CN105056998B - A kind of zinc oxide nano-particle is uniformly distributed in the preparation method of nano zine oxide/cyclization polyacrylonitrile composite microsphere material in polymer - Google Patents
A kind of zinc oxide nano-particle is uniformly distributed in the preparation method of nano zine oxide/cyclization polyacrylonitrile composite microsphere material in polymer Download PDFInfo
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Abstract
A kind of preparation method for the nano zine oxide/cyclization polyacrylonitrile composite microsphere material being uniformly distributed in the invention discloses zinc oxide nano-particle in polymer, belongs to depollution of environment photochemical catalyst new material technology field.First by polyacrylonitrile and zinc nitrate solid dissolving in dimethyl sulfoxide solvent, then the mixed solution is slowly dropped into dilute ammonia solution, zinc nitrate reacts in-situ preparation zinc hydroxide with hydroxide ion while polyacrylonitrile is condensed into microballoon in water, the complex microsphere that zinc hydroxide nano-particle is dispersed in polyacrylonitrile is obtained, roasting can obtain nano zine oxide/cyclization polyacrylonitrile composite microsphere material under separating, washing, drying, inert gas afterwards.It is an advantage of the current invention that preparation method is simple, without complex device, polyacrylonitrile used is cheap and easy to get, and zinc oxide nano-particle is dispersed in cyclization polyacrylonitrile microballoon, and obtained composite microsphere material has excellent visible light catalysis activity.
Description
Technical field
Nano zine oxide/the cyclisation being uniformly distributed in present invention relates particularly to a kind of zinc oxide nano-particle in polymer gathers
The preparation method of acrylonitrile composite microsphere material, 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 most development potentiality and application
The elimination environmental contaminants of prospect, the green technology for solving energy crisis.It is nano oxidized in numerous conductor photocatalysis materials
Zinc is because having the advantages that photohole oxidability is strong, catalytic activity is high, chemical stability good, cost is low, nontoxic, wide material sources
And receive much concern.But zinc oxide is wide bandgap semiconductor, photocatalysis, and its photoproduction electricity can only be produced by ultraviolet excitation
Son/hole-recombination probability is higher, seriously constrains zinc oxide as the practical application of photochemical catalyst.In order to solve the above problems,
Current lot of domestic and foreign researcher is adjusted by number of ways such as nano zine oxide crystal formation, crystal face, pattern, size, metal ion
Or nonmetal doping, noble metal loading, semiconductors coupling etc. is modified to photocatalyst of zinc oxide, and electricity is improved to reach
Son/hole separative efficiency, the purpose for widening absorption spectrum ranges.
Recent studies indicate that, compound using the carbon material with conjugated structure and nano zine oxide is that to improve its visible
The effective way of photocatalytic activity.Using in zinc oxide nano-particle surface recombination football alkene (C60) such as Zhu Yongfa
(Environmental Science and Technology,2008,42：8064–8069)；Fu Li etc. use hydro-thermal legal system
Standby reduced graphene/zinc oxide composite photocatalyst (Ceramics International, 2015,41：4007–4013)；
Chen Daimei etc. pass through mesoporous carbonitride (mg-C3N4) and zinc oxide (ZnO) particle ultrasonic disperse in methyl alcohol be made
ZnO@mpg-C3N4Composite photo-catalyst (Applied Catalysis B:Environmental, 2014,147：554–561)；
Liu Ping etc. are by cold plasma treatment technology and chemical deposition in zinc oxide nano-particle Surface coating monolayer
Polyaniline (PANI) (Journal of Physical Chemistry C, 2014,118:9570-9577), this is as a result shown
A little methods significantly improve the photocatalytic activity of gained composite photo-catalyst, and photocatalytic activity improves degree and existed with carbon material
The cladding degree on zinc oxide particles surface is closely related.But football alkene (C60) molecule is spherical, graphene in above-mentioned carbon material
And carbonitride is lamellar structure, molecule chain rigidity is larger, with zinc oxide particles compound tense, it is difficult to which zinc oxide particles are complete, tight
Thickly wrap up, and the lamella number of plies of graphene and carbonitride is difficult to effective control in liquid medium, causes zinc oxide
The thickness and distribution of surface graphene or carbonitride are difficult to control to.And the shortcoming of polyaniline is water insoluble and general molten
Agent, its molecular weight and the more difficult control of compound uniformity coefficient, are unsuitable for a large amount of production and applications.In addition, using well prepared in advance
When zinc oxide particles carry out surface recombination, also it is difficult to thoroughly solve zinc oxide nano-particle because of surface energy even if ultrasonic disperse is carried out
Agglomeration traits caused by height, this will necessarily influence distributing homogeneity of the zinc oxide in compound, and then influence composite
Photocatalysis performance.
