CN106082317B - 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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- CN106082317B CN106082317B CN201610378913.6A CN201610378913A CN106082317B CN 106082317 B CN106082317 B CN 106082317B CN 201610378913 A CN201610378913 A CN 201610378913A CN 106082317 B CN106082317 B CN 106082317B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920002223 polystyrene Polymers 0.000 claims abstract description 27
- 239000004793 Polystyrene Substances 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 12
- 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 57
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 51
- 239000000243 solution Substances 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 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 12
- 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
- 238000001354 calcination Methods 0.000 claims description 7
- 239000002105 nanoparticle Substances 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000005119 centrifugation Methods 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
- 239000003999 initiator Substances 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000005395 methacrylic acid group Chemical class 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
- 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 10
- 239000002253 acid Substances 0.000 claims 1
- 150000007513 acids Chemical class 0.000 claims 1
- 239000003795 chemical substances by application Substances 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 5
- 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
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000010276 construction Methods 0.000 abstract 1
- 239000011859 microparticle Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 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
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011807 nanoball Substances 0.000 description 2
- 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 description 1
- 241000208340 Araliaceae Species 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
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy 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
- 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
- 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, using the nano pipe/polyhenylethylene ball of surfactant- free emulsion polymerization synthesis as template, by mixed solvent method in Surfaces of Polystyrene Microparticles cladding titanium dioxide shell, coated by titanium dioxide polystyrene core-shell microsphere is obtained after eccentric cleaning, drying, carrying out high-temperature calcination to it makes inner polystyrene fusion and decomposition, titanium dioxide shell sections collapse to form half-spherical construction, obtain the excellent hollow hemisphere titanium dioxide of photocatalysis performance；The present invention can realize the controllable adjustment to titanium dioxide hemisphere size and thickness, simple to operate, be easy to mass produce, and prepared hollow hemisphere titanium dioxide has the characteristics of 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, more particularly to a kind of system of hollow hemisphere titanium dioxide
Preparation Method.
Background technology
1972, Fujishima and Honda were first by TiO2Application of electrode is in decomposition water.Since then, TiO2Photocatalysis,
The potentiality of solar energy conversion, gas sensor etc., are widely studied it.TiO2Photocatalytic activity depend on
Its form and macrostructure.At present, researcher is to synthesize a variety of TiO2Nanostructured, such as nanometer rods, nano wire, nanotube
And hollow ball structure.Wherein, hollow ball structure is obtained wide due to its low-density, high surface area and good photocatalysis performance
General concern.Synthesize TiO2The most frequently used method of hollow ball is template, using organic granular as template, in organic granular surface attachment
Titanium dioxide, template is then removed by way of calcining or dissolving, obtain TiO2Hollow ball.In recent years, researcher was to TiO2It is empty
The research of bulbus cordis is increasingly deepened, and constantly has new synthetic method to occur.Chinese invention issued patents CN103816887A is disclosed
A kind of meso-porous hollow nano titanium dioxide ball of gadolinium ion doping, its unique structure improve the utilization rate in photon and hole,
With excellent photocatalysis performance, but its template used is difficult to remove completely for silica, in actual production, is limited
It is applied, in addition, this invention preparation is a kind of spherical tio2, specific surface area is difficult further to improve.Chinese patent
CN1442367A discloses the method for production rutile type nano titanic oxide and thus obtained nano titanium oxide, has
Higher application prospect, there is good control to particle diameter of product etc., but its acquisition is rutile titanium dioxide, not
It is suitably applied in photocatalysis field.
The content of the invention
The defects of in order to overcome above-mentioned prior art, it is an object of the invention to provide a kind of system of hollow hemisphere titanium dioxide
Preparation Method, the nano pipe/polyhenylethylene ball that this method is synthesized using surfactant- free emulsion polymerization is template, by mixed solvent method in polyphenyl
Ethene microsphere surface cladding titanium dioxide shell, coated by titanium dioxide polystyrene Core-Shell Structures are obtained after eccentric cleaning, drying
Microballoon, high-temperature calcination is carried out to it makes inner polystyrene fusion and decomposition, and titanium dioxide shell sections collapse to form hemispherical structure
Make, obtain the excellent hollow hemisphere titanium dioxide of photocatalysis performance, hollow hemisphere titanium dioxide purity prepared by the present invention is high, instead
Mild condition is answered, simple to operate, repeatability is high and size is controllable.
