CN110436511A - A kind of preparation method of reticular structure nano zine oxide - Google Patents
A kind of preparation method of reticular structure nano zine oxide Download PDFInfo
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- CN110436511A CN110436511A CN201910850196.6A CN201910850196A CN110436511A CN 110436511 A CN110436511 A CN 110436511A CN 201910850196 A CN201910850196 A CN 201910850196A CN 110436511 A CN110436511 A CN 110436511A
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- cellulose
- zine oxide
- reticular structure
- nano zine
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000001913 cellulose Substances 0.000 claims abstract description 59
- 229920002678 cellulose Polymers 0.000 claims abstract description 59
- ONIOAEVPMYCHKX-UHFFFAOYSA-N carbonic acid;zinc Chemical compound [Zn].OC(O)=O ONIOAEVPMYCHKX-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000001354 calcination Methods 0.000 claims abstract description 27
- 239000000725 suspension Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 22
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011591 potassium Substances 0.000 claims abstract description 22
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 22
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 22
- 239000011975 tartaric acid Substances 0.000 claims abstract description 22
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 21
- 239000004964 aerogel Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 20
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011701 zinc Substances 0.000 claims abstract description 17
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 17
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 15
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 12
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 12
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 12
- 238000004090 dissolution Methods 0.000 claims abstract description 11
- IIQJBVZYLIIMND-UHFFFAOYSA-J potassium;antimony(3+);2,3-dihydroxybutanedioate Chemical compound [K+].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O IIQJBVZYLIIMND-UHFFFAOYSA-J 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 230000010355 oscillation Effects 0.000 claims abstract description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 32
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 31
- 239000011521 glass Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 11
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 10
- 238000006073 displacement reaction Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 8
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 8
- 239000011240 wet gel Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 5
- 229910001626 barium chloride Inorganic materials 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 239000000499 gel Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000004570 mortar (masonry) Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000004448 titration Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 3
- 230000001934 delay Effects 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 238000004108 freeze drying Methods 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- 229940007424 antimony trisulfide Drugs 0.000 description 9
- NVWBARWTDVQPJD-UHFFFAOYSA-N antimony(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Sb+3].[Sb+3] NVWBARWTDVQPJD-UHFFFAOYSA-N 0.000 description 9
- 239000013078 crystal Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000009777 vacuum freeze-drying Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000005291 magnetic effect Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical compound [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003242 anti bacterial agent Substances 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
- 239000000919 ceramic Substances 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- 239000001393 triammonium citrate Substances 0.000 description 1
- 235000011046 triammonium citrate Nutrition 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Cosmetics (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a kind of preparation methods of reticular structure nano zine oxide, and the specific method is as follows: 1) being add to deionized water potassium antimony tartrate, PVP and TAA is added after dissolution, tartaric acid ladder potassium/PVP/TAA mixture solution is made；2) cellulose fento suspension is titrated in calcium chloride solution, obtained by freeze drying cellulose aerogels；3) polyethylene glycol is added in Zinc vitriol and ammonium hydrogen carbonate and is ground, obtain carbonic acid zinc nanocrystalline presoma；4) carbonic acid zinc nanocrystalline presoma is added in mixture solution, adds cellulose aerogels, the laggard expert of supersonic oscillations presses heating reaction, and then carrying out calcining again can be prepared by the nano zine oxide of reticular structure.Preparation method provided by the invention has the advantages that process conditions are easy to control and low in cost, and prepared nano zine oxide reaches nanometer scale, and has uniform Nanostructure Network, and the topographical difference of reticular structure is small, and structural stability is good.
Description
Technical field
The invention belongs to field of nanometer technology, and in particular to a kind of preparation method of reticular structure nano zine oxide.
Background technique
Nano zine oxide is a kind of new inorganic material of multifunctionality, and granular size is about at 1-100 nanometers.Due to crystalline substance
The imperceptibility of grain, Electronic Structure and crystal structure change, produce skin effect that macro object do not have,
The features such as bulk effect, quantum size effect and macroscopical tunnel-effect and the high grade of transparency, polymolecularity.Discovered in recent years it
Catalysis, optics, magnetics, mechanics etc. show many specific functions, make it in ceramics, chemical industry, electronics, optics, biology, doctor
There is important application value in many fields such as medicine, the particularity and purposes that can not compare with common zinc oxide.It is nano oxidized
Zinc can be used for ultraviolet light masking material, antibacterial agent, fluorescent material, catalysis material etc. in fields such as weaving, coating.Due to nanometer
The a series of superiority of zinc oxide and very tempting application prospect, therefore research and develop nano zine oxide and have become many scientific and technical personnel
Focus of attention.