The content of the invention
The present invention is uniformly distributed in polymer to solve the problems of the prior art there is provided a kind of zinc oxide nano-particle
Nano zine oxide/cyclization polyacrylonitrile composite microsphere material preparation method.It is original i.e. using general polymer polyacrylonitrile
Expect that modified nano zinc oxide prepares efficient visible light catalyst.
The thinking of the present invention is that the dimethyl sulfoxide (DMSO) mixed solution containing polyacrylonitrile and zinc nitrate is slowly dropped into dilute ammonia
In the aqueous solution, zinc nitrate and hydroxide ion reaction in the aqueous solution are in situ raw while polyacrylonitrile is condensed into microballoon in water
Into zinc hydroxide nano-particle, the complex microsphere that zinc hydroxide uniform particle is dispersed in polyacrylonitrile is obtained, then through indifferent gas
Roasting obtains nano zine oxide/cyclization polyacrylonitrile composite microsphere material under body.
Technical scheme mainly comprises the steps：.
A. polyacrylonitrile is dissolved in dimethyl sulfoxide solvent, polyacrylonitrile mass concentration is made into after being completely dissolved is
20.0g/L dimethyl sulphoxide solution；Separately take zinc nitrate hexahydrate (Zn (NO3)2·6H2O) solid is dissolved in dimethyl sulfoxide solvent
In obtain nitric acid zinc concentration be 1.3mol/L~1.4mol/L dimethyl sulphoxide solution；By concentrated ammonia solution in distilled water it is dilute
Release the ammonia spirit for being made into that ammonia density is 0.1%~0.4%；
B. the dimethyl sulphoxide solution 5.0mL of zinc nitrate described in step a is taken, the diformazan of polyacrylonitrile described in removing step a
Base sulfoxide solution 9.0mL~27.0mL, it is closed well mixed, 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 dropped to ammonia described in step a
In the aqueous solution, the volume ratio for controlling dimethyl sulfoxide (DMSO) mixed solution and ammonia spirit is 1:10~1:20, time for adding is 20min
Continue to stir 20min~40min after~40min, completion of dropping, 8h~12h is stood afterwards, product is filtered, washed 3 times, is done
Nanometer zinc hydroxide/polyacrylonitrile complex microsphere that zinc hydroxide nano-particle is evenly distributed in polyacrylonitrile is obtained after dry；
D. by nanometer zinc hydroxide/polyacrylonitrile complex microsphere obtained by step c in a nitrogen atmosphere in 230 DEG C~260 DEG C
30min~120min is calcined, nano zine oxide/cyclization polyacrylonitrile composite microsphere material is obtained.
It is preferred that, the mass ratio of zinc nitrate and polyacrylonitrile is 2 in step b:1~8:1.
It is preferred that, the mol ratio of ammonia and zinc nitrate is 4 in step c:1~5:1.
It is preferred that, the volume ratio of dimethyl sulfoxide (DMSO) mixed solution and ammonia spirit is 1 in step c:10~1:15.
It is preferred that, nanometer zinc hydroxide/polyacrylonitrile complex microsphere sintering temperature described in step d is 240 DEG C~250
DEG C, roasting time is 30min~90min.
It is preferred that, the mass ratio of polyacrylonitrile and zinc oxide in nano zine oxide/cyclization polyacrylonitrile composite microsphere material
For 1:1~1:3.
The outstanding advantages that have compared with prior art of the present invention are：
(1) conjugated structure polymer is prepared by raw material of general polymer polyacrylonitrile, it is cheap and easy to get, and polymerization process and
Polymer molecular weight is easily controlled；
(2) zinc oxide nano-particle can be made to be uniformly distributed in cyclization polyacrylonitrile microballoon, it is to avoid the zinc oxide nano grain of rice
Influence of the reunion of son to photocatalytic activity, the preparation method is simple, it is not necessary to complex device, is suitable for industrialized production；
(3) nano zine oxide/cyclization polyacrylonitrile composite microsphere material prepared by absorbs in visible region to be significantly improved,
With excellent visible light catalysis activity.
