig. 6 is carbon distribution map in nano zine oxide/cyclization polyacrylonitrile complex microsphere grain material, Fig. 7 is nitrogen distribution diagram of element in nano zine oxide/cyclization polyacrylonitrile complex microsphere grain material, as can be seen from Fig. 4 ~ Fig. 7, oxygen in prepared material, zinc, carbon, nitrogen four kinds of elements are substantially all presenting equally distributed state within sweep of the eye, zinc, oxygen element distribution density is similar to, belong to zinc oxide (ZnO), carbon and nitrogen element belong to cyclization polyacrylonitrile, because carbon and nitrogen atoms in polyacrylonitrile strand is than being 3:1, therefore nitrogen Elemental redistribution density is relatively little.Fig. 4 ~ Fig. 7 demonstrates method therefor of the present invention can make nano zine oxide be uniformly distributed in cyclization polyacrylonitrile microballoon, reaches the equally distributed object of zinc oxide in composite.The UV-Vis DRS of the zinc oxide prepared under the nano zine oxide prepared by Fig. 8 shows/cyclization polyacrylonitrile composite microsphere material and the same terms absorbs spectrogram, the nano zine oxide prepared by the present invention/cyclization polyacrylonitrile composite microsphere material in the absorption (as shown in curve a) of whole spectral region interior focusing all higher than the zinc oxide prepared under the same terms (as shown in curve b).
The photocatalysis performance test of prepared nano zine oxide/cyclization polyacrylonitrile composite microsphere material is as follows: add photochemical catalyst prepared by 0.12g in the reactor and 120g concentration is the methyl orange solution of 20mg/L, stir after 2.0h reaches adsorption equilibrium under dark condition, open visible light source (adding a cover the 300W iodine-tungsten lamp of optical filter) to irradiate, sample from reaction system in a certain time interval, after centrifugation catalyst, get supernatant liquor spectrophotometer and measure absorbance under methyl orange maximum absorption wavelength 464nm, the change in concentration situation of methyl orange in solution is obtained by working curve, concentration absorption before illumination being reached methyl orange during balance is designated as c
0, during illumination different time, methyl orange concentration is designated as c
t, the degradation rate D/%=(c of illumination degrading methyl orange can be calculated
0-c
t)/c
0× 100%, thus the catalytic activity drawing photochemical catalyst.The zinc oxide visible light photocatalytic degradation methyl orange situation prepared under Fig. 9 nano zine oxide prepared by embodiment 1/cyclization polyacrylonitrile composite microsphere material and the same terms.Experimental result is known as shown in Figure 9, pure zinc oxide is only 1.7% (as shown in Fig. 9 curve b) for the degradation rate of catalyst to methyl orange, substantially visible light catalysis activity is not had, and nano zine oxide/cyclization polyacrylonitrile composite microsphere material prepared by the present embodiment reaches 94.9% (as shown in Fig. 9 curve a) to the degradation rate of 20mg/L methyl orange, visible light catalytic performance highly significant when radiation of visible light 60min for catalyst.
Embodiment 2
Taking polyacrylonitrile solid 1.00g is dissolved in 50mL dimethyl sulfoxide solvent, separately getting zinc nitrate hexahydrate solid 2.00g is dissolved in 5.0mL dimethyl sulfoxide solvent, then pipette polyacrylonitrile dimethyl sulphoxide solution 9.0mL to mix with the dimethyl sulphoxide solution of above-mentioned zinc nitrate is airtight, obtain zinc nitrate and polyacrylonitrile dimethyl sulfoxide (DMSO) mixed solution.By ammonia density be again 25% ammonia spirit 2.20g distill dilution with water at 140mL, be made into the dilute ammonia solution that mass concentration is 0.39%.Then under rapid mixing conditions, the dimethyl sulfoxide (DMSO) mixed solution of described zinc nitrate and polyacrylonitrile is slowly added drop-wise in described dilute ammonia solution, time for adding is 20min, dropwising continuation stirring 30min makes it fully react, leave standstill 12h afterwards, product is filtered, washing 3 times, obtain zinc hydroxide nano particle at 60 DEG C after drying and be dispersed in zinc hydroxide/polyacrylonitrile complex microsphere in polyacrylonitrile.Finally by gained nanometer zinc hydroxide/polyacrylonitrile complex microsphere 240 DEG C of roasting 60min in a nitrogen atmosphere, obtain nano zine oxide/cyclization polyacrylonitrile composite microsphere material.Experiment records, and the nano zine oxide prepared by the present embodiment/cyclization polyacrylonitrile composite microsphere material is that catalyst reaches 91.9% when radiation of visible light 60min to the degradation rate of 20mg/L methyl orange.
