CN108640149B - Titanium dioxide nano hollow ball and preparation method thereof - Google Patents
Titanium dioxide nano hollow ball and preparation method thereof Download PDFInfo
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- CN108640149B CN108640149B CN201810529196.1A CN201810529196A CN108640149B CN 108640149 B CN108640149 B CN 108640149B CN 201810529196 A CN201810529196 A CN 201810529196A CN 108640149 B CN108640149 B CN 108640149B
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- hollow ball
- ethyl alcohol
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 240
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 114
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 58
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 26
- 239000004005 microsphere Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 21
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 238000005260 corrosion Methods 0.000 claims abstract description 9
- 230000007797 corrosion Effects 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 238000005253 cladding Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 132
- 229960004756 ethanol Drugs 0.000 claims description 54
- 235000019441 ethanol Nutrition 0.000 claims description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 35
- 239000002904 solvent Substances 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000011258 core-shell material Substances 0.000 claims description 17
- 230000001376 precipitating effect Effects 0.000 claims description 17
- 239000013049 sediment Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 15
- 239000012498 ultrapure water Substances 0.000 claims description 15
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 239000000908 ammonium hydroxide Substances 0.000 claims description 10
- 239000002585 base Substances 0.000 claims description 10
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000004090 dissolution Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 239000003518 caustics Substances 0.000 claims description 2
- 229910003087 TiOx Inorganic materials 0.000 claims 1
- 229910002026 crystalline silica Inorganic materials 0.000 claims 1
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 14
- 238000007146 photocatalysis Methods 0.000 abstract description 14
- 239000013078 crystal Substances 0.000 abstract description 13
- 239000002245 particle Substances 0.000 abstract description 7
- 230000002776 aggregation Effects 0.000 abstract description 5
- 238000011109 contamination Methods 0.000 abstract description 5
- 239000003344 environmental pollutant Substances 0.000 abstract description 5
- 230000002349 favourable effect Effects 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 231100000719 pollutant Toxicity 0.000 abstract description 5
- 238000005245 sintering Methods 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 12
- 230000015556 catabolic process Effects 0.000 description 9
- 238000006731 degradation reaction Methods 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 9
- 238000005216 hydrothermal crystallization Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 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
- 238000013459 approach Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 241000790917 Dioxys <bee> Species 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 229910003978 SiClx Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000002155 anti-virotic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- -1 it dries Chemical compound 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
Classifications
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
-
- 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—
-
- B01J35/51—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- 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
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The invention discloses a kind of preparation methods of titanium dioxide nano hollow ball.The preparation method uses first using tetraethyl orthosilicate as silicon sourceLegal system obtains silicon dioxide microsphere, then in silicon dioxide microsphere surface cladding titanium dioxide predecessor, then using alkali corrosion removal silica kernel, finally carries out hydro-thermal process, the crystalline titania nano-hollow ball that surface has sheet branched structure is made.Invention additionally discloses a kind of titanium dioxide nano hollow balls prepared using above-mentioned preparation method.Method of the invention is easy to operate, reproducible, without carrying out high temperature sintering, is suitble to large-scale production, avoids titanium dioxide powder and agglomeration occurs, process contamination is small, and product yield is high, and production cost is low；Obtained titanium dioxide nano hollow ball purity is high, particle is uniform, and well-crystallized, crystal form is controllable, favorable dispersibility, and many sheet branches are contained on surface, and large specific surface area is strong to the adsorption capacity and capture ability of pollutant, and photocatalysis efficiency is high.
Description
Technical field
The invention belongs to field of nanometer material technology, it is related to a kind of preparation method of titanium dioxide nano hollow ball, and uses
Its titanium dioxide nano hollow ball prepared.
Background technique
Nano material due to its structure and in terms of unique advantage, make current material supply section
The research hotspot in field.Nano-titanium dioxide have unique optical property and higher chemical stability, it is nontoxic, low at
This, catalytic activity it is high, and completely can with food and human contact, therefore nano-titanium dioxide suffered from numerous areas it is potential
Development prospect.Especially in photocatalysis field, it can use titanium dioxide semiconductor photochemical catalyst and convert solar energy into electricity
Energy and chemical energy.Titanium dioxide semiconductor photochemical catalyst can generate light induced electron and hole in illumination, and photohole has very
Strong oxidisability can achieve the purpose that antibacterial, antivirus, self-cleaning with photocatalysis degradation organic contaminant；And light induced electron has
Very strong reproducibility, can be not only used in environmental photocatlytsis, can prepare new energy with photocatalysis Decomposition aquatic products hydrogen.Therefore,
Titanium dioxide semiconductor photocatalysis technology has huge economy and environmental benefit in environmental improvement.