Brief description of the drawings
Fig. 1 is the nano zine oxide/cyclization polyacrylonitrile complex microsphere X ray diffracting spectrum and oxygen prepared by embodiment 1
Change zinc standard X-ray diffraction collection of illustrative plates；
Fig. 2 is in polyacrylonitrile and nano zine oxide/cyclization polyacrylonitrile composite microsphere material Fu prepared by embodiment 1
Leaf transformation infrared spectrum；
Fig. 3 is nano zine oxide/cyclization polyacrylonitrile composite microsphere material scanning electron microscope (SEM) photograph prepared by embodiment 1；
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 map in nano zine oxide/cyclization polyacrylonitrile complex microsphere grain material；
Fig. 8 makes under the nano zine oxide/cyclization polyacrylonitrile composite microsphere material and the same terms prepared by embodiment 1
The UV-Vis DRS of standby zinc oxide absorbs spectrogram；
Fig. 9 makes under the nano zine oxide/cyclization polyacrylonitrile composite microsphere material and the same terms prepared by embodiment 1
Standby zinc oxide visible light photocatalytic degradation methyl orange situation.
Embodiment
Embodiment 1
Weigh polyacrylonitrile solid 1.00g to be dissolved completely in dimethyl sulfoxide (DMSO), be made into 50mL polyacrylonitrile dimethyl
Sulfoxide solution, separately takes zinc nitrate hexahydrate solid 2.00g to be dissolved in 5.0mL dimethyl sulfoxide (DMSO)s, then pipettes above-mentioned polyacrylonitrile
Dimethyl sulphoxide solution 27.0mL is well mixed with zinc nitrate dimethyl sulphoxide solution, obtains the diformazan of zinc nitrate and polyacrylonitrile
Base sulfoxide mixed solution.Ammonia density is diluted for 25% ammonia spirit 2.20g in 320mL distilled water again, quality is made into dense
Spend the dilute ammonia solution for 0.17%.Then by the zinc nitrate and the dimethyl sulfoxide (DMSO) of polyacrylonitrile under rapid mixing conditions
Mixed solution is slowly dropped in the dilute ammonia solution, and time for adding is 30min, and completion of dropping continues to stir 30min, afterwards
12h is stood, product is filtered, wash at 3 times, 60 DEG C and to be obtained zinc hydroxide nano-particle after drying and be dispersed in polyacrylonitrile
In zinc hydroxide/polyacrylonitrile complex microsphere.Finally by gained nanometer zinc hydroxide/polyacrylonitrile complex microsphere in nitrogen gas
The lower 250 DEG C of roastings 60min of atmosphere, obtains nano zine oxide/cyclization polyacrylonitrile composite microsphere material.
X ray diffracting spectrum such as Fig. 1 of nano zine oxide prepared by the present embodiment/cyclization polyacrylonitrile composite microsphere material
Shown in middle spectral line (a), it can be seen that nano zine oxide prepared by this method/cyclization polyacrylonitrile composite microsphere material exists
31.78 °, 34.43 °, 36.27 °, 47.54 ° etc. there is diffraction maximum, with the zinc oxide standard of hexagonal wurtzite type shown in spectral line (b)
X ray diffracting spectrum (PDF#01-089-0510) correspondence completely, it is hexagonal wurtzite type to illustrate prepared nano zine oxide.Fig. 2
For polyacrylonitrile and the Fourier transform infrared spectrogram of prepared nano zine oxide/cyclization polyacrylonitrile composite microsphere material,
Spectral line a is polyacrylonitrile Fourier transform infrared spectrogram in figure, and spectral line b is nano zine oxide/cyclization polyacrylonitrile complex microsphere
Material Fourier transform infrared spectrogram.Wave number is in 400cm in spectral line b-1~500cm-1Between absworption peak be zinc oxide signature peaks,
By spectral line b and polyacrylonitrile infrared spectrum, (spectral line a) is contrasted it can be found that spectral line b is in 2245cm-1Locate itrile group (- C ≡ N) vibration
Peak substantially weakens, and in wave number 1580cm-1、1610cm-1Place occurs belonging to carbon-to-nitrogen double bon (- C=N -), carbon-carbon double bond (- C=
C -) relatively strong absworption peak, and 1455cm-1Hydrocarbon (C-H) flexural vibrations peak in place is moved to lower wave number, shown in composite microsphere material