Embodiment 3
Take polyacrylonitrile solid 1.00g to be dissolved in completely in dimethyl sulfoxide (DMSO), be made into the polyacrylonitrile dimethyl sulphoxide solution of 50mL, separately getting zinc nitrate hexahydrate solid 2.00g is dissolved in 5.0mL dimethyl sulfoxide (DMSO), then pipette above-mentioned polyacrylonitrile dimethyl sulphoxide solution 27.0mL to mix with zinc nitrate dimethyl sulphoxide solution, obtain the dimethyl sulfoxide (DMSO) mixed solution of zinc nitrate and polyacrylonitrile.By ammonia density be again 25% ammonia spirit 2.20g distill dilution with water at 320mL, be made into the dilute ammonia solution that mass concentration is 0.17%.Then under rapid mixing conditions, the dimethyl sulfoxide (DMSO) mixed solution of described zinc nitrate and polyacrylonitrile is slowly added drop-wise in described dilute ammonia solution, time for adding is 25min, dropwise and continue to stir 30min, leave standstill 10h afterwards, product is filtered, washing 3 times, obtain zinc hydroxide nano particle at 60 DEG C after drying and be dispersed in zinc hydroxide/polyacrylonitrile complex microsphere in polyacrylonitrile.Finally by gained nanometer zinc hydroxide/polyacrylonitrile complex microsphere 250 DEG C of roasting 90min in a nitrogen atmosphere, make polyacrylonitrile cyclisation form conjugated structure, obtain nano zine oxide/cyclization polyacrylonitrile composite microsphere material.Experiment records, and the nano zine oxide prepared by the present embodiment/cyclization polyacrylonitrile composite microsphere material is that catalyst reaches 92.0% when radiation of visible light 60min to the degradation rate of 20mg/L methyl orange.
Embodiment 4
Take polyacrylonitrile solid 1.00g to be dissolved in completely in dimethyl sulfoxide (DMSO), be made into the polyacrylonitrile dimethyl sulphoxide solution of 50mL, separately getting zinc nitrate hexahydrate solid 2.00g is dissolved in 5.0mL dimethyl sulfoxide (DMSO), then pipette above-mentioned polyacrylonitrile dimethyl sulphoxide solution 27.0mL to mix with zinc nitrate dimethyl sulphoxide solution, obtain the dimethyl sulfoxide (DMSO) mixed solution of zinc nitrate and polyacrylonitrile.By ammonia density be again 25% ammonia spirit 2.20g distill dilution with water at 480mL, be made into the dilute ammonia solution that mass concentration is 0.115%.Then under rapid mixing conditions, the dimethyl sulfoxide (DMSO) mixed solution of described zinc nitrate and polyacrylonitrile is slowly added drop-wise in described dilute ammonia solution, time for adding is 30min, dropwise and continue to stir 40min, leave standstill 10h afterwards, product is filtered, washing 3 times, obtain zinc hydroxide nano particle at 60 DEG C after drying and be dispersed in zinc hydroxide/polyacrylonitrile complex microsphere in polyacrylonitrile.Finally by gained nanometer zinc hydroxide/polyacrylonitrile complex microsphere 250 DEG C of roasting 60min in a nitrogen atmosphere, make polyacrylonitrile cyclisation form conjugated structure, obtain nano zine oxide/cyclization polyacrylonitrile composite microsphere material.Experiment records, and the nano zine oxide prepared by the present embodiment/cyclization polyacrylonitrile composite microsphere material is that catalyst reaches 95.4% when radiation of visible light 60min to the degradation rate of 20mg/L methyl orange.
Claims (8)
1. zinc oxide nano-particle is uniformly distributed in a preparation method for the nano zine oxide/cyclization polyacrylonitrile composite microsphere material in polymer, it is characterized in that comprising the steps:
A. polyacrylonitrile is dissolved in dimethyl sulfoxide (DMSO) completely and is made into the dimethyl sulphoxide solution that polyacrylonitrile mass concentration is 20.0g/L; Separately get zinc nitrate hexahydrate solid to be dissolved in dimethyl sulfoxide solvent and to obtain the dimethyl sulphoxide solution that zinc nitrate concentration is 1.3mol/L ~ 1.4mol/L; Concentrated ammonia solution is made at distillation dilution with water the ammonia spirit that ammonia density is 0.1% ~ 0.4%;
B. get the dimethyl sulphoxide solution 5.0mL of zinc nitrate described in step a, the dimethyl sulphoxide solution 9.0mL ~ 27.0mL of polyacrylonitrile described in removing step a, airtightly to mix, obtain zinc nitrate and polyacrylonitrile dimethyl sulfoxide (DMSO) mixed solution;
C. zinc nitrate described in step b and polyacrylonitrile dimethyl sulfoxide (DMSO) mixed solution are slowly added drop-wise in ammonia spirit described in step a, the volume ratio controlling dimethyl sulfoxide (DMSO) mixed solution and ammonia spirit is 1:10 ~ 1:20, time for adding is 20min ~ 40min, dropwise rear continuation and stir 20min ~ 40min, leave standstill 8h ~ 12h afterwards, product is filtered, washing 3 times, after drying zinc hydroxide nano particle is evenly distributed on nanometer zinc hydroxide/polyacrylonitrile complex microsphere in polyacrylonitrile;
D. by step c gained nanometer zinc hydroxide/polyacrylonitrile complex microsphere in a nitrogen atmosphere in 230 DEG C ~ 260 DEG C roasting 30min ~ 120min, obtain nano zine oxide/cyclization polyacrylonitrile composite microsphere material.