But titanium dioxide is absorbed optical range and is concentrated mainly on ultraviolet light due to wider band gap (3.0~3.2eV)
Region, and account in sunlight 90% visible light and be not used；In addition, light induced electron and hole-recombination rate are higher, light quantum
Utilization rate is lower, causes photocatalysis efficiency not high, limits its application range significantly.In order to which the photocatalysis for improving titanium dioxide is living
Property, people modify and are modified to it using various methods, including the control of ion doping, pattern, noble-metal-supported, semiconductor
It is the methods of compound.Wherein, pattern is controlled with easy to operate, mild condition, process contamination is small, easy to control, at low cost, yield is high
The advantages that.
It is the special of air or other gases that titanium dioxide nano hollow ball by pattern control preparation, which is a kind of kernel,
The core-shell particles of structure.Compared with the material of other patterns, the titanium dioxide nanometer microballoons of hollow structure have the advantage that tool
There are physical properties and the application values such as biggish specific surface area, lesser density, special mechanics, light, electricity.Therefore, titanium dioxide
Titanium nano-hollow ball can be used as covering material, catalyst carrier, nano-reactor and nano material, large biological molecule and drug
The carrier of sustained release has broad application prospects in the fields such as biology, medicine, bioengineering.
And using the universal surface of titanium dioxide nano hollow ball of existing method preparation round and smooth, specific surface area is not big enough, inhales
Attached ability is restricted, and then causes photocatalysis performance not high enough.In addition, in existing preparation titanium dioxide nano hollow ball
In method, need to handle by high temperature sintering, and sintering process not only causes high production cost, pollutes environment, product yield is not
Height is not suitable for large-scale production, and powder is easy to cause to generate hard aggregation phenomenon, and particle is uneven, bad dispersibility, product product
Matter is poor.
Summary of the invention
(1) technical problems to be solved
In order to solve the above problem of the prior art, the present invention provides a kind of preparation side of titanium dioxide nano hollow ball
Method, the preparation method is easy to operate, without carrying out high temperature sintering, is suitble to large-scale production, avoids titanium dioxide powder
Agglomeration, process contamination is small, and product yield is high, and production cost is low.
The present invention provides nano titania made from a kind of preparation method using above-mentioned titanium dioxide nano hollow ball
Hollow sphere, titanium dioxide nano hollow ball purity is high, particle is uniform, well-crystallized, favorable dispersibility, and many pieces are contained on surface
Shape branch can increase specific surface area, improve adsorption capacity and capture ability to pollutant, enhance photocatalysis efficiency.
(2) technical solution
In order to achieve the above object, the main technical schemes that the present invention uses are as follows:
The present invention provides a kind of titanium dioxide nano hollow ball, first using tetraethyl orthosilicate as silicon source, uses
Legal system obtains silicon dioxide microsphere, then in silicon dioxide microsphere surface cladding titanium dioxide predecessor, then is gone using alkali corrosion
Except silica kernel, hydro-thermal process is finally carried out, surface, which is made, has the crystalline titania nanometer of sheet branched structure empty
Bulbus cordis.
In a preferred embodiment, described using tetraethyl orthosilicate as silicon source, it usesLegal system obtains dioxy
SiClx microballoon includes:
Water, ethyl alcohol and ammonium hydroxide are mixed, solvent liquid I is prepared；
Tetraethyl orthosilicate is added in solvent liquid I, reaction is hydrolyzed in stirring at room temperature, is cleaned using ethyl alcohol, it dries,
Silicon dioxide microsphere is made.
In a preferred embodiment, during preparing solvent liquid I, the volume ratio of water, ethyl alcohol and ammonium hydroxide is
5:35-40:1；And/or
During silicon dioxide microsphere is made, the tetraethyl orthosilicate of 0.5-1.5mL is slowly added to solvent liquid I
In；And/or
Drying temperature is 50-80 DEG C.
In a preferred embodiment, described to include: in silicon dioxide microsphere surface cladding titanium dioxide predecessor
Water and ethyl alcohol are mixed, solvent liquid II is prepared；
Hydroxypropylcelliloxe is added in solvent liquid II, after completely dissolution, it is micro- that the silica prepared is added
Ball sufficiently dissolves, obtained solution A；
Butyl titanate and ethyl alcohol are mixed, solution B is prepared；
Solution B is added in solution A, mixed liquor is obtained, mixed liquor flows back later, is centrifugated, ethyl alcohol is finally used
The core-shell nano complex of titanium dioxide predecessor coated silica microballoon is made in cleaning.
In a preferred embodiment, during preparing solvent liquid II, the volume ratio of water and ethyl alcohol is 1:
150-300；And/or
During obtained solution A, the additive amount of Hydroxypropylcelliloxe is 50-150mg, silicon dioxide microsphere
Additive amount be 0.15-0.3g；And/or
During preparing solution B, the volume ratio of butyl titanate and ethyl alcohol is 1:3.5-5.5；And/or
During the core-shell nano complex of titanium dioxide predecessor coated silica microballoon is made, by 4-7mL
Solution B be added drop-wise in solution A in 10-20min, obtain mixed liquor, the reflux temperature of the mixed liquor is 70-95 DEG C, is returned
The stream time is 80-150min.