To achieve the above object, the technical scheme is that：
A kind of preparation method of hollow hemisphere titanium dioxide, comprises the following steps：
Step 1：Using styrene as monomer, methacrylic acid is comonomer, in the 100mL aqueous solution, sequentially adds 5-
9mL styrene, 0.3-0.7mL methacrylic acid, 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 centrifugation, obtain Properties of Polystyrene Nano Particles powder；
Step 2：0.2-0.5g Properties of Polystyrene Nano Particles powder, 0.2-0.5mL ammoniacal liquor are added into 100mL ethanol/acetonitriles
Mixed solution in, ethanol/acetonitrile volume ratio is (1~9):1,5-15min is stirred, labeled as reaction solution 1；By 0.5-1.5mL
Butyl titanate adds the mixed solution of 20mL ethanol/acetonitriles, and ethanol/acetonitrile volume ratio is (1~9):1, stirring is after its dissolving
Labeled as reaction solution 2；Then reaction solution 2 is added dropwise in reaction solution 1, after the completion of stirring reaction 5h, eccentric cleaning drying after
To coated by titanium dioxide polystyrene core-shell microsphere；
Step 3：Coated by titanium dioxide polystyrene core-shell microsphere prepared by step 2 is placed in into electric furnace at 500 DEG C to be incubated
3-6h, hollow hemisphere titanium dioxide is obtained after the completion of calcining.
Water soluble starter includes potassium peroxydisulfate, ammonium persulfate or azodiisobutyronitrile in the step 1.
The volume ratio of ethanol and acetonitrile is 3 in the mixed solution of step 2 ethanol/acetonitrile:1, its preparation method is will
Acetonitrile solution agitation and dropping is into ethanol solution.
The speed that reaction solution 2 is added dropwise to reaction solution 1 in the step 2 is 30-40 drops/min.
Heating rate when electric furnace is warming up to 500 DEG C in the step 3 is 2-4 DEG C/min.
Hollow hemisphere titanium dioxide process of the present invention at least has advantages below：
1. the hollow hemisphere titanium dioxide prepared is pure phase anatase type, specific surface area is big, and size can be controlled in 100-
500nm, shell thickness can be controlled in 6-19nm；
2. photocatalysis performance protrudes, after ultraviolet light 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, repeatability is high, especially low for equipment requirements, suitable for a wide range of production.
Brief description of the drawings
Fig. 1 is the hollow hemisphere titanium dioxide Raman collection of illustrative plates prepared by embodiment 1.
Fig. 2 a are hollow hemisphere titanium dioxide ESEM (SEM) photos prepared by embodiment 1.
Fig. 2 b are hollow hemisphere titanium dioxide transmission electron microscope (TEM) photos prepared by embodiment 1.
Fig. 3 a are the hollow hemisphere titanium dioxide degradable rhodamine B abosrption spectrograms prepared by embodiment 1.
Fig. 3 b are that different sample photocatalysis performances compare figure.
Embodiment
Embodiment one
The present embodiment comprises the following steps：
Step 1：Using 6mL styrene as monomer, 0.5mL methacrylic acids are comonomer, are warming up to 75 in aqueous
DEG C, 0.1273g potassium peroxydisulfate initiators are added, react 8h, milky white solution is obtained, after washing centrifugation, obtains polystyrene and receive
Meter Wei Qiu powders.
Step 2：The mixing that 0.3g Properties of Polystyrene Nano Particles powder, 0.5mL ammoniacal liquor are added to 100mL ethanol/acetonitriles is molten
In liquid, ethanol/acetonitrile volume ratio is 3:1,10min is stirred, labeled as reaction solution 1；0.5mL butyl titanates are added into 20mL second
The mixed solution of alcohol/acetonitrile, ethanol/acetonitrile volume ratio are 3:1, stirring mark after its dissolving is 2；Then will reaction
Liquid 2 is added dropwise in reaction solution 1,30 drops/min, after the completion of stirring reaction 5h, obtain coated by titanium dioxide after eccentric cleaning drying and gather
Styrene core-shell particles.
Step 3：Coated by titanium dioxide polystyrene core-shell microsphere prepared by step 2 is placed in electric furnace, with 2 DEG C/min liters
Temperature is to 500 DEG C and is incubated 3h, and hollow hemisphere titanium dioxide, reference picture 1 are obtained after the completion of calcining.
