CN108640149A - 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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- CN108640149A CN108640149A CN201810529196.1A CN201810529196A CN108640149A CN 108640149 A CN108640149 A CN 108640149A CN 201810529196 A CN201810529196 A CN 201810529196A CN 108640149 A CN108640149 A CN 108640149A
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- titanium dioxide
- hollow ball
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- 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 260
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 115
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 113
- 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 22
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 10
- 238000005253 cladding Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 132
- 235000019441 ethanol Nutrition 0.000 claims description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 36
- 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
- 238000001556 precipitation Methods 0.000 claims description 17
- 239000013049 sediment Substances 0.000 claims description 17
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 15
- 239000012498 ultrapure water Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 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
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 241000790917 Dioxys <bee> Species 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 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
- 230000008859 change Effects 0.000 claims description 2
- 229910003087 TiOx Inorganic materials 0.000 claims 1
- 230000003628 erosive effect Effects 0.000 claims 1
- 238000005530 etching Methods 0.000 claims 1
- 125000004494 ethyl ester group Chemical group 0.000 claims 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 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
- 238000005260 corrosion Methods 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 7
- 239000003513 alkali Substances 0.000 abstract description 6
- 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
- 239000000843 powder Substances 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
- 238000002156 mixing Methods 0.000 description 18
- 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
- 239000002585 base Substances 0.000 description 6
- 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
- 239000003054 catalyst Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000013459 approach Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000005119 centrifugation Methods 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
- 238000005516 engineering process Methods 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
- 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
- 239000003518 caustics Substances 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
- 230000005611 electricity Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 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
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000011230 binding agent Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- -1 dries Chemical compound 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 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
- 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
- 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
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005215 recombination Methods 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
-
- 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
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- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
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- 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
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- 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
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- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01P2004/00—Particle morphology
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- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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Abstract
The invention discloses a kind of preparation methods of titanium dioxide nano hollow ball.The preparation method is first using tetraethyl orthosilicate as silicon source, silicon dioxide microsphere is obtained using Stobe legal systems, then in silicon dioxide microsphere surface cladding titanium dioxide predecessor, alkali corrosion is used to remove silica kernel again, hydro-thermal process is finally carried out, surface, which is made, has the crystalline titania nano-hollow ball of sheet branched structure.Invention additionally discloses a kind of titanium dioxide nano hollow balls prepared using above-mentioned preparation method.The method of the present 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, and 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, are related to a kind of preparation method of titanium dioxide nano hollow ball, and use
Its titanium dioxide nano hollow ball prepared.
Background technology
Nano material makes current material supply section since it is in the unique advantage of structure and photoelectrochemical behaviour etc.
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, electricity can be converted solar energy into using titanium dioxide semiconductor photochemical catalyst
Energy and chemical energy.Titanium dioxide semiconductor photochemical catalyst will produce 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 relatively low, causes photocatalysis efficiency not high, limits its application range significantly.Photocatalysis in order to improve titanium dioxide is lived
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.
The titanium dioxide nano hollow ball prepared by pattern control is that a kind of kernel is the special of air or other gases
The core-shell particles of structure.Compared with the material of other patterns, the titanium dioxide nanometer microballoons of hollow-core construction have the following advantages：Tool
There are physical properties and the application values such as larger specific surface area, smaller 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 the universal surface of titanium dioxide nano hollow ball for using existing method to prepare is 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 production cost high, pollutes environment, product yield is not
Height is not suitable for large-scale production, and is easy to cause powder and generates hard aggregation phenomenon, and particle is uneven, bad dispersibility, product product
Matter is poor.
Invention content
(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 ball, the titanium dioxide nano hollow ball purity is high, and 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, using Stobe methods
Silicon dioxide microsphere is made, then in silicon dioxide microsphere surface cladding titanium dioxide predecessor, then using alkali corrosion removal
Silica kernel finally carries out hydro-thermal process, and surface, which is made, has the crystalline titania nano-hollow of sheet branched structure
Ball.