2. a kind of zinc oxide nano-particle as claimed in claim 1 is uniformly distributed in the preparation method of the nano zine oxide/cyclization polyacrylonitrile composite microsphere material in polymer, it is characterized in that, in step b, the mass ratio of zinc nitrate and polyacrylonitrile is 2:1 ~ 8:1.
3. a kind of zinc oxide nano-particle as claimed in claim 1 is uniformly distributed in the preparation method of the nano zine oxide/cyclization polyacrylonitrile composite microsphere material in polymer, it is characterized in that, in step c, the volume ratio of dimethyl sulfoxide (DMSO) mixed solution and ammonia spirit is 1:10 ~ 1:15.
4. a kind of zinc oxide nano-particle as claimed in claim 1 is uniformly distributed in the preparation method of the nano zine oxide/cyclization polyacrylonitrile composite microsphere material in polymer, it is characterized in that, in step c, the mol ratio of ammonia and zinc nitrate is 4:1 ~ 5:1.
5. a kind of zinc oxide nano-particle as claimed in claim 1 is uniformly distributed in the preparation method of the nano zine oxide/cyclization polyacrylonitrile composite microsphere material in polymer, it is characterized in that, nanometer zinc hydroxide described in steps d/polyacrylonitrile complex microsphere sintering temperature is 240 DEG C ~ 250 DEG C, and roasting time is 30min ~ 90min.
6. a kind of zinc oxide nano-particle as claimed in claim 1 is uniformly distributed in the preparation method of the nano zine oxide/cyclization polyacrylonitrile composite microsphere material in polymer, it is characterized in that, when zinc nitrate and polyacrylonitrile dimethyl sulfoxide (DMSO) mixed solution instill in dilute ammonia solution, while polyacrylonitrile is condensed into microballoon, zinc ion and hydroxide ion react in-situ preparation zinc hydroxide, zinc hydroxide nano particle is made to be uniformly distributed in polyacrylonitrile microballoon, roasting under nitrogen atmosphere again, zinc hydroxide is decomposed into zinc oxide polyacrylonitrile reaction simultaneously and generates the cyclization polyacrylonitrile with conjugated structure, obtain zinc oxide nano-particle equally distributed nano zine oxide/cyclization polyacrylonitrile composite microsphere material, wherein the mass ratio of polyacrylonitrile and zinc oxide is 1:1 ~ 1:3.
7. zinc oxide nano-particle as claimed in claim 1 is uniformly distributed in the preparation method of the nano zine oxide/cyclization polyacrylonitrile composite microsphere material in polymer, it is characterized in that comprising following concrete steps:
A. 1.00g polyacrylonitrile is dissolved in completely in 50mL dimethyl sulfoxide (DMSO) and obtains polyacrylonitrile dimethyl sulphoxide solution; Separately get zinc nitrate hexahydrate solid 2.00g and be dissolved in the dimethyl sulphoxide solution obtaining zinc nitrate in 5.0mL dimethyl sulfoxide (DMSO);
B. get the dimethyl sulphoxide solution 5.0mL of zinc nitrate described in step a, the dimethyl sulphoxide solution 9.0mL ~ 27.0mL of polyacrylonitrile described in removing step a, airtightly to mix, obtain zinc nitrate and polyacrylonitrile dimethyl sulfoxide (DMSO) mixed solution;
C. be that the ammonia spirit 2.20g of 25% is at distillation dilution with water by ammonia density, the volume ratio of dimethyl sulfoxide (DMSO) mixed solution described in gained dilute ammonia solution and step b is made to be 10:1, zinc nitrate described in step b and polyacrylonitrile dimethyl sulfoxide (DMSO) mixed solution are slowly added drop-wise in described ammonia spirit under agitation, time for adding is 20min ~ 30min, dropwise rear continuation and stir 30min ~ 40min, leave standstill 8h ~ 12h afterwards, product is filtered, washing, obtain zinc hydroxide nano particle after drying and be evenly distributed on nanometer zinc hydroxide/polyacrylonitrile complex microsphere in polyacrylonitrile,
D. by step c gained nanometer zinc hydroxide/polyacrylonitrile complex microsphere 240 DEG C in a nitrogen atmosphere ~ 250 DEG C roasting 30min ~ 90min, nano zine oxide/cyclization polyacrylonitrile composite microsphere material is obtained.