Currently, the method for preparing nano zine oxide specifically includes that chemical deposition method, sol-gal process, microemulsion method, is sprayed
Pyrolysismethod, hydrothermal synthesis method, solid reaction process, laser-induced chemical method etc., the knot of nano zine oxide made from different methods
Structure and size and its uniformity have biggish difference, and the morphology and size of nano zine oxide and its uniformity directly affect product
Performance, the performances such as different structure, the light of various sizes of zinc oxide, electricity, magnetic have very big difference.Such as Publication No.
A kind of preparation method of novel nano zinc oxide, uses high hydroscopic resin for template disclosed in CN102774874B, using thirdly
The nano zine oxide of reticular structure is made in the characteristics of tieing up reticular structure and slow release, but this method preparation is nano oxidized
The topographical difference of zinc, Nanostructure Network is larger, and it is poor to cause to exist between the structure snd size and the uniformity of nano zine oxide
It is different, so that the performance to nano zine oxide impacts.
Summary of the invention
The purpose of the present invention is being directed to existing problem, a kind of preparation method of reticular structure nano zine oxide is provided.
The present invention is achieved by the following technical solutions:
A kind of preparation method of reticular structure nano zine oxide, which is characterized in that it is specific the preparation method is as follows:
1) potassium antimony tartrate is add to deionized water, stirs 10-15min in the case where revolving speed is 130-180r/min, fills it
Polyvinylpyrrolidone is added after dividing dissolution, continues to stir 15-20min, after its dissolution, thio second is added into mixed solution
Amide continues to stir 30-35min, obtains tartaric acid ladder potassium/PVP/TAA mixture solution；Tartaric acid ladder potassium is utilized in the application
As antimony source, TAA forms antimony trisulfide crystal grain as sulphur source, by subsequent hydro-thermal reaction；The PVP of addition can reduce antimony trisulfide
The probability mutually collided between crystal grain reduces the surface energy of antimony trisulfide crystal grain, so as to inhibit between antimony trisulfide crystal grain
Agglomeration, controls the growth of antimony trisulfide crystal grain, to help to reduce the netted of subsequent carbonic acid zinc nanocrystalline presoma cladding
The aperture of structure, so that carbonic acid zinc nanocrystalline presoma surface forms the reticular structure clad of small-bore；
2) cellulose fento suspension is placed in the large beaker equipped with ice cube, handles 30-50s under 150-180W ultrasonic wave,
After treatment stands 7-10min at room temperature, and it is molten that cellulose fento suspension is then titrated to calcium chloride with glass syringe
In liquid, ball shaped cellulose wet gel will be obtained and be immersed in progress solvent displacement in t-butanol solution, completely rear progress to be replaced is true
Vacuum freecing-dry can be prepared by spherical cellulose aerogel；By the way that cellulose fento suspension to be placed in the big burning equipped with ice cube
It is ultrasonically treated in cup, can prevent ultrasonic treatment from causing the fracture of cellulose hydrogen bond, so as to avoid cellulose airsetting
The collapsing of glue pore structure, to help to improve the stability of cellulose aerogels pore structure；
3) Zinc vitriol powder and ammonium hydrogen carbonate are placed in mortar, a small amount of polyethylene glycol is added, be 50- in revolving speed
40-50min is ground under 70r/min, stands 4-6h at room temperature, carries out washing with distilled water until being examined in cleaning solution with barium chloride
It can not test sulfate ion, wash 10-15min with dehydrated alcohol after suction filtration, be equipped with 200-300W's in washing process