In a preferred embodiment, described using tetraethyl orthosilicate as silicon source, dioxy is obtained using Stobe legal systems
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, 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, fully after dissolving, it is micro- that the silica prepared is added
Ball fully 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, later by mixed-liquor return, centrifuges, finally uses ethyl alcohol
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 of titanium dioxide predecessor coated silica microballoon in water, it is added strong
Aqueous slkali stirs at 30-70 DEG C, forms solution C；
Precipitation is centrifuged in solution C, sediment is washed using ultra-pure water and absolute ethyl 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 volume of a concentration of 1-3mol/L of the strong base solution, the strong base solution are 0.5-2ml, are added
After strong base solution 6-12h is stirred at 30-70 DEG C；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 centrifuges
Precipitation, washs sediment using ultra-pure water and absolute ethyl alcohol, dry, and surface, which is made, has the crystalline state of sheet branched structure
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 the titanium dioxide nano hollow ball described in any of the above-described embodiment
Titanium dioxide nano hollow ball made from method.
(3) advantageous effect
The present invention obtains silicon dioxide microsphere first using tetraethyl orthosilicate as silicon source, using Stobe legal systems, then in dioxy
SiClx microsphere surface cladding titanium dioxide predecessor, then silica kernel is removed using alkali corrosion, finally carry out at hydro-thermal
Reason, surface, which is made, has the crystalline titania nano-hollow ball of sheet branched structure.The nano titania of the present invention is hollow
The preparation method of ball is easy to operate, reproducible, without carrying out high temperature sintering, is suitble to large-scale production, avoids titanium dioxide
Agglomeration occurs for powder, and process contamination is small, and product yield is high, and production cost is low.The titanium dioxide prepared using the method is received
Rice hollow ball purity is high, and particle is uniform, and well-crystallized, crystal form is controllable, favorable dispersibility, and many sheet branches, energy are contained in surface
Enough increase specific surface area, improves adsorption capacity and capture ability to pollutant, enhance photocatalysis efficiency.
Description of the drawings
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
Collection of illustrative plates；
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 implementation mode
In order to preferably explain the present invention, in order to understand, below by specific implementation mode, present invention work is retouched in detail
It states.
Present embodiment proposes a kind of method of titanium dioxide nano hollow ball, first using tetraethyl orthosilicate as silicon source,
Silicon dioxide microsphere is obtained using Stobe legal systems, 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 surface, which is made, has the crystalline silica of sheet branched structure
Titanium nano-hollow ball.
In the present embodiment, using tetraethyl orthosilicate as silicon source, use Stobe legal systems obtain silicon dioxide microsphere include with
Lower step：
By water, ethyl alcohol and ammonium hydroxide according to volume ratio be 5:35-40:1 ratio mixing, prepares 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, on silicon dioxide microsphere surface, cladding titanium dioxide predecessor includes the following steps：
According to volume ratio it is 1 by water and ethyl alcohol:The ratio of 150-300 mixes, and prepares solvent liquid II；
The Hydroxypropylcelliloxe of 50-150mg is added drop-wise in solvent liquid II, fully after dissolving, 0.15- is added
The silicon dioxide microsphere that 0.3g is prepared fully dissolves, and uniform mixed liquor is made, is denoted as solution A；
According to volume ratio it is 1 by butyl titanate and ethyl alcohol:The ratio of 3.5-5.5 mixes, and prepares solution B；
The solution B of 4-7ml is added drop-wise in 10-20min in solution A, mixed liquor is obtained, later by mixed liquor in 70-
95 DEG C of reflux 80-150min, centrifuge, finally adopt and be 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, included the following steps using alkali corrosion removal silica kernel：
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 of a concentration of 1-3mol/L of 0.5-2ml 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.