In a preferred embodiment, described to include: using alkali corrosion removal silica kernel
By the core-shell nano complex ultrasonic disperse Yu Shuizhong of titanium dioxide predecessor coated silica microballoon, it is added strong
Aqueous slkali stirs at 30-70 DEG C, forms solution C；
Precipitating is centrifuged in solution C, sediment is washed using ultrapure water and dehydrated alcohol, until solution connects
Sediment is dried weakly acidic pH, and amorphous titanium dioxide predecessor nano-hollow ball is made.
In a preferred embodiment, during forming solution C, the strong base solution be sodium hydroxide and/
Or potassium hydroxide solution, the concentration of the strong base solution are 1-3mol/L, the volume of the strong base solution is 0.5-2mL, is added
6-12h is stirred at 30-70 DEG C after strong base solution；And/or
During amorphous titanium dioxide predecessor nano-hollow ball is made, the temperature of the drying is 50-80
DEG C, the dry time is 8-15h.
In a preferred embodiment, the hydro-thermal process includes:
Water and ethyl alcohol are mixed, solution D is prepared；
By amorphous titanium dioxide predecessor nano-hollow ball ultrasonic disperse in solution D, hydro-thermal process, centrifuge separation
Precipitating, washs sediment using ultrapure water and dehydrated alcohol, dry, and the crystalline state that surface has sheet branched structure is made
Titanium dioxide nano hollow ball.
In a preferred embodiment, during preparing solution D, the volume ratio of water and ethyl alcohol is 1-2.5:1；
And/or
The temperature of the hydro-thermal process is 100-250 DEG C, and the time of hydro-thermal process is 6-12h, and the temperature of the drying is
50-80 DEG C, the dry time is 8-15h.
The present invention also provides a kind of preparation sides using titanium dioxide nano hollow ball described in any of the above-described embodiment
Titanium dioxide nano hollow ball made from method.
(3) beneficial effect
The present invention uses first using tetraethyl orthosilicate as silicon sourceLegal system obtains silicon dioxide microsphere, then two
Silicon oxide microsphere surface cladding titanium dioxide predecessor, then silica kernel is removed using alkali corrosion, finally carry out hydro-thermal
The crystalline titania nano-hollow ball that surface has sheet branched structure is made in processing.Nano titania of the invention is empty
The preparation method of bulbus cordis is easy to operate, reproducible, without carrying out high temperature sintering, is suitble to large-scale production, avoids titanium dioxide
Agglomeration occurs for titanium valve body, and process contamination is small, and product yield is high, and production cost is low.The titanium dioxide prepared using the method
Nano-hollow ball purity is high, particle is uniform, and well-crystallized, crystal form is controllable, favorable dispersibility, and many sheet branches are contained on surface,
Specific surface area can be increased, adsorption capacity and capture ability to pollutant is improved, enhance photocatalysis efficiency.
Detailed description of the invention
Fig. 1 is the flow diagram of titanium dioxide nano hollow ball preparation method in the embodiment of the present invention 1.
Fig. 2 is the X ray diffracting spectrum of titanium dioxide nano hollow ball in the embodiment of the present invention 1；
Fig. 3 is the transmission electron microscope picture of titanium dioxide nano hollow ball in the embodiment of the present invention 1；
Fig. 4 is the absorption of titanium dioxide nano hollow ball rhodamine B degradation solution under ultraviolet light in the embodiment of the present invention 1
Map；
Fig. 5 is titanium dioxide nano hollow ball and pure titinium dioxide ball rhodamine B degradation solution in the embodiment of the present invention 1
Linear fit curve spectrum.
Specific embodiment
In order to preferably explain the present invention, in order to understand, below by specific embodiment, present invention work is retouched in detail
It states.
A kind of method that present embodiment proposes titanium dioxide nano hollow ball, first using tetraethyl orthosilicate as silicon source,
UsingLegal system obtains silicon dioxide microsphere, then in silicon dioxide microsphere surface cladding titanium dioxide predecessor, then uses
Alkali corrosion removes silica kernel, finally carries out hydro-thermal process, and the crystalline state dioxy that surface has sheet branched structure is made
Change titanium nano-hollow ball.
In the present embodiment, it using tetraethyl orthosilicate as silicon source, usesLegal system obtains silicon dioxide microsphere
Following steps:
Water, ethyl alcohol and ammonium hydroxide are mixed according to the ratio that volume ratio is 5:35-40:1, prepare solvent liquid I；
The tetraethyl orthosilicate of 0.5-1.5mL is slowly added in solvent liquid I, stirs 5-12h at room temperature, is hydrolyzed anti-
It answers, then adopts and be washed several times with ethanol, dried at 50-80 DEG C, silicon dioxide microsphere is made.