Product after washing is dried at 100-120 DEG C 1-1.5h, obtains carbonic acid zinc nanocrystalline presoma by supersonic oscillations；It utilizes
Zinc vitriol and ammonium hydrogen carbonate obtain carbonic acid zinc nanocrystalline presoma as raw material；
4) carbonic acid zinc nanocrystalline presoma is added in tartaric acid ladder potassium/PVP/TAA mixture solution, is 150- in revolving speed
30-40min is stirred under 200r/min, spherical cellulose aerogel is then added, and vibrates 30- under 300-400W ultrasonic wave
40min is then placed in reaction kettle, is forced into 5-8MPa, the heated at constant temperature 12-16h at 180-200 DEG C, to after the reaction was completed
It is cooled to room temperature, then moves in calcining furnace, be heated to 430-460 DEG C, calcine 2-3h, can be prepared by the nano oxidized of reticular structure
Zinc；The application using spherical cellulose aerogel as carrier, the characteristics of using its water absorption and swelling, by carbonic acid zinc nanocrystalline forerunner
Body and tartaric acid ladder potassium/PVP/TAA mixture solution be adsorbed in the hole of aeroge to formed solvent be tartaric acid ladder potassium/
PVP/TAA mixture solution, and it is filled with the cellulose wet gel of carbonic acid zinc nanocrystalline presoma, pass through the heating under pressurization
Reaction forms antimony sulfide nano particle on the surface of carbonic acid zinc nanocrystalline presoma, and with the progress of hydro-thermal reaction, antimony trisulfide is brilliant
Agglomeration occurs between grain and from surface grows some reticular structures, with the continuous growth of antimony trisulfide crystal grain reticular structure,
Antimony sulfide nano particle is progressively reduced until disappearance, covers carbonic acid zinc nanocrystalline presoma by reticular structure completely
Lid, so that the carbonic acid zinc nanocrystalline presoma filled in cellulose wet gel is coated and connected by reticular structure；
By pressurizeing in heating reaction process, the aperture of reticular structure can be not only further decreased, prevents subsequent calcination from generating
Nano zine oxide is escaped from hole, but also the close of carbonic acid zinc nanocrystalline presoma surface mesh structure cladding can be improved
Degree prevents that agglomeration occurs between the nano zine oxide of subsequent calcination generation；By carrying out high-temperature calcination in calcining furnace, make
It obtains carbonic acid zinc nanocrystalline presoma and is decomposed to form zinc oxide grain completely, oxygen is constantly passed through in calcination process, can be made
Cellulose aerogels are sufficiently decomposed, and cellulose aerogels is prevented to be carbonized in decomposable process, so as to improve nano oxygen
Change the purity of zinc.
Preferably, a kind of preparation method of reticular structure nano zine oxide, wherein in step 1), the potassium antimony tartrate,
The mass volume ratio of polyvinylpyrrolidone, thioacetamide and deionized water is 7-9g:0.2-0.5g:1.2-1.8g:30-
35ml。
Preferably, a kind of preparation method of reticular structure nano zine oxide, wherein in step 2, the cellulose is micro-
The content of cellulose is 1.2-1.8% in fine suspension；The concentration of the calcium chloride solution is 0.5-0.7mol/L；The solvent
The displaced time is 24-30h, and replaces a solvent at interval of 5-8h；The titration method of the cellulose suspension is as follows:
Liquid level 6-8mm of the end of glass syringe apart from calcium chloride solution during dropwise addition, then slowly by glass syringe end
The gel of end suspension balling-up instills in calcium chloride solution.
Preferably, a kind of preparation method of reticular structure nano zine oxide, wherein in step 3), seven hydrated sulfuric acid
The mass volume ratio of zinc, ammonium hydrogen carbonate and polyethylene glycol is 2-3g:1.3-1.7g:20-25uL；The molecular weight of the polyethylene glycol
It is 400.