Precipitation is centrifuged in solution C under the conditions of 3000-4000rpm, using ultra-pure water and absolute ethyl 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 includes the following steps：
According to volume ratio it is 1-2.5 by water and ethyl alcohol:1 ratio mixing, prepares solution D；
Amorphous titanium dioxide predecessor nano-hollow ball sample ultrasonic is scattered in solution D, reaction kettle is moved to,
Hydro-thermal 6-12h at 100-250 DEG C is centrifuged precipitation, is washed to sediment using ultra-pure water and absolute ethyl alcohol, in 50-
Dry 8-15h at 80 DEG C, surface, which is made, has the crystalline titania nano-hollow ball of 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 templates to generate titanium dioxide nano hollow ball, i.e., produces two first with one step of Stobe methods
Then silica coats upper titanium dioxide predecessor coating on its surface, titanium dioxide is removed using alkali corrosion as template
Silicon 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, conditioning agent of the ammonium hydroxide as pH
And the catalyst that reaction occurs, so that tetraethyl orthosilicate is slowly hydrolyzed 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
Dispersant 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 pass through ultra-pure 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, to 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, and advantageous condition is provided to the generation of laminated structure, then these
Particle derives sheet branch by self assembly, in titanium dioxide surface, obtains that there is the crystalline titania of sheet branch to receive
Rice hollow ball.
The preparation method of the titanium dioxide nano hollow ball of the present 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.
Titanium dioxide nano hollow ball purity prepared by method using the present invention is high, and 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
Suddenly：
1、SiO2The preparation of ball
1.1, Jiang Shui, ethyl alcohol and ammonium hydroxide are 5 according to volume ratio:37:1 ratio mixing, prepares 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, is dried at 60 DEG C, and the SiO of dispersion is made2Ball.
2、TiO2Predecessor coating
2.1, it is 1 according to volume ratio by water and ethyl alcohol:80 ratio mixing, prepares solvent liquid II；
2.2, the Hydroxypropylcelliloxe of 80mg is added drop-wise in above-mentioned solvent liquid II.Fully after dissolving, it is added
The SiO that 0.18g steps 1 prepare2Ball fully dissolves, obtains uniform mixed liquor, be denoted as solution A；
2.3, it is 1 according to volume ratio by butyl titanate and ethyl alcohol:4 ratio mixing, prepares solution B；
2.4, the solution B of 6ml is added drop-wise in 10min in solution A, obtains mixed liquor, above-mentioned mixed liquor exists later
75 DEG C of reflux 90min, after centrifugation, finally adopt and are washed several times with ethanol, 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 of a concentration of 1mol/L of 0.7ml is added, 8h is stirred at 40 DEG C, forms solution C；
3.2, solution C is taken out, precipitation is centrifuged under the conditions of 3500rpm, with ultra-pure water and absolute ethyl alcohol to precipitation
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 ball are noncrystal, need to carry out the hydrothermal crystallization of step 4 to it, it is made to have semiconductor crystal
Energy.
4, hydrothermal crystallization
4.1, it is 1.5 according to volume ratio by water and ethyl alcohol:1 ratio mixing, forms solution D；
4.2, amorphous titanium dioxide predecessor nano-hollow ball sample ultrasonic is scattered in solution D, moves to reaction
Kettle, hydro-thermal 10h at 120 DEG C are centrifuged precipitation, are washed to sediment using ultra-pure water and absolute ethyl alcohol, at 60 DEG C
Dry 12h, surface, which is made, has the crystalline titania nano-hollow ball of sheet branched structure.
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 ball.
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 ball is 230-300nm, wall thickness 45-65nm, meanwhile, sheet point is derived in hollow ball surface
The thickness of branch structure, lamella is 3-5nm.
Embodiment 2
Embodiment 2 proposes a kind of preparation method of titanium dioxide nano hollow ball, specifically includes following steps：
1、SiO2The preparation of ball
1.1, Jiang Shui, ethyl alcohol and ammonium hydroxide are 5 according to volume ratio:38:1 ratio mixing, prepares 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, is dried at 50 DEG C, and the SiO of dispersion is made2Ball.