Polyacrylonitrile after heat treatment forms the cyclization polyacrylonitrile with-C=C-C=N-conjugated structure.Receiving prepared by embodiment 1
Rice zinc oxide/cyclization polyacrylonitrile composite microsphere material ESEM is illustrated in Fig. 3, it can be seen that prepared is nano oxidized
Zinc/cyclization polyacrylonitrile complex microsphere particle diameter distribution is more uniform, about 30nm~50nm.Fig. 4 is nano zine oxide/cyclisation poly- third
Zn-ef ficiency distribution map in alkene nitrile complex microsphere grain material, Fig. 5 is in nano zine oxide/cyclization polyacrylonitrile complex microsphere grain material
Oxygen element distribution map, Fig. 6 is carbon distribution map in nano zine oxide/cyclization polyacrylonitrile complex microsphere grain material, and Fig. 7 is to receive
Nitrogen distribution map, the prepared material it can be seen from Fig. 4~Fig. 7 in rice zinc oxide/cyclization polyacrylonitrile complex microsphere grain material
Equally distributed state, zinc, oxygen element distribution density is all being presented in oxygen, zinc, carbon, four kinds of elements of nitrogen substantially within sweep of the eye in material
Approximately, zinc oxide (ZnO) is belonged to, carbon belongs to cyclization polyacrylonitrile with nitrogen, due in polyacrylonitrile strand
Carbon and nitrogen atoms ratio is 3:1, therefore nitrogen distribution density is relatively small.Fig. 4~Fig. 7, which demonstrates method therefor of the present invention, can make to receive
Rice zinc oxide is uniformly distributed in cyclization polyacrylonitrile microballoon, has reached the equally distributed purpose of zinc oxide in composite.By
The zinc oxide prepared under prepared nano zine oxide/cyclization polyacrylonitrile composite microsphere material and the same terms that Fig. 8 is shown
UV-Vis DRS absorb nano zine oxide/cyclization polyacrylonitrile for can be seen that prepared by the present invention of spectrogram be combined it is micro-
Ball material is above the zinc oxide prepared under the same terms (such as in the absorption (as shown in curve a) of whole spectral region interior focusing
Shown in curve b).
The photocatalysis performance test of prepared nano zine oxide/cyclization polyacrylonitrile composite microsphere material is as follows：Anti-
The methyl orange solution that photochemical catalyst prepared by 0.12g and 120g concentration are added in device for 20mg/L is answered, is stirred under dark condition
2.0h is reached after adsorption equilibrium, opens visible light source (the 300W iodine-tungsten lamps of capping optical filter) irradiation, in a certain time interval
Sampled from reaction system, be centrifuged after catalyst, take supernatant liquor spectrophotometer in methyl orange maximum absorption wave
Absorbance is determined under long 464nm, the change in concentration situation of methyl orange in solution is obtained by working curve, absorption before illumination is reached flat
The concentration of methyl orange is designated as c during weighing apparatus0, methyl orange concentration is designated as c during illumination different timet, illumination degrading methyl orange can be calculated
Degradation rate D/%=(c0-ct)/c0× 100%, so as to draw the catalytic activity of photochemical catalyst.Fig. 9 is prepared by embodiment 1
The zinc oxide visible light photocatalytic degradation methyl prepared under nano zine oxide/cyclization polyacrylonitrile composite microsphere material and the same terms
Orange situation.Experimental result is understood as shown in Figure 9, and pure zinc oxide is that catalyst is only 1.7% (such as Fig. 9 to the degradation rate of methyl orange
Shown in curve b), substantially without visible light catalysis activity, and nano zine oxide/cyclization polyacrylonitrile prepared by the present embodiment is multiple
It is that catalyst reaches 94.9% (such as Fig. 9 songs in radiation of visible light 60min to the degradation rate of 20mg/L methyl oranges to close micro-sphere material
Shown in line a), it is seen that photocatalysis performance highly significant.