Preferably, a kind of preparation method of reticular structure nano zine oxide, wherein in step 4), the carbonic acid zinc nanocrystalline
The mass volume ratio of presoma, tartaric acid ladder potassium/PVP/TAA mixture solution and spherical cellulose aerogel is 15-25g:
100-130ml:40-50g；Need constantly to be passed through oxygen in the calcination process into calcining furnace, the flow of oxygen is 100-
150ml/min, the heating rate of calcining furnace are 20-30 DEG C/min
The present invention has the advantage that compared with prior art
Preparation method provided by the invention has the advantages that process conditions are easy to control and low in cost, using ball shaped cellulose airsetting
Glue is as carrier, and the characteristics of using its water absorption and swelling, carbonic acid zinc nanocrystalline presoma and tartaric acid ladder potassium/PVP/TAA are mixed
Object solution is adsorbed in the hole of aeroge to form solvent to be tartaric acid ladder potassium/PVP/TAA mixture solution, and fills
There is the cellulose wet gel of carbonic acid zinc nanocrystalline presoma, reacted by pressurized, heated, is formed using antimony trisulfide hydro-thermal reaction
Even reticular structure, and the characteristics of pattern no significant difference, so that carbonic acid zinc nanocrystalline presoma is before calcination by netted knot
The antimony trisulfide of structure is closely coated and is connected, to control the size and shape for the nano zine oxide that calcining generates, is made made
Standby nano zine oxide reaches nanometer scale, and has uniform Nanostructure Network, and the topographical difference of reticular structure
Small, structural stability is good.
Specific embodiment
Below with reference to specific implementation method, the present invention is described further.
Embodiment 1
A kind of preparation method of reticular structure nano zine oxide, it is specific the preparation method is as follows:
1) potassium antimony tartrate is add to deionized water, stirs 15min in the case where revolving speed is 130r/min, makes it after completely dissolution
Polyvinylpyrrolidone is added, continues to stir 20min, after its dissolution, thioacetamide is added into mixed solution, continues to stir
35min is mixed, tartaric acid ladder potassium/PVP/TAA mixture solution is obtained；
2) cellulose fento suspension is placed in the large beaker equipped with ice cube, handles 50s under 150W ultrasonic wave, processing terminate
It stands 10min at room temperature afterwards, then cellulose fento suspension is titrated in calcium chloride solution with glass syringe, will be obtained
Ball shaped cellulose wet gel, which is immersed in t-butanol solution, carries out solvent displacement, completely rear progress vacuum freeze drying to be replaced,
It can be prepared by spherical cellulose aerogel；
3) Zinc vitriol powder and ammonium hydrogen carbonate are placed in mortar, a small amount of polyethylene glycol is added, be 50r/ in revolving speed
50min is ground under min, stands 6h at room temperature, carries out washing with distilled water until can not examine sulphur with barium chloride in cleaning solution
Acid ion washs 15min with dehydrated alcohol after suction filtration, the supersonic oscillations of 200W is equipped in washing process, will be washed
Product after washing dries 1.5h at 100 DEG C, obtains carbonic acid zinc nanocrystalline presoma；
4) carbonic acid zinc nanocrystalline presoma is added in tartaric acid ladder potassium/PVP/TAA mixture solution, is 150r/ in revolving speed
40min is stirred under min, spherical cellulose aerogel is then added, vibrates 40min under 300W ultrasonic wave, is then placed in reaction
In kettle, it is forced into 5MPa, the heated at constant temperature 16h at 180 DEG C is then moved in calcining furnace, added to be cooled to room temperature after the reaction was completed
Heat calcines 3h, can be prepared by the nano zine oxide of reticular structure to 430 DEG C.
Preferably, wherein in step 1), the potassium antimony tartrate, polyvinylpyrrolidone, thioacetamide and go from
The mass volume ratio of sub- water is 7g:0.2g:1.2g:30ml.
Preferably, the content of cellulose is 1.2% in the cellulose fento suspension wherein in step 2；Institute
The concentration for stating calcium chloride solution is 0.5mol/L；The time of solvent displacement be for 24 hours, and it is primary molten at interval of 5h replacement
Agent；The titration method of the cellulose suspension is as follows: the end of glass syringe is apart from calcium chloride solution during dropwise addition
Liquid level 6mm, then slowly by glass syringe end suspension balling-up gel instill calcium chloride solution in.
Preferably, wherein in step 3), the mass volume ratio of the Zinc vitriol, ammonium hydrogen carbonate and polyethylene glycol
For 2g:1.3g:20uL；The molecular weight of the polyethylene glycol is 400.
Preferably, wherein in step 4), the carbonic acid zinc nanocrystalline presoma, tartaric acid ladder potassium/PVP/TAA mixture
Solution and the mass volume ratio of spherical cellulose aerogel are 15g:100ml:40g；It is needed in the calcination process continuous
Oxygen is passed through into calcining furnace, the flow of oxygen is 100ml/min, and the heating rate of calcining furnace is 20 DEG C/min.