2、TiO2Predecessor coating
2.1, it is 1 according to volume ratio by water and ethyl alcohol:130 ratio mixing, prepares solvent liquid II；
2.2, the Hydroxypropylcelliloxe of 100mg is added drop-wise in above-mentioned solvent liquid II.Fully after dissolving, it is added
The SiO that 0.25g steps 1 prepare2Ball fully dissolves, obtains uniform mixed liquor, be denoted as solution A；
2.3, it is 1 according to volume ratio by butyl titanate and ethyl alcohol:4.8 ratio mixing, prepares solution B；
2.4, the solution B of 5ml is added drop-wise in 10min in solution A, obtains mixed liquor, above-mentioned mixed liquor exists later
85 DEG C of reflux 120min, after centrifugation, finally adopt and are washed several times with ethanol, 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 of a concentration of 2.0mol/L of 1.8ml is added, 12h is stirred at 50 DEG C, forms solution C；
3.2, solution C is taken out, precipitation is centrifuged under the conditions of 3800rpm, with ultra-pure water and absolute ethyl alcohol to precipitation
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 ball are noncrystal, need to carry out the hydrothermal crystallization of step 4 to it, it is made to have semiconductor crystal
Energy.
4, hydrothermal crystallization
4.1, it is 2 according to volume ratio by water and ethyl alcohol:1 ratio mixing, forms solution D；
4.2, amorphous titanium dioxide predecessor nano-hollow ball sample ultrasonic is scattered in solution D, moves to reaction
Kettle, hydro-thermal 12h at 150 DEG C are centrifuged precipitation, are washed to sediment using ultra-pure water and absolute ethyl alcohol, at 80 DEG C
Dry 8h, surface, which is made, has the crystalline titania nano-hollow ball of sheet branched structure.
Embodiment 3
Embodiment 3 proposes a kind of preparation method of titanium dioxide nano hollow ball, specifically includes following steps：
1、SiO2The preparation of ball
1.1, Jiang Shui, ethyl alcohol and ammonium hydroxide are 5 according to volume ratio:35:1 ratio mixing, prepares 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, is dried at 60 DEG C, and the SiO of dispersion is made2Ball.
2、TiO2Predecessor coating
2.1, it is 1 according to volume ratio by water and ethyl alcohol:200 ratio mixing, prepares solvent liquid II；
2.2, the Hydroxypropylcelliloxe of 80mg is added drop-wise in above-mentioned solvent liquid II.Fully after dissolving, it is added
The SiO that 0.2g steps 1 prepare2Ball fully dissolves, obtains uniform mixed liquor, be denoted as solution A；
2.3, it is 1 according to volume ratio by butyl titanate and ethyl alcohol:5 ratio mixing, prepares solution B；
2.4, the solution B of 7ml is added drop-wise in 15min in solution A, obtains mixed liquor, above-mentioned mixed liquor exists later
90 DEG C of reflux 90min, after centrifugation, finally adopt and are washed several times with ethanol, 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 of a concentration of 2.6mol/L of 1.8ml is added, 12h is stirred at 60 DEG C, forms solution C；
3.2, solution C is taken out, precipitation is centrifuged under the conditions of 4000rpm, with ultra-pure water and absolute ethyl alcohol to precipitation
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 ball are noncrystal, need to carry out the hydrothermal crystallization of step 4 to it, it is made to have semiconductor crystal
Energy.
4, hydrothermal crystallization
4.1, it is 2.5 according to volume ratio by water and ethyl alcohol:1 ratio mixing, forms solution D；
4.2, amorphous titanium dioxide predecessor nano-hollow ball sample ultrasonic is scattered in solution D, moves to reaction
Kettle, hydro-thermal 6h at 200 DEG C are centrifuged precipitation, are washed to sediment using ultra-pure water and absolute ethyl alcohol, are done at 70 DEG C
Dry 10h, surface, which is made, has the crystalline titania nano-hollow ball of sheet branched structure.