Embodiment 2
Weigh polyacrylonitrile solid 1.00g to be dissolved in 50mL dimethyl sulfoxide solvents, separately take zinc nitrate hexahydrate solid 2.00g
It is dissolved in 5.0mL dimethyl sulfoxide solvents, then pipettes the two of polyacrylonitrile dimethyl sulphoxide solution 9.0mL and above-mentioned zinc nitrate
Methyl sulfoxide solution is closed well mixed, obtains zinc nitrate and polyacrylonitrile dimethyl sulfoxide (DMSO) mixed solution.It is by ammonia density again
25% ammonia spirit 2.20g dilutes in 140mL distilled water, is made into the dilute ammonia solution that mass concentration is 0.39%.Then
The dimethyl sulfoxide (DMSO) mixed solution of the zinc nitrate and polyacrylonitrile is slowly dropped to dilute ammonia under rapid mixing conditions
In the aqueous solution, time for adding is 20min, and completion of dropping, which continues stirring 30min, makes it fully react, and 12h is stood afterwards, by product
Obtained after being dried at filtering, washing 3 times, 60 DEG C zinc hydroxide that zinc hydroxide nano-particle is dispersed in polyacrylonitrile/
Polyacrylonitrile complex microsphere.Finally by the 240 DEG C of roastings in a nitrogen atmosphere of gained nanometer zinc hydroxide/polyacrylonitrile complex microsphere
60min, obtains nano zine oxide/cyclization polyacrylonitrile composite microsphere material.Experiment is measured, the nano oxygen prepared by the present embodiment
Change zinc/cyclization polyacrylonitrile composite microsphere material is degraded of the catalyst in radiation of visible light 60min to 20mg/L methyl oranges
Rate reaches 91.9%.
Embodiment 3
Weigh polyacrylonitrile solid 1.00g to be dissolved completely in dimethyl sulfoxide (DMSO), be made into 50mL polyacrylonitrile dimethyl
Sulfoxide solution, separately takes zinc nitrate hexahydrate solid 2.00g to be dissolved in 5.0mL dimethyl sulfoxide (DMSO)s, then pipettes above-mentioned polyacrylonitrile
Dimethyl sulphoxide solution 27.0mL is well mixed with zinc nitrate dimethyl sulphoxide solution, obtains the diformazan of zinc nitrate and polyacrylonitrile
Base sulfoxide mixed solution.Ammonia density is diluted for 25% ammonia spirit 2.20g in 320mL distilled water again, quality is made into dense
Spend the dilute ammonia solution for 0.17%.Then by the zinc nitrate and the dimethyl sulfoxide (DMSO) of polyacrylonitrile under rapid mixing conditions
Mixed solution is slowly dropped in the dilute ammonia solution, and time for adding is 25min, and completion of dropping continues to stir 30min, afterwards
10h is stood, product is filtered, wash at 3 times, 60 DEG C and to be obtained zinc hydroxide nano-particle after drying and be dispersed in polyacrylonitrile
In zinc hydroxide/polyacrylonitrile complex microsphere.Finally by gained nanometer zinc hydroxide/polyacrylonitrile complex microsphere in nitrogen gas
The lower 250 DEG C of roastings 90min of atmosphere, makes polyacrylonitrile be cyclized to form conjugated structure, obtains nano zine oxide/cyclization polyacrylonitrile and be combined
Micro-sphere material.Experiment is measured, and the nano zine oxide prepared by the present embodiment/cyclization polyacrylonitrile composite microsphere material is catalyst
92.0% is reached to the degradation rate of 20mg/L methyl oranges in radiation of visible light 60min.