Embodiment 2
A kind of preparation method of reticular structure nano zine oxide, it is specific the preparation method is as follows:
1) potassium antimony tartrate is add to deionized water, stirs 13min in the case where revolving speed is 150r/min, makes it after completely dissolution
Polyvinylpyrrolidone is added, continues to stir 18min, after its dissolution, thioacetamide is added into mixed solution, continues to stir
32min is mixed, tartaric acid ladder potassium/PVP/TAA mixture solution is obtained；
2) cellulose fento suspension is placed in the large beaker equipped with ice cube, handles 40s under 170W ultrasonic wave, processing terminate
It stands 8min at room temperature afterwards, then cellulose fento suspension is titrated in calcium chloride solution with glass syringe, will be obtained
Ball shaped cellulose wet gel, which is immersed in t-butanol solution, carries out solvent displacement, completely rear progress vacuum freeze drying to be replaced,
It can be prepared by spherical cellulose aerogel；
3) Zinc vitriol powder and ammonium hydrogen carbonate are placed in mortar, a small amount of polyethylene glycol is added, be 60r/ in revolving speed
45min is ground under min, stands 5h at room temperature, carries out washing with distilled water until can not examine sulphur with barium chloride in cleaning solution
Acid ion washs 13min with dehydrated alcohol after suction filtration, the supersonic oscillations of 250W is equipped in washing process, will be washed
Product after washing dries 1.3h at 110 DEG C, obtains carbonic acid zinc nanocrystalline presoma；
4) carbonic acid zinc nanocrystalline presoma is added in tartaric acid ladder potassium/PVP/TAA mixture solution, is 180r/ in revolving speed
35min is stirred under min, spherical cellulose aerogel is then added, vibrates 35min under 350W ultrasonic wave, is then placed in reaction
In kettle, it is forced into 7MPa, the heated at constant temperature 15h at 190 DEG C is then moved in calcining furnace, added to be cooled to room temperature after the reaction was completed
Heat calcines 2.5h, can be prepared by the nano zine oxide of reticular structure to 450 DEG C.
Preferably, wherein in step 1), the potassium antimony tartrate, polyvinylpyrrolidone, thioacetamide and go from
The mass volume ratio of sub- water is 8g:0.3g:1.5g:32ml.
Preferably, the content of cellulose is 1.5% in the cellulose fento suspension wherein in step 2；Institute
The concentration for stating calcium chloride solution is 0.6mol/L；The time of the solvent displacement is 28h, and primary molten at interval of 7h replacement
Agent；The titration method of the cellulose suspension is as follows: the end of glass syringe is apart from calcium chloride solution during dropwise addition
Liquid level 7mm, then slowly by glass syringe end suspension balling-up gel instill calcium chloride solution in.
Preferably, wherein in step 3), the mass volume ratio of the Zinc vitriol, ammonium hydrogen carbonate and polyethylene glycol
For 2.5g:1.5g:23uL；The molecular weight of the polyethylene glycol is 400.
Preferably, wherein in step 4), the carbonic acid zinc nanocrystalline presoma, tartaric acid ladder potassium/PVP/TAA mixture
Solution and the mass volume ratio of spherical cellulose aerogel are 20g:120ml:45g；It is needed in the calcination process continuous
Oxygen is passed through into calcining furnace, the flow of oxygen is 130ml/min, and the heating rate of calcining furnace is 25 DEG C/min.