Embodiment 4
Embodiment 4 proposes a kind of preparation method of titanium dioxide nano hollow ball, specifically includes following steps：
1、SiO2The preparation of ball
1.1, Jiang Shui, ethyl alcohol and ammonium hydroxide are 5 according to volume ratio:40:1 ratio mixing, prepares 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, carried out
Then hydrolysis is washed several times with ethanol, dried at 80 DEG C, and the SiO of dispersion is made2Ball.
2、TiO2Predecessor coating
2.1, it is 1 according to volume ratio by water and ethyl alcohol:280 ratio mixing, prepares solvent liquid II；
2.2, the Hydroxypropylcelliloxe of 140mg is added drop-wise in above-mentioned solvent liquid II.Fully after dissolving, it is added
The SiO that 0.3g steps 1 prepare2Ball fully dissolves, obtains uniform mixed liquor, be denoted as solution A；
2.3, it is 1 according to volume ratio by butyl titanate and ethyl alcohol:5.5 ratio mixing, prepares solution B；
2.4, the solution B of 7ml is added drop-wise in 20min in solution A, obtains mixed liquor, above-mentioned mixed liquor exists later
75 DEG C of reflux 150min, after centrifugation, finally adopt and are washed several times with ethanol, 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 of a concentration of 1.5mol/L of 1.2ml is added, 6h is stirred at 70 DEG C, forms solution C；
3.2, solution C is taken out, precipitation is centrifuged under the conditions of 3000rpm, with ultra-pure water and absolute ethyl alcohol to precipitation
Object is washed, until solution, close to neutrality, by sediment, dry 8h, obtained amorphous titanium dioxide predecessor are received at 80 DEG C
Rice hollow ball, the hollow ball are noncrystal, need to carry out the hydrothermal crystallization of step 4 to it, it is made to have semiconductor crystal performance.
4, hydrothermal crystallization
4.1, it is 1 according to volume ratio by water and ethyl alcohol:1 ratio mixing, forms solution D；
4.2, amorphous titanium dioxide predecessor nano-hollow ball sample ultrasonic is scattered in solution D, moves to reaction
Kettle, hydro-thermal 12h at 120 DEG C are centrifuged precipitation, are washed to sediment using ultra-pure water and absolute ethyl alcohol, at 65 DEG C
Dry 15h, surface, which is made, has the crystalline titania nano-hollow ball of sheet branched structure.
Application examples
Use ultraviolet source for 300W ultraviolet lamps, 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 is with its concentration at just
Than.The absorption collection of illustrative plates 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 is：(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, implement
Slope (the 0.32339min of titanium dioxide hollow ball prepared by example 1-1) than the slope (0.0223min of pure titinium dioxide ball-1) big
Very much, 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
Three aspects below：1. hollow shell structure greatly enhances the specific surface area of product, the reaction of degradation of contaminant is increased
Position；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
Electronics 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
Many sheet branches, these branches improve its adsorption capacity and capture to pollutant in entire hollow ball surface extension
Ability, to greatly enhance photocatalysis efficiency.
Above in association with the technical principle that detailed description of the preferred embodimentsthe present invention has been described.These descriptions are intended merely to explain the present invention
Principle, and limiting the scope of the invention cannot be construed in any way.Based on the explanation herein, art technology
Personnel need not make the creative labor the other specific implementation modes that can associate the present invention, these modes fall within this
Within invention protection domain.
Claims (10)
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
Silicon dioxide microsphere is obtained with Stobe legal systems, then in silicon dioxide microsphere surface cladding titanium dioxide predecessor, then uses highly basic
Erosion removal silica kernel, finally carries out hydro-thermal process, and surface, which is made, has the crystalline titania of sheet branched structure
Nano-hollow ball.