In the present embodiment, in silicon dioxide microsphere surface cladding titanium dioxide predecessor the following steps are included:
Water and ethyl alcohol are mixed according to the ratio that volume ratio is 1:150-300, prepare solvent liquid II；
The Hydroxypropylcelliloxe of 50-150mg is added drop-wise in solvent liquid II, after completely dissolution, 0.15- is added
The silicon dioxide microsphere that 0.3g is prepared sufficiently dissolves, uniform mixed liquor is made, is denoted as solution A；
Butyl titanate and ethyl alcohol are mixed according to the ratio that volume ratio is 1:3.5-5.5, prepare solution B；
The solution B of 4-7mL is added drop-wise in solution A in 10-20min, mixed liquor is obtained, later by mixed liquor in 70-
95 DEG C of reflux 80-150min, centrifuge separation, finally adopt and are washed several times with ethanol, and titanium dioxide predecessor is made and coats titanium dioxide
The core-shell nano complex of silicon microballoon.
In the present embodiment, using alkali corrosion remove silica kernel the following steps are included:
By the core-shell nano complex ultrasonic disperse of above-mentioned titanium dioxide predecessor coated silica microballoon in 10-
In the water of 30mL, the strong base solution that 0.5-2mL concentration is 1-3mol/L is added, 6-12h is stirred at 30-70 DEG C, forms solution
C；Wherein strong base solution is sodium hydroxide solution and/or potassium hydroxide solution.
Precipitating is centrifuged in solution C under the conditions of 3000-4000rpm, using ultrapure water and dehydrated alcohol to heavy
Starch is washed, until solution approaches neutrality, sediment is dried 8-15h at 50-80 DEG C, amorphous titanium dioxide is made
Predecessor nano-hollow ball.
In the present embodiment, in order to make amorphous titanium dioxide predecessor nano-hollow ball have semiconductor crystal
Can, hydro-thermal process need to be carried out to amorphous titanium dioxide predecessor nano-hollow ball.Wherein hydro-thermal process the following steps are included:
Water and ethyl alcohol are mixed according to the ratio that volume ratio is 1-2.5:1, prepare solution D；
It disperses amorphous titanium dioxide predecessor nano-hollow ball sample ultrasonic in solution D, moves to reaction kettle,
Hydro-thermal 6-12h at 100-250 DEG C, centrifuge separation precipitating, washs sediment using ultrapure water and dehydrated alcohol, in 50-
Dry 8-15h at 80 DEG C, is made the crystalline titania nano-hollow ball that surface has sheet branched structure.
The present invention also provides titanium dioxide made from a kind of preparation method using above-mentioned titanium dioxide nano hollow ball
Nano-hollow ball.
Present invention employs template generate titanium dioxide nano hollow ball, i.e., first withOne step of method produces
Then silica coats upper titanium dioxide predecessor coating on its surface, removes dioxy using alkali corrosion as template
SiClx template finally carries out hydro-thermal process, obtains the titanium dioxide nano hollow ball of crystalline state.
Specifically, when manufacturing silica template, using tetraethyl orthosilicate as silicon source, regulator of the ammonium hydroxide as pH
And the catalyst that reaction occurs, it hydrolyzes tetraethyl orthosilicate slowly in the mixed liquor of water and ethyl alcohol, it is equal to generate size
One, the silicon dioxide microsphere of favorable dispersibility.
When carrying out titanium dioxide predecessor coating, using butyl titanate as titanium source, Hydroxypropylcelliloxe conduct
Dispersing agent and binder are attached to silicon dioxide molecules surface and form one layer of bilayer, and then adsorb titanium dioxide forerunner
Object makes titanium dioxide predecessor be uniformly adhered to silica layer surface, forms one layer of uniformly complete titanium dioxide forerunner
Object clad.
When removing silica kernel, use the sodium hydroxide solution of high concentration as corrosive agent, the hydroxyl in highly basic
Ion and silicon dioxde reaction generate silicate and water, and then get rid of silica kernel, then by ultrapure water and anhydrous
Ethyl alcohol is cleaned multiple times, and removes extra sodium hydroxide and Hydroxypropylcelliloxe.
Finally, hydro-thermal reaction is carried out in the mixed liquor of water and ethyl alcohol, since predecessor is in subcritical and postcritical water
Under heat condition, reaction is in molecular level, and reactivity improves, and predecessor is decomposed thermally to form oxide, is changed into crystalline state, then
By self assembly, the micro nano structure of different-shape is generated.
Ethyl alcohol is added in hydro-thermal solvent, the reactants and products of whole process is made to be uniformly dispersed, mobility increases, molecule
Between collision probability tend towards stability, thus the hydrolysis for inhibiting titanium dioxide predecessor violent.Therefore, the nucleation rate of crystal
Relatively slow with growth rate, crystal is intended to different growth, provides advantageous condition to the generation of laminated structure, then these
Particle derives sheet branch in titanium dioxide surface, obtains that there is the crystalline titania of sheet branch to receive by self assembly
Rice hollow sphere.