Reference picture 2, the hollow hemisphere titanium dioxide particle diameter obtained by the present embodiment are 180nm, shell thickness 9nm, ginseng
According to Fig. 3, ultraviolet irradiation is after 10 minutes, and degradation rate reaches 100% after reaching 67%, 35min to rhodamine B degradation rate.
Embodiment two
The present embodiment comprises the following steps：
Step 1：Using 6mL styrene as monomer, 0.5mL methacrylic acids are comonomer, are warming up to 75 in aqueous
DEG C, 0.1273g potassium peroxydisulfate initiators, 8h is reacted, obtains milky white solution.After washing centrifugation, it is micro- to obtain pipe/polyhenylethylene nano
Ball powder；
Step 2：0.3g polystyrene, 0.5mL ammoniacal liquor are added into 100mL (3:1 volume ratio) ethanol/acetonitrile mixed solution
In, 10min is stirred, labeled as reaction solution 1；1mL butyl titanates are added into 20mL (3:1 volume ratio) ethanol/acetonitrile mixing it is molten
Liquid, stirring mark after its dissolving is 2；Then reaction solution 2 is added dropwise in reaction solution 1,30 drops/min, after the completion of stir
Reaction 5h is mixed, coated by titanium dioxide polystyrene core-shell microsphere is obtained after eccentric cleaning drying.
Step 3：Coated by titanium dioxide polystyrene core-shell microsphere prepared by step 2 is placed in electric furnace, with 2 DEG C/min liters
Temperature is to 500 DEG C and is incubated 3h, and hollow hemisphere titanium dioxide is obtained after the completion of calcining.
Hollow hemisphere titanium dioxide particle diameter obtained by the present embodiment is 180nm, shell thickness 15nm, ultraviolet irradiation 10
After minute, degradation rate reaches 100% after reaching 70%, 25min to rhodamine B degradation rate.
Embodiment three
The present embodiment comprises the following steps：
Step 1：Using 7mL styrene as monomer, 0.4mL methacrylic acids are comonomer, are warming up to 75 in aqueous
DEG C, 0.1273g potassium peroxydisulfate initiators, 8h is reacted, obtains milky white solution；After washing centrifugation, it is micro- to obtain pipe/polyhenylethylene nano
Ball powder.
Step 2：0.3g polystyrene, 0.5mL ammoniacal liquor are added into 100mL (3:1 volume ratio) ethanol/acetonitrile mixed solution
In, 10min is stirred, labeled as reaction solution 1；1.5mL butyl titanates are added into 20mL (3:1 volume ratio) ethanol/acetonitrile mixing
Solution, stirring mark after its dissolving is 2；Then reaction solution 2 is added dropwise in reaction solution 1,30 drops/min, after the completion of
Stirring reaction 5h, coated by titanium dioxide polystyrene core-shell microsphere is obtained after eccentric cleaning drying.
Step 3：Coated by titanium dioxide polystyrene core-shell microsphere prepared by step 2 is placed in electric furnace, with 2 DEG C/min liters
Temperature is to 500 DEG C and is incubated 3h, and hollow hemisphere titanium dioxide is obtained after the completion of calcining.
Hollow hemisphere titanium dioxide particle diameter obtained by the present embodiment is 230nm, shell thickness 20nm, ultraviolet irradiation 10
After minute, degradation rate reaches 100% after reaching 75%, 20min to rhodamine B degradation rate.