8. zinc oxide nano-particle as claimed in claim 1 is uniformly distributed in the preparation method of the nano zine oxide/cyclization polyacrylonitrile composite microsphere material in polymer, it is characterized in that comprising following concrete steps:
Take polyacrylonitrile solid 1.00g to be dissolved in completely in dimethyl sulfoxide (DMSO), be made into the polyacrylonitrile dimethyl sulphoxide solution of 50mL, separately getting zinc nitrate hexahydrate solid 2.00g is dissolved in 5.0mL dimethyl sulfoxide (DMSO), then pipette above-mentioned polyacrylonitrile dimethyl sulphoxide solution 27.0mL to mix with zinc nitrate dimethyl sulphoxide solution, obtain the dimethyl sulfoxide (DMSO) mixed solution of zinc nitrate and polyacrylonitrile.By ammonia density be again 25% ammonia spirit 2.20g distill dilution with water at 320mL, be made into the dilute ammonia solution that mass concentration is 0.17%.Then under rapid mixing conditions, the dimethyl sulfoxide (DMSO) mixed solution of described zinc nitrate and polyacrylonitrile is slowly added drop-wise in described dilute ammonia solution, time for adding is 30min, dropwise and continue to stir 30min, leave standstill 12h afterwards, product is filtered, washing 3 times, obtain zinc hydroxide nano particle at 60 DEG C after drying and be dispersed in zinc hydroxide/polyacrylonitrile complex microsphere in polyacrylonitrile.Finally by gained nanometer zinc hydroxide/polyacrylonitrile complex microsphere 250 DEG C of roasting 60min in a nitrogen atmosphere, obtain nano zine oxide/cyclization polyacrylonitrile composite microsphere material.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109939651A (en) * | 2018-12-31 | 2019-06-28 | 邯郸派瑞电器有限公司 | A kind of ZnO/PAN composite material, preparation method and application |
| CN110240670A (en) * | 2019-06-19 | 2019-09-17 | 河北科技大学 | A kind of preparation method of the polyacrylonitrile with spherical microscopic appearance |
| CN115364865A (en) * | 2022-08-11 | 2022-11-22 | 株洲安特新材料科技有限公司 | Preparation and modification method of nano zinc oxide catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59163715A (en) * | 1983-03-08 | 1984-09-14 | 三菱電機株式会社 | Method of producing electrodeposited insulated wire |
| CN102451762A (en) * | 2010-11-01 | 2012-05-16 | 上海大学 | Preparation method of cyclizing polyacrylonitrile compound multi-metal oxide |
| CN102908961A (en) * | 2012-09-10 | 2013-02-06 | 上海交通大学医学院附属新华医院 | Functional nanometer particle composite non-crosslinking microspheres and preparation method and application thereof |
-
2015
- 2015-09-02 CN CN201510555529.4A patent/CN105056998B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59163715A (en) * | 1983-03-08 | 1984-09-14 | 三菱電機株式会社 | Method of producing electrodeposited insulated wire |
| CN102451762A (en) * | 2010-11-01 | 2012-05-16 | 上海大学 | Preparation method of cyclizing polyacrylonitrile compound multi-metal oxide |
| CN102908961A (en) * | 2012-09-10 | 2013-02-06 | 上海交通大学医学院附属新华医院 | Functional nanometer particle composite non-crosslinking microspheres and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| JI SUN IM等: "Preparation of PAN-based electrospun nanofiber webs containing TiO2 for photocatalytic degradation", 《MATERIALS LETTERS》 * |
| 李跃军: "ZnO/PAN 亚微米复合纤维的制备及光催化性能", 《无机化学学报》 * |
| 李雪艳等: "ZnO/环化聚丙烯腈纳米复合微粒的光催化活性研究", 《中国化学会第十五届胶体与界面化学会议论文集（第二分会）》 * |
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| CN109939651A (en) * | 2018-12-31 | 2019-06-28 | 邯郸派瑞电器有限公司 | A kind of ZnO/PAN composite material, preparation method and application |
| CN110240670A (en) * | 2019-06-19 | 2019-09-17 | 河北科技大学 | A kind of preparation method of the polyacrylonitrile with spherical microscopic appearance |
| CN110240670B (en) * | 2019-06-19 | 2021-07-20 | 河北科技大学 | Preparation method of polyacrylonitrile with spherical micro-morphology |
| CN115364865A (en) * | 2022-08-11 | 2022-11-22 | 株洲安特新材料科技有限公司 | Preparation and modification method of nano zinc oxide catalyst |
| CN115364865B (en) * | 2022-08-11 | 2023-06-20 | 株洲安特新材料科技有限公司 | Preparation and modification methods of nano zinc oxide catalyst |
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