The preparation method of titanium dioxide nano hollow ball of the invention is easy to operate, reproducible, without carrying out high temperature burning
Knot is suitble to large-scale production, avoids titanium dioxide powder and agglomeration occurs, and process contamination is small, and product yield is high, is produced into
This is low.
The titanium dioxide nano hollow ball purity is high prepared using method of the invention, particle is uniform, well-crystallized, crystal form
Controllably, many sheet branches are contained on favorable dispersibility, surface, can increase specific surface area, improve the adsorption capacity to pollutant
And capture ability, enhance photocatalysis efficiency.
It is further illustrated by the examples that follow the present invention.
Embodiment 1
As shown in Figure 1, embodiment 1 proposes a kind of preparation method of titanium dioxide nano hollow ball, following step is specifically included
It is rapid:
1、SiO2The preparation of ball
1.1, Jiang Shui, ethyl alcohol and ammonium hydroxide are mixed according to the ratio that volume ratio is 5:37:1, prepare solvent liquid I；
1.2, the tetraethyl orthosilicate of 0.8mL is slowly added into above-mentioned solvent liquid I, stirs 8h at room temperature, carry out water
Solution reaction, is then washed several times with ethanol, dries at 60 DEG C, and the SiO of dispersion is made2Ball.
2、TiO2Predecessor coating
2.1, water and ethyl alcohol are mixed according to the ratio that volume ratio is 1:80, prepares solvent liquid II；
2.2, the Hydroxypropylcelliloxe of 80mg is added drop-wise in above-mentioned solvent liquid II.After completely dissolution, it is added
The SiO that 0.18g step 1 prepares2Ball sufficiently dissolves, obtains uniform mixed liquor, be denoted as solution A；
2.3, butyl titanate and ethyl alcohol are mixed according to the ratio that volume ratio is 1:4, prepares solution B；
2.4, the solution B of 6mL is added drop-wise in solution A in 10min, obtains mixed liquor, above-mentioned mixed liquor exists later
75 DEG C of reflux 90min, after centrifuge separation, finally adopt and are washed several times with ethanol, and titanium dioxide predecessor coated silica is made
The core-shell nano complex of microballoon.
3, SiO is removed2Core
3.1, by the core-shell nano complex ultrasound of titanium dioxide predecessor coated silica microballoon prepared above point
It dissipates in 10mL water, the sodium hydroxide solution that 0.7mL concentration is 1mol/L is added, stirs 8h at 40 DEG C, forms solution C；
3.2, solution C is taken out, precipitating is centrifugated under the conditions of 3500rpm, with ultrapure water and dehydrated alcohol to precipitating
Object is washed, until solution approaches neutrality, sediment is dried 12h at 60 DEG C, amorphous titanium dioxide predecessor is made
Nano-hollow ball, the hollow sphere be it is noncrystal, need to carry out it hydrothermal crystallization of step 4, it made to have semiconductor crystal
Energy.
4, hydrothermal crystallization
4.1, water and ethyl alcohol are mixed according to the ratio that volume ratio is 1.5:1, forms solution D；
4.2, it disperses amorphous titanium dioxide predecessor nano-hollow ball sample ultrasonic in solution D, moves to reaction
Kettle, hydro-thermal 10h at 120 DEG C, centrifuge separation precipitating wash sediment using ultrapure water and dehydrated alcohol, at 60 DEG C
The crystalline titania nano-hollow ball that surface has sheet branched structure is made in dry 12h.
Fig. 2 is the X ray diffracting spectrum of titanium dioxide nano hollow ball in embodiment 1, from figure 2 it can be seen that X-ray
Only there is TiO in diffracting spectrum2Anatase crystal diffraction maximum, without other crystal forms diffraction maximum generate, illustrate embodiment 1
Simple anatase crystal TiO is prepared2Hollow sphere.
Fig. 3 is the transmission electron microscope picture of titanium dioxide nano hollow ball in embodiment 1, as shown in figure 3, prepared by embodiment 1
TiO2The cavity diameter of hollow sphere is 230-300nm, wall thickness 45-65nm, meanwhile, sheet point is derived in hollow ball surface
Branch structure, lamella with a thickness of 3-5nm.
Embodiment 2
Embodiment 2 proposes a kind of preparation method of titanium dioxide nano hollow ball, specifically includes the following steps:
1、SiO2The preparation of ball
1.1, Jiang Shui, ethyl alcohol and ammonium hydroxide are mixed according to the ratio that volume ratio is 5:38:1, prepare solvent liquid I；
1.2, the tetraethyl orthosilicate of 1.0mL is slowly added into above-mentioned solvent liquid I, stirs 10h at room temperature, carry out water
Solution reaction, is then washed several times with ethanol, dries at 50 DEG C, and the SiO of dispersion is made2Ball.