Claims (4)
1. a kind of preparation method of hollow hemisphere titanium dioxide, it is characterised in that comprise the following steps：
Step 1：Using styrene as monomer, methacrylic acid is comonomer, in the 100mL aqueous solution, sequentially adds 5-9mL's
Styrene, 0.3-0.7mL methacrylic acid, is warming up to 70-80 DEG C in aqueous, and the water solubility for adding 0.1g-0.2g is drawn
Agent is sent out, reacts 6-9h, milky white solution is obtained, after washing centrifugation, obtains Properties of Polystyrene Nano Particles powder；
Step 2：0.2-0.5g Properties of Polystyrene Nano Particles powder, 0.2-0.5mL ammoniacal liquor are added into the mixed of 100mL ethanol/acetonitriles
Close in solution, ethanol/acetonitrile volume ratio is (1~9):1,5-15min is stirred, labeled as reaction solution 1；By 0.5-1.5mL metatitanic acids
Butyl ester adds the mixed solution of 20mL ethanol/acetonitriles, and ethanol/acetonitrile volume ratio is (1~9):1, stirring marks after its dissolving
For reaction solution 2；Then reaction solution 2 is added dropwise in reaction solution 1, after the completion of stirring reaction 5h, eccentric cleaning drying after obtain two
Titanium-oxide-coated polystyrene core-shell microsphere；
Step 3：Coated by titanium dioxide polystyrene core-shell microsphere prepared by step 2 is placed in electric furnace at 500 DEG C and is incubated 3-6h,
Hollow hemisphere titanium dioxide is obtained after the completion of calcining；
The speed that reaction solution 2 is added dropwise to reaction solution 1 in the step 2 is 30-40 drops/min；
Heating rate when electric furnace is warming up to 500 DEG C in the step 3 is 2-4 DEG C/min.
2. the preparation method of a kind of hollow hemisphere titanium dioxide according to claim 1, it is characterised in that including following step
Suddenly：Water soluble starter includes potassium peroxydisulfate or ammonium persulfate in the step 1.
3. the preparation method of a kind of hollow hemisphere titanium dioxide according to claim 1, it is characterised in that including following step
Suddenly：The volume ratio of ethanol and acetonitrile is 3 in the mixed solution of step 2 ethanol/acetonitrile:1, its preparation method is that acetonitrile is molten
Liquid agitation and dropping is into ethanol solution.
4. the preparation method of a kind of hollow hemisphere titanium dioxide according to claim 1, it is characterised in that including following step
Suddenly：
Step 1：Using 6mL styrene as monomer, 0.5mL methacrylic acids are comonomer, are warming up to 75 DEG C in aqueous, add
Enter 0.1273g potassium peroxydisulfate initiators, react 8h, obtain milky white solution, after washing centrifugation, obtain Properties of Polystyrene Nano Particles
Powder；
Step 2：0.3g Properties of Polystyrene Nano Particles powder, 0.5mL ammoniacal liquor are added in the mixed solution of 100mL ethanol/acetonitriles,
Ethanol/acetonitrile volume ratio is 3:1,10min is stirred, labeled as reaction solution 1；0.5mL butyl titanates are added into 20mL ethanol/acetonitriles
Mixed solution, ethanol/acetonitrile volume ratio be 3:1, stirring mark after its dissolving is 2；Then reaction solution 2 is added dropwise
Into reaction solution 1,30 drops/min, after the completion of stirring reaction 5h, eccentric cleaning drying after obtain coated by titanium dioxide polystyrene
Core-shell particles；
Step 3：Coated by titanium dioxide polystyrene core-shell microsphere prepared by step 2 is placed in electric furnace, is warming up to 2 DEG C/min
500 DEG C and 3h is incubated, hollow hemisphere titanium dioxide is obtained after the completion of calcining.
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| CN112225247B (en) * | 2020-10-20 | 2023-04-07 | 桂林理工大学 | Nano titanium dioxide open hollow sphere and preparation method thereof |
| CN114643077B (en) * | 2022-03-02 | 2023-09-26 | 湖北大学 | Microporous gel polymer with photocatalytic activity and preparation method thereof |
| CN115849447B (en) * | 2022-12-14 | 2023-11-07 | 扬州大学 | Molybdenum dioxide@titanium dioxide@nitrogen doped carbon nanocomposite and preparation method of lithium ion battery negative electrode thereof |
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| CN102174276B (en) * | 2011-03-09 | 2013-03-20 | 东南大学 | Method for preparing cerium-doped hollow nano titanium dioxide yellow pigment for electronic paper |
| CN102275983B (en) * | 2011-07-18 | 2013-04-24 | 北京科技大学 | Titanium dioxide bowl-shaped particles or dumbbell-shaped hollow particles and preparation method thereof |
| CN103848993B (en) * | 2014-01-16 | 2016-01-13 | 南京理工大学 | Hollow TiO 2the preparation method of microsphere surface grafting polyimide composite particles |
| CN103803643B (en) * | 2014-03-03 | 2016-01-27 | 福州大学 | Spherical titanium dioxide of a kind of monodisperse mesoporous hollow Nano and preparation method thereof |
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