CN106082317A - A kind of preparation method of hollow hemisphere titanium dioxide - Google Patents
A kind of preparation method of hollow hemisphere titanium dioxide Download PDFInfo
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- CN106082317A CN106082317A CN201610378913.6A CN201610378913A CN106082317A CN 106082317 A CN106082317 A CN 106082317A CN 201610378913 A CN201610378913 A CN 201610378913A CN 106082317 A CN106082317 A CN 106082317A
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- titanium dioxide
- ethanol
- acetonitrile
- hollow hemisphere
- reactant liquor
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000004793 Polystyrene Substances 0.000 claims abstract description 26
- 229920002223 polystyrene Polymers 0.000 claims abstract description 26
- 239000011258 core-shell material Substances 0.000 claims abstract description 14
- 239000004005 microsphere Substances 0.000 claims abstract description 13
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 78
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 51
- 239000000376 reactant Substances 0.000 claims description 27
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000002105 nanoparticle Substances 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- 235000019394 potassium persulphate Nutrition 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 229960005196 titanium dioxide Drugs 0.000 claims 12
- 239000002253 acid Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000002372 labelling Methods 0.000 claims 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims 1
- 238000007146 photocatalysis Methods 0.000 abstract description 9
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 238000005253 cladding Methods 0.000 abstract description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 2
- 230000004927 fusion Effects 0.000 abstract description 2
- 238000003837 high-temperature calcination Methods 0.000 abstract description 2
- 239000012046 mixed solvent Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000011859 microparticle Substances 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 239000011805 ball Substances 0.000 description 6
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 6
- 229940043267 rhodamine b Drugs 0.000 description 6
- 238000002156 mixing Methods 0.000 description 4
- 230000005855 radiation Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011806 microball Substances 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RJOJUSXNYCILHH-UHFFFAOYSA-N gadolinium(3+) Chemical compound [Gd+3] RJOJUSXNYCILHH-UHFFFAOYSA-N 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Abstract
A kind of preparation method of hollow hemisphere titanium dioxide, with surfactant-free emulsion polymerization synthesis nano pipe/polyhenylethylene ball as template, by mixed solvent method at Surfaces of Polystyrene Microparticles cladding titanium dioxide shell, coated by titanium dioxide polystyrene core-shell microsphere is obtained after eccentric cleaning, drying, it is carried out high-temperature calcination and makes inner polystyrene fusion and decomposition, titanium dioxide shell sections subsides formation half-spherical construction, obtains the hollow hemisphere titanium dioxide that photocatalysis performance is excellent；The present invention can realize titanium dioxide hemisphere size and the controllable adjustment of thickness, simple to operate, be prone to large-scale production, and prepared hollow hemisphere titanium dioxide has the advantages that specific surface area is big, density is low and photocatalysis performance is excellent.
Description
Technical field
The present invention relates to nano-photocatalyst material preparing technical field, particularly to the system of a kind of hollow hemisphere titanium dioxide
Preparation Method.
Background technology
1972, Fujishima and Honda was first by TiO2Application of electrode is in decomposition water.Since then, TiO2Photocatalysis,
The potentiality of the aspects such as solar energy conversion, gas sensor so that it is be widely studied.TiO2Photocatalytic activity depend on
Its form and macrostructure.At present, research worker is to synthesize multiple TiO2Nanostructured, such as nanometer rods, nano wire, nanotube
And hollow ball structure.Wherein, hollow ball structure, due to its low-density, high surface area and good photocatalysis performance, obtains wide
General concern.Synthesis TiO2Hollow ball most common method is template, with organic granular as template, in organic granular surface attachment
Titanium dioxide, removes template by the way of calcining or dissolving subsequently, obtains TiO2Hollow ball.In recent years, researcher was to TiO2Empty
The research of bulbus cordis is deepened day by day, constantly has new synthetic method to occur.Chinese invention issued patents CN103816887A discloses
A kind of meso-porous hollow nano titanium dioxide ball of gadolinium ion doping, the structure of its uniqueness improves the utilization rate in photon and hole,
There is the photocatalysis performance of excellence, but its template used is silicon dioxide, is difficult to completely remove, limits in actual production
Its application, additionally, prepared by this invention is a kind of spherical tio2, specific surface area is difficult to improve further.Chinese patent
CN1442367A discloses and produces the method for rutile type nano titanic oxide and thus obtained nano titanium oxide, has
Higher application prospect, has well control to the particle diameter etc. of product, but its acquisition is rutile titanium dioxide, not
It is suitably applied in photocatalysis field.