2、TiO2Predecessor coating
2.1, water and ethyl alcohol are mixed according to the ratio that volume ratio is 1:130, prepares solvent liquid II；
2.2, the Hydroxypropylcelliloxe of 100mg is added drop-wise in above-mentioned solvent liquid II.After completely dissolution, it is added
The SiO that 0.25g step 1 prepares2Ball sufficiently dissolves, obtains uniform mixed liquor, be denoted as solution A；
2.3, butyl titanate and ethyl alcohol are mixed according to the ratio that volume ratio is 1:4.8, prepares solution B；
2.4, the solution B of 5mL is added drop-wise in solution A in 10min, obtains mixed liquor, above-mentioned mixed liquor exists later
85 DEG C of reflux 120min, after centrifuge separation, finally adopt and are washed several times with ethanol, and titanium dioxide predecessor coated silica is made
The core-shell nano complex of microballoon.
3, SiO is removed2Core
3.1, by the core-shell nano complex ultrasound of titanium dioxide predecessor coated silica microballoon prepared above point
It dissipates in 30mL water, the sodium hydroxide solution that 1.8mL concentration is 2.0mol/L is added, stirs 12h at 50 DEG C, forms solution C；
3.2, solution C is taken out, precipitating is centrifugated under the conditions of 3800rpm, with ultrapure water and dehydrated alcohol to precipitating
Object is washed, until solution approaches neutrality, sediment is dried 10h at 65 DEG C, amorphous titanium dioxide predecessor is made
Nano-hollow ball, the hollow sphere be it is noncrystal, need to carry out it hydrothermal crystallization of step 4, it made to have semiconductor crystal
Energy.
4, hydrothermal crystallization
4.1, water and ethyl alcohol are mixed according to the ratio that volume ratio is 2:1, forms solution D；
4.2, it disperses amorphous titanium dioxide predecessor nano-hollow ball sample ultrasonic in solution D, moves to reaction
Kettle, hydro-thermal 12h at 150 DEG C, centrifuge separation precipitating wash sediment using ultrapure water and dehydrated alcohol, at 80 DEG C
The crystalline titania nano-hollow ball that surface has sheet branched structure is made in dry 8h.
Embodiment 3
Embodiment 3 proposes a kind of preparation method of titanium dioxide nano hollow ball, specifically includes the following steps:
1、SiO2The preparation of ball
1.1, Jiang Shui, ethyl alcohol and ammonium hydroxide are mixed according to the ratio that volume ratio is 5:35:1, prepare solvent liquid I；
1.2, the tetraethyl orthosilicate of 1.2mL is slowly added into above-mentioned solvent liquid I, stirs 8h at room temperature, carry out water
Solution reaction, is then washed several times with ethanol, dries at 60 DEG C, and the SiO of dispersion is made2Ball.
2、TiO2Predecessor coating
2.1, water and ethyl alcohol are mixed according to the ratio that volume ratio is 1:200, prepares solvent liquid II；
2.2, the Hydroxypropylcelliloxe of 80mg is added drop-wise in above-mentioned solvent liquid II.After completely dissolution, it is added
The SiO that 0.2g step 1 prepares2Ball sufficiently dissolves, obtains uniform mixed liquor, be denoted as solution A；
2.3, butyl titanate and ethyl alcohol are mixed according to the ratio that volume ratio is 1:5, prepares solution B；
2.4, the solution B of 7mL is added drop-wise in solution A in 15min, obtains mixed liquor, above-mentioned mixed liquor exists later
90 DEG C of reflux 90min, after centrifuge separation, finally adopt and are washed several times with ethanol, and titanium dioxide predecessor coated silica is made
The core-shell nano complex of microballoon.
3, SiO is removed2Core
3.1, by the core-shell nano complex ultrasound of titanium dioxide predecessor coated silica microballoon prepared above point
It dissipates in 30mL water, the sodium hydroxide solution that 1.8mL concentration is 2.6mol/L is added, stirs 12h at 60 DEG C, forms solution C；
3.2, solution C is taken out, precipitating is centrifugated under the conditions of 4000rpm, with ultrapure water and dehydrated alcohol to precipitating
Object is washed, until solution approaches neutrality, sediment is dried 15h at 70 DEG C, amorphous titanium dioxide predecessor is made
Nano-hollow ball, the hollow sphere be it is noncrystal, need to carry out it hydrothermal crystallization of step 4, it made to have semiconductor crystal
Energy.
4, hydrothermal crystallization
4.1, water and ethyl alcohol are mixed according to the ratio that volume ratio is 2.5:1, forms solution D；
4.2, it disperses amorphous titanium dioxide predecessor nano-hollow ball sample ultrasonic in solution D, moves to reaction
Kettle, hydro-thermal 6h at 200 DEG C, centrifuge separation precipitating are washed sediment using ultrapure water and dehydrated alcohol, are done at 70 DEG C
The crystalline titania nano-hollow ball that surface has sheet branched structure is made in dry 10h.