Embodiment 4
Weigh polyacrylonitrile solid 1.00g to be dissolved completely in dimethyl sulfoxide (DMSO), be made into 50mL polyacrylonitrile dimethyl
Sulfoxide solution, separately takes zinc nitrate hexahydrate solid 2.00g to be dissolved in 5.0mL dimethyl sulfoxide (DMSO)s, then pipettes above-mentioned polyacrylonitrile
Dimethyl sulphoxide solution 27.0mL is well mixed with zinc nitrate dimethyl sulphoxide solution, obtains the diformazan of zinc nitrate and polyacrylonitrile
Base sulfoxide mixed solution.Ammonia density is diluted for 25% ammonia spirit 2.20g in 480mL distilled water again, quality is made into dense
Spend the dilute ammonia solution for 0.115%.Then it is under rapid mixing conditions that the dimethyl of the zinc nitrate and polyacrylonitrile is sub-
Sulfone mixed solution is slowly dropped in the dilute ammonia solution, and time for adding is 30min, and completion of dropping continues to stir 40min, it
After stand 10h, product is filtered, wash dried at 3 times, 60 DEG C after obtain zinc hydroxide nano-particle and be dispersed in polypropylene
Zinc hydroxide/polyacrylonitrile complex microsphere in nitrile.Finally by gained nanometer zinc hydroxide/polyacrylonitrile complex microsphere in nitrogen
The lower 250 DEG C of roastings 60min of atmosphere, makes polyacrylonitrile be cyclized to form conjugated structure, obtains nano zine oxide/cyclization polyacrylonitrile multiple
Close micro-sphere material.Experiment is measured, and the nano zine oxide prepared by the present embodiment/cyclization polyacrylonitrile composite microsphere material is catalysis
Agent reaches 95.4% in radiation of visible light 60min to the degradation rate of 20mg/L methyl oranges.
Claims (6)
1. a kind of zinc oxide nano-particle is uniformly distributed in nano zine oxide/cyclization polyacrylonitrile complex microsphere material in polymer
The preparation method of material, it is characterised in that comprise the steps：
A., polyacrylonitrile is dissolved completely in the dimethyl Asia for being made into that polyacrylonitrile mass concentration is 20.0g/L in dimethyl sulfoxide (DMSO)
Sulfolane solution；It is another take zinc nitrate hexahydrate solid be dissolved in dimethyl sulfoxide solvent obtain nitric acid zinc concentration for 1.3mol/L~
1.4mol/L dimethyl sulphoxide solution；Concentrated ammonia solution dilutes in distilled water to be made into ammonia density be 0.1%~0.4%
Ammonia spirit；
B. the dimethyl sulphoxide solution 5.0mL of zinc nitrate described in step a is taken, the dimethyl of polyacrylonitrile described in removing step a is sub-
Sulfolane solution 9.0mL~27.0mL, it is closed well mixed, obtain zinc nitrate and polyacrylonitrile dimethyl sulfoxide (DMSO) mixed solution；It is described
The mass ratio of zinc nitrate and polyacrylonitrile is 2:1~8:1；
C. zinc nitrate described in step b and polyacrylonitrile dimethyl sulfoxide (DMSO) mixed solution are slowly dropped to ammoniacal liquor described in step a molten
In liquid, the volume ratio for controlling dimethyl sulfoxide (DMSO) mixed solution and ammonia spirit is 1:10~1:15, time for adding be 20min~
Continue to stir 20min~40min after 40min, completion of dropping, 8h~12h is stood afterwards, product is filtered, washed 3 times, is dried
Nanometer zinc hydroxide/polyacrylonitrile complex microsphere that zinc hydroxide nano-particle is evenly distributed in polyacrylonitrile is obtained afterwards；
D. by nanometer zinc hydroxide/polyacrylonitrile complex microsphere obtained by step c in a nitrogen atmosphere in 230 DEG C~260 DEG C roastings
30min~120min, obtains 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 nano zine oxide/cyclisation in polymer
The preparation method of polyacrylonitrile composite microsphere material, it is characterised in that the mol ratio of ammonia and zinc nitrate is 4 in step c:1~5:
1。
3. a kind of zinc oxide nano-particle as claimed in claim 1 is uniformly distributed in nano zine oxide/cyclisation in polymer
The preparation method of polyacrylonitrile composite microsphere material, it is characterised in that nanometer zinc hydroxide/polyacrylonitrile described in step d
Complex microsphere sintering temperature is 240 DEG C~250 DEG C, and roasting time is 30min~90min.