Summary of the invention
In order to overcome the defect of above-mentioned prior art, it is an object of the invention to provide the system of a kind of hollow hemisphere titanium dioxide
Preparation Method, the nano pipe/polyhenylethylene ball that the method synthesizes with surfactant-free emulsion polymerization is as template, by mixed solvent method at polyphenyl
Ethylene microsphere surface cladding titanium dioxide shell, obtains coated by titanium dioxide polystyrene Core-Shell Structures after eccentric cleaning, drying
Microsphere, to its carry out high-temperature calcination make inner polystyrene fusion and decomposition, titanium dioxide shell sections subside formation hemispherical structure
Making, obtain the hollow hemisphere titanium dioxide that photocatalysis performance is excellent, hollow hemisphere titanium dioxide purity prepared by the present invention is high, instead
Answering mild condition, simple to operate, repeatability is high and size is controlled.
For achieving the above object, the technical scheme is that
The preparation method of a kind of hollow hemisphere titanium dioxide, comprises the following steps:
Step 1: with styrene as monomer, methacrylic acid is comonomer, in 100mL aqueous solution, is sequentially added into 5-
The styrene of 9mL, the methacrylic acid of 0.3-0.7mL, it is warming up to 70-80 DEG C in aqueous, adds the water-soluble of 0.1g-0.2g
Property initiator, react 6-9h, obtain milky white solution, after washing is centrifugal, obtain Properties of Polystyrene Nano Particles powder body；
Step 2: 0.2-0.5g Properties of Polystyrene Nano Particles powder body, 0.2-0.5mL ammonia are added 100mL ethanol/acetonitrile
Mixed solution in, ethanol/acetonitrile volume ratio is (1～9): 1, stir 5-15min, be labeled as reactant liquor 1；By 0.5-1.5mL
Butyl titanate adds the mixed solution of 20mL ethanol/acetonitrile, and ethanol/acetonitrile volume ratio is (1～9): 1, stirs after it dissolves
It is labeled as reactant liquor 2；Dropping in reactant liquor 1 by reactant liquor 2 subsequently, stirring reaction 5h after completing, eccentric cleaning obtains after drying
To coated by titanium dioxide polystyrene core-shell microsphere；
Step 3: coated by titanium dioxide polystyrene core-shell microsphere step 2 prepared is placed in electric furnace and is incubated at 500 DEG C
3-6h, obtains hollow hemisphere titanium dioxide after having calcined.
In described step 1, water soluble starter includes potassium peroxydisulfate, Ammonium persulfate. or azodiisobutyronitrile.
In the mixed solution of described step 2 ethanol/acetonitrile, ethanol is 3:1 with the volume ratio of acetonitrile, and its preparation method is will
Acetonitrile solution agitation and dropping is in ethanol solution.
In described step 2, reactant liquor 2 drops to the speed of reactant liquor 1 is that 30-40 drips/min.
Heating rate when electric furnace is warming up to 500 DEG C in described step 3 is 2-4 DEG C/min.
Hollow hemisphere titanium dioxide process of the present invention at least has the advantage that
1. the hollow hemisphere titanium dioxide of preparation is pure phase anatase type, and specific surface area is big, and size can be controlled in 100-
500nm, shell thickness can control at 6-19nm；
2. photocatalysis performance highlights, and ultraviolet light irradiates after 10min, to the degradation rate of rhodamine B reach 65-70%；30-
After 40min, the degradation rate of rhodamine B reaches 100%；
3. reaction condition is gentle, simple to operate, and repeatability is high, the most low for equipment requirements, is suitable to produce on a large scale.
Accompanying drawing explanation
Fig. 1 is the hollow hemisphere titanium dioxide Raman collection of illustrative plates prepared by embodiment 1.
Fig. 2 a is hollow hemisphere titanium dioxide scanning electron microscope (SEM) photo prepared by embodiment 1.
Fig. 2 b is hollow hemisphere titanium dioxide transmission electron microscope (TEM) photo prepared by embodiment 1.
Fig. 3 a is the hollow hemisphere titanium dioxide degradable rhodamine B abosrption spectrogram prepared by embodiment 1.
Fig. 3 b is different sample photocatalysis performance comparison diagrams.
Detailed description of the invention
Embodiment one
The present embodiment comprises the following steps:
Step 1: with 6mL styrene as monomer, 0.5mL methacrylic acid is comonomer, is warming up to 75 in aqueous
DEG C, add 0.1273g potassium peroxydisulfate initiator, react 8h, obtain milky white solution, after washing is centrifugal, obtains polystyrene and receive
Meter Wei Qiu powder body.