Embodiment 4
Embodiment 4 proposes a kind of preparation method of titanium dioxide nano hollow ball, specifically includes the following steps:
1、SiO2The preparation of ball
1.1, Jiang Shui, ethyl alcohol and ammonium hydroxide are mixed according to the ratio that volume ratio is 5:40:1, prepare solvent liquid I；
1.2, the tetraethyl orthosilicate of 1.5mL is slowly added into above-mentioned solvent liquid I, stirs 12h at room temperature, carry out water
Solution reaction, is then washed several times with ethanol, dries at 80 DEG C, and the SiO of dispersion is made2Ball.
2、TiO2Predecessor coating
2.1, water and ethyl alcohol are mixed according to the ratio that volume ratio is 1:280, prepares solvent liquid II；
2.2, the Hydroxypropylcelliloxe of 140mg is added drop-wise in above-mentioned solvent liquid II.After completely dissolution, it is added
The SiO that 0.3g step 1 prepares2Ball sufficiently dissolves, obtains uniform mixed liquor, be denoted as solution A；
2.3, butyl titanate and ethyl alcohol are mixed according to the ratio that volume ratio is 1:5.5, prepares solution B；
2.4, the solution B of 7mL is added drop-wise in solution A in 20min, obtains mixed liquor, above-mentioned mixed liquor exists later
75 DEG C of reflux 150min, after centrifuge separation, finally adopt and are washed several times with ethanol, and titanium dioxide predecessor coated silica is made
The core-shell nano complex of microballoon.
3, SiO is removed2Core
3.1, by the core-shell nano complex ultrasound of titanium dioxide predecessor coated silica microballoon prepared above point
It dissipates in 20mL water, the sodium hydroxide solution that 1.2mL concentration is 1.5mol/L is added, stirs 6h at 70 DEG C, forms solution C；
3.2, solution C is taken out, precipitating is centrifugated under the conditions of 3000rpm, with ultrapure water and dehydrated alcohol to precipitating
Object is washed, until solution approaches neutrality, sediment is dried 8h at 80 DEG C, amorphous titanium dioxide predecessor is made and receives
Rice hollow sphere, the hollow sphere be it is noncrystal, need to carry out it hydrothermal crystallization of step 4, it made to have semiconductor crystal performance.
4, hydrothermal crystallization
4.1, water and ethyl alcohol are mixed according to the ratio that volume ratio is 1:1, forms solution D；
4.2, it disperses amorphous titanium dioxide predecessor nano-hollow ball sample ultrasonic in solution D, moves to reaction
Kettle, hydro-thermal 12h at 120 DEG C, centrifuge separation precipitating wash sediment using ultrapure water and dehydrated alcohol, at 65 DEG C
The crystalline titania nano-hollow ball that surface has sheet branched structure is made in dry 15h.
Application examples
Use ultraviolet source for 300W ultraviolet lamp, organic dyestuff is the rhodamine B solution of 30mg/L, utilizes UV, visible light point
Light photometer detects the titanium dioxide nano hollow ball of embodiment 1 as photochemical catalyst, and sieve in sample is sampled under different time
The absorbance of red bright B.According to bright ratio-Beer law, under Same Wavelength, the intensity of organic dyestuff absorption peak and its concentration are at just
Than.The absorption map of titanium dioxide nano hollow ball rhodamine B degradation solution under ultraviolet light is as shown in figure 4, UV Light
Time is followed successively by 0min, 5min, 10min, 15min, 20min from top to bottom.As seen from Figure 4, rhodamine B is in visibility region
The absorption peak of (wavelength is 500nm to 700nm) is as the time reduces, and the titanium dioxide nano hollow ball of embodiment 1 is in 20min
Ultraviolet degradation rate can reach 100%, wherein the calculation formula of degradation rate are as follows: (initial concentration C0Certain moment concentration Ci)/
C0* 100%.
As a comparison, the pure titinium dioxide ball of diameter similar is prepared for using sol-gal process, then respectively to pure dioxy
Change the survey of the titanium dioxide nano hollow ball progress ultraviolet catalytic degradating organic dye performance of titanium ball and the preparation of embodiment 1
The linear fit curve of examination, the two rhodamine B degradation solution under ultraviolet light is as shown in Figure 5.Linear matched curve is oblique in Fig. 5
Rate reflects photocatalysis efficiency (kinetics constant), i.e., slope is bigger, and photocatalysis efficiency is better.As seen from Figure 5, embodiment
Slope (the 0.32339min of the titanium dioxide hollow ball of 1 preparation-1) than the slope (0.0223min of pure titinium dioxide ball-1) big very
It is more, therefore the catalytic degradation efficiency of titanium dioxide hollow ball under ultraviolet light is higher than titanium dioxide ball.Main cause can be attributed to
Lower three aspects: 1. hollow shell structures greatly enhance the specific surface area of product, increase the reaction position of degradation of contaminant；
2. the main composition of hollow shell structure is the atom (surfaces externally and internally) on surface, when hollow shell structure is excited by illumination, more electricity
Son is excited to valence band, and surface has more holes and generates；3. titanium dioxide hollow ball surface prepared by the present invention is contained very
Splintery branch, these branches improve it to the adsorption capacity of pollutant and capture energy in entire hollow sphere surface extension
Power, to greatly enhance photocatalysis efficiency.