4. a kind of zinc oxide nano-particle as claimed in claim 1 is uniformly distributed in nano zine oxide/cyclisation in polymer
The preparation method of polyacrylonitrile composite microsphere material, it is characterised in that zinc nitrate and polyacrylonitrile dimethyl sulfoxide (DMSO) mixed solution
When instilling in dilute ammonia solution, zinc ion reacts in-situ preparation hydrogen-oxygen with hydroxide ion while polyacrylonitrile is condensed into microballoon
Change zinc, zinc hydroxide nano-particle is uniformly distributed in polyacrylonitrile microballoon, then through being calcined under nitrogen atmosphere, zinc hydroxide point
The cyclization polyacrylonitrile that there is conjugated structure for the zinc oxide generation of polyacrylonitrile reaction simultaneously is solved, zinc oxide nano-particle is obtained equal
The nano zine oxide of even distribution/cyclization polyacrylonitrile composite microsphere material, the wherein mass ratio of polyacrylonitrile and zinc oxide are 1:1
~1:3.
5. zinc oxide nano-particle as claimed in claim 1 is uniformly distributed in nano zine oxide/cyclisation poly- third in polymer
The preparation method of alkene nitrile composite microsphere material, it is characterised in that including step in detail below：
A. 1.00g polyacrylonitrile is dissolved completely in 50mL dimethyl sulfoxide (DMSO)s and obtains polyacrylonitrile dimethyl sulphoxide solution；Separately take
Zinc nitrate hexahydrate solid 2.00g is dissolved in the dimethyl sulphoxide solution that zinc nitrate is obtained in 5.0mL dimethyl sulfoxide (DMSO)s；
B. the dimethyl sulphoxide solution 5.0mL of zinc nitrate described in step a is taken, the dimethyl of polyacrylonitrile described in removing step a is sub-
Sulfolane solution 9.0mL~27.0mL, it is closed well mixed, obtain zinc nitrate and polyacrylonitrile dimethyl sulfoxide (DMSO) mixed solution；
C. ammonia density is diluted for 25% ammonia spirit 2.20g in distilled water, made described in gained dilute ammonia solution and step b
The volume ratio of dimethyl sulfoxide (DMSO) mixed solution is 10:1, zinc nitrate described in step b is mixed molten with polyacrylonitrile dimethyl sulfoxide (DMSO)
Liquid is slowly dropped in the ammonia spirit under agitation, and time for adding is continuation after 20min~30min, completion of dropping
Stir 30min~40min, 8h~12h stood afterwards, product is filtered, washed, dry after to obtain zinc hydroxide nano-particle equal
The even nanometer zinc hydroxide/polyacrylonitrile complex microsphere being distributed in polyacrylonitrile；
D. nanometer zinc hydroxide/240 DEG C in a nitrogen atmosphere~250 DEG C of polyacrylonitrile complex microsphere obtained by step c is calcined
30min~90min, obtains nano zine oxide/cyclization polyacrylonitrile composite microsphere material.
6. zinc oxide nano-particle as claimed in claim 1 is uniformly distributed in nano zine oxide/cyclisation poly- third in polymer
The preparation method of alkene nitrile composite microsphere material, it is characterised in that including step in detail below：
Weigh polyacrylonitrile solid 1.00g to be dissolved completely in dimethyl sulfoxide (DMSO), be made into 50mL polyacrylonitrile dimethyl sulfoxide (DMSO)
Solution, separately takes zinc nitrate hexahydrate solid 2.00g to be dissolved in 5.0mL dimethyl sulfoxide (DMSO)s, then pipettes above-mentioned polyacrylonitrile diformazan
Base sulfoxide solution 27.0mL is well mixed with zinc nitrate dimethyl sulphoxide solution, and the dimethyl for obtaining zinc nitrate and polyacrylonitrile is sub-
Sulfone mixed solution, then ammonia density is diluted for 25% ammonia spirit 2.20g in 320mL distilled water, being made into mass concentration is
0.17% dilute ammonia solution, then mixes the zinc nitrate with the dimethyl sulfoxide (DMSO) of polyacrylonitrile under rapid mixing conditions
Solution is slowly dropped in the dilute ammonia solution, and time for adding is 30min, and completion of dropping continues to stir 30min, stood afterwards
12h, product is filtered, wash dried at 3 times, 60 DEG C after obtain zinc hydroxide nano-particle and be dispersed in polyacrylonitrile
Zinc hydroxide/polyacrylonitrile complex microsphere, finally complex microsphere by gained nanometer zinc hydroxide/polyacrylonitrile in a nitrogen atmosphere
250 DEG C of roasting 60min, obtain nano zine oxide/cyclization polyacrylonitrile composite microsphere material.
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