Step 2: by molten for the mixing of 0.3g Properties of Polystyrene Nano Particles powder body, 0.5mL ammonia addition 100mL ethanol/acetonitrile
In liquid, ethanol/acetonitrile volume ratio is 3:1, stirs 10min, is labeled as reactant liquor 1；0.5mL butyl titanate is added 20mL second
The mixed solution of alcohol/acetonitrile, ethanol/acetonitrile volume ratio is 3:1, stirs and is labeled as reactant liquor 2 after it dissolves；Subsequently will reaction
Liquid 2 drops in reactant liquor 1,30/min, stirring reaction 5h after completing, and eccentric cleaning obtains coated by titanium dioxide and gathers after drying
Styrene core-shell particles.
Step 3: coated by titanium dioxide polystyrene core-shell microsphere step 2 prepared is placed in electric furnace, with 2 DEG C/min liter
Temperature is to 500 DEG C and is incubated 3h, obtains hollow hemisphere titanium dioxide after having calcined, with reference to Fig. 1.
With reference to Fig. 2, the hollow hemisphere titanium dioxide particle diameter obtained by the present embodiment is 180nm, and shell thickness is 9nm, ginseng
According to Fig. 3, ultra-vioket radiation, after 10 minutes, reaches 67% to rhodamine B degradation rate, and after 35min, degradation rate reaches 100%.
Embodiment two
The present embodiment comprises the following steps:
Step 1: with 6mL styrene as monomer, 0.5mL methacrylic acid is comonomer, is warming up to 75 in aqueous
DEG C, 0.1273g potassium peroxydisulfate initiator, reacts 8h, obtains milky white solution.After washing is centrifugal, obtain pipe/polyhenylethylene nano micro-
Ball powder body；
Step 2: by 0.3g polystyrene, the mixed solution of 0.5mL ammonia addition 100mL (3:1 volume ratio) ethanol/acetonitrile
In, stir 10min, be labeled as reactant liquor 1；By molten for the mixing of 1mL butyl titanate addition 20mL (3:1 volume ratio) ethanol/acetonitrile
Liquid, stirs and is labeled as reactant liquor 2 after it dissolves；Drop to reactant liquor 2 subsequently, in reactant liquor 1,30/min, stir after completing
Mixing reaction 5h, eccentric cleaning obtains coated by titanium dioxide polystyrene core-shell microsphere after drying.
Step 3: coated by titanium dioxide polystyrene core-shell microsphere step 2 prepared is placed in electric furnace, with 2 DEG C/min liter
Temperature is to 500 DEG C and is incubated 3h, obtains hollow hemisphere titanium dioxide after having calcined.
Hollow hemisphere titanium dioxide particle diameter obtained by the present embodiment is 180nm, and shell thickness is 15nm, ultra-vioket radiation 10
After minute, rhodamine B degradation rate being reached 70%, after 25min, degradation rate reaches 100%.
Embodiment three
The present embodiment comprises the following steps:
Step 1: with 7mL styrene as monomer, 0.4mL methacrylic acid is comonomer, is warming up to 75 in aqueous
DEG C, 0.1273g potassium peroxydisulfate initiator, reacts 8h, obtains milky white solution；After washing is centrifugal, obtain pipe/polyhenylethylene nano micro-
Ball powder body.
Step 2: by 0.3g polystyrene, the mixed solution of 0.5mL ammonia addition 100mL (3:1 volume ratio) ethanol/acetonitrile
In, stir 10min, be labeled as reactant liquor 1；1.5mL butyl titanate is added the mixing of 20mL (3:1 volume ratio) ethanol/acetonitrile
Solution, stirs and is labeled as reactant liquor 2 after it dissolves；Subsequently reactant liquor 2 is dropped in reactant liquor 1,30/min, after completing
Stirring reaction 5h, eccentric cleaning obtains coated by titanium dioxide polystyrene core-shell microsphere after drying.
Step 3: coated by titanium dioxide polystyrene core-shell microsphere step 2 prepared is placed in electric furnace, with 2 DEG C/min liter
Temperature is to 500 DEG C and is incubated 3h, obtains hollow hemisphere titanium dioxide after having calcined.
Hollow hemisphere titanium dioxide particle diameter obtained by the present embodiment is 230nm, and shell thickness is 20nm, ultra-vioket radiation 10
After minute, rhodamine B degradation rate being reached 75%, after 20min, degradation rate reaches 100%.