Embodiment 3
A kind of preparation method of reticular structure nano zine oxide, it is specific the preparation method is as follows:
1) potassium antimony tartrate is add to deionized water, stirs 10min in the case where revolving speed is 180r/min, makes it after completely dissolution
Polyvinylpyrrolidone is added, continues to stir 15min, after its dissolution, thioacetamide is added into mixed solution, continues to stir
30min is mixed, tartaric acid ladder potassium/PVP/TAA mixture solution is obtained；
2) cellulose fento suspension is placed in the large beaker equipped with ice cube, handles 30s under 180W ultrasonic wave, processing terminate
It stands 7min at room temperature afterwards, then cellulose fento suspension is titrated in calcium chloride solution with glass syringe, will be obtained
Ball shaped cellulose wet gel, which is immersed in t-butanol solution, carries out solvent displacement, completely rear progress vacuum freeze drying to be replaced,
It can be prepared by spherical cellulose aerogel；
3) Zinc vitriol powder and ammonium hydrogen carbonate are placed in mortar, a small amount of polyethylene glycol is added, be 70r/ in revolving speed
40min is ground under min, stands 4h at room temperature, carries out washing with distilled water until can not examine sulphur with barium chloride in cleaning solution
Acid ion washs 15min with dehydrated alcohol after suction filtration, the supersonic oscillations of 200W is equipped in washing process, will be washed
Product after washing dries 1h at 120 DEG C, obtains carbonic acid zinc nanocrystalline presoma；
4) carbonic acid zinc nanocrystalline presoma is added in tartaric acid ladder potassium/PVP/TAA mixture solution, is 200r/ in revolving speed
30min is stirred under min, spherical cellulose aerogel is then added, vibrates 30min under 400W ultrasonic wave, is then placed in reaction
In kettle, it is forced into 8MPa, the heated at constant temperature 12h at 200 DEG C is then moved in calcining furnace, added to be cooled to room temperature after the reaction was completed
Heat calcines 2h, can be prepared by the nano zine oxide of reticular structure to 460 DEG C.
Preferably, wherein in step 1), the potassium antimony tartrate, polyvinylpyrrolidone, thioacetamide and go from
The mass volume ratio of sub- water is 9g:0.5g:1.8g:35ml.
Preferably, the content of cellulose is 1.8% in the cellulose fento suspension wherein in step 2；Institute
The concentration for stating calcium chloride solution is 0.7mol/L；The time of the solvent displacement is 30h, and primary molten at interval of 8h replacement
Agent；The titration method of the cellulose suspension is as follows: the end of glass syringe is apart from calcium chloride solution during dropwise addition
Liquid level 8mm, then slowly by glass syringe end suspension balling-up gel instill calcium chloride solution in.
Preferably, wherein in step 3), the mass volume ratio of the Zinc vitriol, ammonium hydrogen carbonate and polyethylene glycol
For 3g:1.7g:25uL；The molecular weight of the polyethylene glycol is 400.
Preferably, wherein in step 4), the carbonic acid zinc nanocrystalline presoma, tartaric acid ladder potassium/PVP/TAA mixture
Solution and the mass volume ratio of spherical cellulose aerogel are 25g:130ml:50g；It is needed in the calcination process continuous
Oxygen is passed through into calcining furnace, the flow of oxygen is 150ml/min, and the heating rate of calcining furnace is 30 DEG C/min.
Comparative example 1: the polyvinylpyrrolidone in removal step 1), remaining is same as Example 1.
Comparative example 2: step 2 is removed, mixes carbonic acid zinc nanocrystalline presoma and tartaric acid ladder potassium/PVP/TAA in step 4)
Polymer solution is directly mixed, remaining is same as Example 1.
Comparative example 3: using zinc sulfate as raw material, nano zine oxide is made using solid phase method.
Comparative example 4: it using zinc acetate, Triammonium citrate as primary raw material, is repaired by surface of cetyl trimethylammonium bromide
Agent is adornd, nano zine oxide is made using sol-gel method.
Control group: nano zine oxide is made using the method in notification number CN102774874B disclosed embodiment 1.
Test example: preparing nano zine oxide product using the method for embodiment 1-3, comparative example 1-4 and control group respectively,
Then nano zine oxide 0.1g is taken, 1m is put into3Closed glass case in, be injected separately into the glass box of Xiang Butong formaldehyde, toluene,
Ammonia and VTOC detect the change of gas concentration in each glass box in the case where room temperature is 28 DEG C ± 3 DEG C and sunlight irradiation after 45 minutes
Change situation, as a result as shown in the table:
As can be seen from the above table, reticular structure nano zine oxide prepared by the present invention has fabulous photocatalytic degradation, in sky
Gas purification aspect is with a wide range of applications.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
It transforms or replaces, should be covered by the scope of protection of the present invention without what creative work was expected.