The technical principle that detailed description of the preferred embodimentsthe present invention has been described is combined above.These descriptions are intended merely to explain the present invention
Principle, and shall not be construed in any way as a limitation of the scope of protection of the invention.Based on the explanation herein, art technology
Personnel, which do not need to make the creative labor, can associate other specific embodiments of the invention, these modes fall within this
Within invention protection scope.
Claims (2)
1. a kind of preparation method of titanium dioxide nano hollow ball, it is characterised in that: first using tetraethyl orthosilicate as silicon source, adopt
WithLegal system obtains silicon dioxide microsphere, then in silicon dioxide microsphere surface cladding titanium dioxide predecessor, then using strong
Caustic corrosion removes silica kernel, finally carries out hydro-thermal process, and the crystalline silica that surface has sheet branched structure is made
Titanium nano-hollow ball；
Wherein, described using tetraethyl orthosilicate as silicon source, it usesLegal system obtains silicon dioxide microsphere
Water, ethyl alcohol and ammonium hydroxide are mixed, solvent liquid I is prepared；
Tetraethyl orthosilicate is added in solvent liquid I, reaction is hydrolyzed in stirring at room temperature, is cleaned using ethyl alcohol, dries, and is made
Silicon dioxide microsphere；
During preparing solvent liquid I, the volume ratio of water, ethyl alcohol and ammonium hydroxide is 5:35-40:1；
During silicon dioxide microsphere is made, the tetraethyl orthosilicate of 0.5-1.5mL is slowly added in solvent liquid I；It dries
Dry temperature is 50-80 DEG C；
It is described to include: in silicon dioxide microsphere surface cladding titanium dioxide predecessor
Water and ethyl alcohol are mixed, solvent liquid II is prepared；
Hydroxypropylcelliloxe is added in solvent liquid II, after completely dissolution, the silicon dioxide microsphere prepared is added, fills
Divide dissolution, obtained solution A；
Butyl titanate and ethyl alcohol are mixed, solution B is prepared；
Solution B is added in solution A, mixed liquor is obtained, mixed liquor flows back later, is centrifugated, is finally cleaned using ethyl alcohol,
The core-shell nano complex of titanium dioxide predecessor coated silica microballoon is made；
During preparing solvent liquid II, the volume ratio of water and ethyl alcohol is 1:150-300；
During obtained solution A, the additive amount of Hydroxypropylcelliloxe is 50-150mg, and silicon dioxide microsphere adds
Dosage is 0.15-0.3g；
During preparing solution B, the volume ratio of butyl titanate and ethyl alcohol is 1:3.5-5.5；Before titanium dioxide is made
During the core-shell nano complex for driving object coated silica microballoon, the solution B of 4-7mL is added drop-wise in 10-20min
In solution A, mixed liquor is obtained, the reflux temperature of the mixed liquor is 70-95 DEG C, return time 80-150min；
It is described to include: using alkali corrosion removal silica kernel
By the core-shell nano complex ultrasonic disperse Yu Shuizhong of titanium dioxide predecessor coated silica microballoon, it is molten that highly basic is added
Liquid stirs at 30-70 DEG C, forms solution C；
Precipitating is centrifuged in solution C, sediment is washed using ultrapure water and dehydrated alcohol, until solution is in
Property, sediment is dried, amorphous titanium dioxide predecessor nano-hollow ball is made；
During forming solution C, the strong base solution is sodium hydroxide and/or potassium hydroxide solution, the strong base solution
Concentration be 1-3mol/L, the volume of the strong base solution is 0.5-2mL, stirs 6- at 30-70 DEG C after strong base solution is added
12h；
During amorphous titanium dioxide predecessor nano-hollow ball is made, the temperature of the drying is 50-80 DEG C, is done
The dry time is 8-15h；
The hydro-thermal process includes:
Water and ethyl alcohol are mixed, solution D is prepared；
By amorphous titanium dioxide predecessor nano-hollow ball ultrasonic disperse in solution D, hydro-thermal process, centrifuge separation is sunk
It forms sediment, sediment is washed using ultrapure water and dehydrated alcohol, it is dry, the crystalline state two that surface has sheet branched structure is made
TiOx nano hollow sphere.
2. the preparation method of titanium dioxide nano hollow ball as described in claim 1, it is characterised in that: preparing solution D
In the process, the volume ratio of water and ethyl alcohol is 1-2.5:1；
The temperature of the hydro-thermal process is 100-250 DEG C, and the time of hydro-thermal process is 6-12h, and the temperature of the drying is 50-80
DEG C, the dry time is 8-15h.
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