2. the preparation method of titanium dioxide nano hollow ball as described in claim 1, it is characterised in that：It is described with positive silicic acid four
Ethyl ester is silicon source, and obtaining silicon dioxide microsphere using Stobe legal systems 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, dries, and is made
Silicon dioxide microsphere.
3. the preparation method of titanium dioxide nano hollow ball as claimed in claim 2, it is characterised in that：Preparing solvent liquid I
During, 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 in solvent liquid I；With/
Or
Drying temperature is 50-80 DEG C.
4. the preparation method of titanium dioxide nano hollow ball as claimed in claim 3, it is characterised in that：It is described in silica
Microsphere surface cladding titanium dioxide predecessor includes：
Water and ethyl alcohol are mixed, solvent liquid II is prepared；
Hydroxypropylcelliloxe is added in solvent liquid II, fully after dissolving, the silicon dioxide microsphere prepared is added, fills
Divide dissolving, 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, later by mixed-liquor return, centrifuges, finally ethyl alcohol is used to clean,
The core-shell nano complex of titanium dioxide predecessor coated silica microballoon is made.
5. the preparation method of titanium dioxide nano hollow ball as claimed in claim 4, it is characterised in that：Preparing solvent liquid II
During, 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, and silicon dioxide microsphere adds
Dosage is 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 the molten of 4-7ml
Liquid B is added drop-wise in 10-20min in solution A, obtains mixed liquor, and the reflux temperature of the mixed liquor is 70-95 DEG C, when reflux
Between be 80-150min.
6. the preparation method of titanium dioxide nano hollow ball as claimed in claim 5, it is characterised in that：It is described rotten using highly basic
Etching off includes except silica kernel：
By the core-shell nano complex ultrasonic disperse of titanium dioxide predecessor coated silica microballoon in water, it is molten that highly basic is added
Liquid stirs at 30-70 DEG C, forms solution C；
Precipitation is centrifuged in solution C, sediment is washed using ultra-pure water and absolute ethyl alcohol, until solution is in
Property, sediment is dried, amorphous titanium dioxide predecessor nano-hollow ball is made.
7. the preparation method of titanium dioxide nano hollow ball as claimed in claim 6, it is characterised in that：Forming solution C
In the process, the strong base solution be sodium hydroxide and/or potassium hydroxide solution, a concentration of 1-3mol/L of the strong base solution,
The volume of the strong base solution is 0.5-2ml, and 6-12h is stirred at 30-70 DEG C after strong base solution is added；And/or
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.
8. the preparation method of titanium dioxide nano hollow ball as claimed in claims 6 or 7, it is characterised in that：At the hydro-thermal
Reason 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, it is heavy to centrifuge
It forms sediment, sediment is washed using ultra-pure water and absolute ethyl alcohol, dry, surface, which is made, has the crystalline state two of sheet branched structure
TiOx nano hollow ball.
9. the preparation method of titanium dioxide nano hollow ball as claimed in claim 8, it is characterised in that：Preparing solution D
In the process, 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.
10. dioxy made from a kind of preparation method using claim 1-9 any one of them titanium dioxide nano hollow balls
Change titanium nano-hollow ball.
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| CN110759705B (en) * | 2019-11-13 | 2021-08-13 | 湖北工业大学 | Preparation method of composite functional ceramsite |
| CN111617633A (en) * | 2020-07-02 | 2020-09-04 | 江苏博霖环保科技有限公司 | Preparation method for composite degradation of VOCs (volatile organic compounds) by multi-shell photocatalyst and activated carbon |
| CN114132959A (en) * | 2021-11-15 | 2022-03-04 | 武汉科技大学 | Core-shell structure B4C@TiO2Composite powder and preparation method thereof |
| CN114132959B (en) * | 2021-11-15 | 2024-04-02 | 武汉科技大学 | Core-shell structure B 4 C@TiO 2 Composite powder and preparation method thereof |
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