Claims (5)
1. a kind of preparation method of reticular structure nano zine oxide, which is characterized in that it is specific the preparation method is as follows:
1) potassium antimony tartrate is add to deionized water, stirs 10-15min in the case where revolving speed is 130-180r/min, fills it
Polyvinylpyrrolidone is added after dividing dissolution, continues to stir 15-20min, after its dissolution, thio second is added into mixed solution
Amide continues to stir 30-35min, obtains tartaric acid ladder potassium/PVP/TAA mixture solution；
2) cellulose fento suspension is placed in the large beaker equipped with ice cube, handles 30-50s under 150-180W ultrasonic wave,
After treatment stands 7-10min at room temperature, and it is molten that cellulose fento suspension is then titrated to calcium chloride with glass syringe
In liquid, ball shaped cellulose wet gel will be obtained and be immersed in progress solvent displacement in t-butanol solution, completely rear progress to be replaced is true
Vacuum freecing-dry can be prepared by spherical cellulose aerogel；
3) Zinc vitriol powder and ammonium hydrogen carbonate are placed in mortar, a small amount of polyethylene glycol is added, be 50- in revolving speed
40-50min is ground under 70r/min, stands 4-6h at room temperature, carries out washing with distilled water until being examined in cleaning solution with barium chloride
It can not test sulfate ion, wash 10-15min with dehydrated alcohol after suction filtration, be equipped with 200-300W's in washing process
Product after washing is dried at 100-120 DEG C 1-1.5h, obtains carbonic acid zinc nanocrystalline presoma by supersonic oscillations；
4) carbonic acid zinc nanocrystalline presoma is added in tartaric acid ladder potassium/PVP/TAA mixture solution, is 150- in revolving speed
30-40min is stirred under 200r/min, spherical cellulose aerogel is then added, and vibrates 30- under 300-400W ultrasonic wave
40min is then placed in reaction kettle, is forced into 5-8MPa, the heated at constant temperature 12-16h at 180-200 DEG C, to after the reaction was completed
It is cooled to room temperature, then moves in calcining furnace, be heated to 430-460 DEG C, calcine 2-3h, can be prepared by the nano oxidized of reticular structure
Zinc.
2. a kind of preparation method of reticular structure nano zine oxide as described in claim 1, which is characterized in that in step 1),
The potassium antimony tartrate, polyvinylpyrrolidone, thioacetamide and deionized water mass volume ratio be 7-9g:0.2-
0.5g:1.2-1.8g:30-35ml.
3. a kind of preparation method of reticular structure nano zine oxide as described in claim 1, which is characterized in that in step 2,
The content of cellulose is 1.2-1.8% in the cellulose fento suspension；The concentration of the calcium chloride solution is 0.5-
0.7mol/L；The time of the solvent displacement is 24-30h, and replaces a solvent at interval of 5-8h；The cellulose suspends
The titration method of liquid is as follows: then liquid level 6-8mm of the end of glass syringe apart from calcium chloride solution during dropwise addition delays
Slowly the gel by the suspension balling-up of glass syringe end instills in calcium chloride solution.
4. a kind of preparation method of reticular structure nano zine oxide as described in claim 1, which is characterized in that in step 3),
The mass volume ratio of the Zinc vitriol, ammonium hydrogen carbonate and polyethylene glycol is 2-3g:1.3-1.7g:20-25uL；It is described poly-
The molecular weight of ethylene glycol is 400.
5. a kind of preparation method of reticular structure nano zine oxide as described in claim 1, which is characterized in that in step 4),
The quality of the carbonic acid zinc nanocrystalline presoma, tartaric acid ladder potassium/PVP/TAA mixture solution and spherical cellulose aerogel
Volume ratio is 15-25g:100-130ml:40-50g；It needs constantly to be passed through oxygen, oxygen into calcining furnace in the calcination process
The flow of gas is 100-150ml/min, and the heating rate of calcining furnace is 20-30 DEG C/min.
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Application publication date: 20191112 Assignee: Xinghua Hongda zinc products factory Assignor: ANHUI JINHUA ZINC OXIDE Co.,Ltd. Contract record no.: X2024980002980 Denomination of invention: A preparation method of nano zinc oxide with a network structure Granted publication date: 20211210 License type: Common License Record date: 20240322 |