Claims (6)
1. the preparation method of a hollow hemisphere titanium dioxide, it is characterised in that comprise the following steps:
Step 1: with styrene as monomer, methacrylic acid is comonomer, in 100mL aqueous solution, is sequentially added into 5-9mL's
Styrene, the methacrylic acid of 0.3-0.7mL, it is warming up to 70-80 DEG C in aqueous, the water solublity adding 0.1g-0.2g draws
Send out agent, react 6-9h, obtain milky white solution, after washing is centrifugal, obtain Properties of Polystyrene Nano Particles powder body；
Step 2: 0.2-0.5g Properties of Polystyrene Nano Particles powder body, 0.2-0.5mL ammonia are added the mixed of 100mL ethanol/acetonitrile
Closing in solution, ethanol/acetonitrile volume ratio is (1～9): 1, stirs 5-15min, is labeled as reactant liquor 1；By 0.5-1.5mL metatitanic acid
Butyl ester adds the mixed solution of 20mL ethanol/acetonitrile, and ethanol/acetonitrile volume ratio is (1～9): 1, stirs labelling after it dissolves
For reactant liquor 2；Dropping in reactant liquor 1 by reactant liquor 2 subsequently, stirring reaction 5h after completing, eccentric cleaning obtains two after drying
Titanium-oxide-coated polystyrene core-shell microsphere；
Step 3: coated by titanium dioxide polystyrene core-shell microsphere step 2 prepared is placed in electric furnace and is incubated 3-6h at 500 DEG C,
Hollow hemisphere titanium dioxide is obtained after having calcined.
The preparation method of a kind of hollow hemisphere titanium dioxide the most according to claim 1, it is characterised in that include following step
Rapid: in described step 1, water soluble starter includes potassium peroxydisulfate, Ammonium persulfate. or azodiisobutyronitrile.
The preparation method of a kind of hollow hemisphere titanium dioxide the most according to claim 1, it is characterised in that include following step
Rapid: in the mixed solution of described step 2 ethanol/acetonitrile, ethanol is 3:1 with the volume ratio of acetonitrile, and its preparation method is that acetonitrile is molten
Liquid agitation and dropping is in ethanol solution.
The preparation method of a kind of hollow hemisphere titanium dioxide the most according to claim 1, it is characterised in that include following step
Rapid: in described step 2, reactant liquor 2 drops to the speed of reactant liquor 1 is that 30-40 drips/min.
The preparation method of a kind of hollow hemisphere titanium dioxide the most according to claim 1, it is characterised in that include following step
Rapid: heating rate when electric furnace is warming up to 500 DEG C in described step 3 is 2-4 DEG C/min.
The preparation method of a kind of hollow hemisphere titanium dioxide the most according to claim 1, it is characterised in that include following step
Rapid:
Step 1: with 6mL styrene as monomer, 0.5mL methacrylic acid is comonomer, is warming up to 75 DEG C in aqueous, adds
Enter 0.1273g potassium peroxydisulfate initiator, react 8h, obtain milky white solution, after washing is centrifugal, obtain Properties of Polystyrene Nano Particles
Powder body；
Step 2: by 0.3g Properties of Polystyrene Nano Particles powder body, 0.5mL ammonia add 100mL ethanol/acetonitrile mixed solution in,
Ethanol/acetonitrile volume ratio is 3:1, stirs 10min, is labeled as reactant liquor 1；0.5mL butyl titanate is added 20mL ethanol/acetonitrile
Mixed solution, ethanol/acetonitrile volume ratio is 3:1, stir until its dissolve after be labeled as reactant liquor 2；Subsequently reactant liquor 2 is dripped
To reactant liquor 1,30/min, stirring reaction 5h after completing, eccentric cleaning obtains coated by titanium dioxide polystyrene after drying
Core-shell particles；
Step 3: coated by titanium dioxide polystyrene core-shell microsphere step 2 prepared is placed in electric furnace, is warming up to 2 DEG C/min
500 DEG C and be incubated 3h, after having calcined, obtain hollow hemisphere titanium dioxide.
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| CN109455759A (en) * | 2018-11-30 | 2019-03-12 | 东莞南玻太阳能玻璃有限公司 | A kind of hollow nano titanium dioxide microballoon sphere and preparation method thereof with low-refraction and high catalytic activity |
| CN109485093A (en) * | 2018-11-23 | 2019-03-19 | 陕西科技大学 | A kind of anatase titanium dioxide hollow ball shell and preparation method thereof that spherical shape is intact |
| CN109534685A (en) * | 2018-11-23 | 2019-03-29 | 陕西科技大学 | A kind of schemochrome film of underwater oleophobic and its preparation method and application |
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| CN112225247A (en) * | 2020-10-20 | 2021-01-15 | 桂林理工大学 | Nano titanium dioxide open hollow sphere and preparation method thereof |
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