CN101077792A - Method for synthesizing anatase type crystallized titanium dioxide nano core-shell or hollow-shell structure material by aqueous phase one-step - Google Patents
Method for synthesizing anatase type crystallized titanium dioxide nano core-shell or hollow-shell structure material by aqueous phase one-step Download PDFInfo
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- CN101077792A CN101077792A CN 200610011968 CN200610011968A CN101077792A CN 101077792 A CN101077792 A CN 101077792A CN 200610011968 CN200610011968 CN 200610011968 CN 200610011968 A CN200610011968 A CN 200610011968A CN 101077792 A CN101077792 A CN 101077792A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 title claims abstract description 18
- 239000011258 core-shell material Substances 0.000 title abstract 2
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- 239000008346 aqueous phase Substances 0.000 title 1
- 239000004793 Polystyrene Substances 0.000 claims abstract description 38
- 229920002223 polystyrene Polymers 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 238000000746 purification Methods 0.000 claims abstract description 5
- 239000004005 microsphere Substances 0.000 claims description 26
- 239000000839 emulsion Substances 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 238000005119 centrifugation Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- -1 ammonium salt compound Chemical class 0.000 claims description 10
- 240000002853 Nelumbo nucifera Species 0.000 claims description 9
- 235000006508 Nelumbo nucifera Nutrition 0.000 claims description 9
- 235000006510 Nelumbo pentapetala Nutrition 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 230000005611 electricity Effects 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 241000282326 Felis catus Species 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 150000003512 tertiary amines Chemical group 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002243 precursor Substances 0.000 abstract description 5
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005245 sintering Methods 0.000 abstract description 4
- 238000003980 solgel method Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000004038 photonic crystal Substances 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 29
- 238000001132 ultrasonic dispersion Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000003916 acid precipitation Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002003 electron diffraction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 239000012867 bioactive agent Substances 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229940094522 laponite Drugs 0.000 description 1
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- SVBAPZTYWZGPKN-UHFFFAOYSA-N n-methyldodecan-1-amine;hydrochloride Chemical compound Cl.CCCCCCCCCCCCNC SVBAPZTYWZGPKN-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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Abstract
The invention relates to a preparation method of a core-shell-hollow-shell structure material, in particular to a method for synthesizing an anatase type crystallized titanium dioxide nano core-shell or hollow-shell structure material by one step in a water phase. The invention firstly utilizes the water-soluble titanium peroxide precursor to coat the nano titanium oxide layer on the surface of the polystyrene by a sol-gel method, and the shell layer titanium oxide is directly crystallized into anatase nano titanium dioxide in a water phase at a relatively low temperature without sintering. Furthermore, by controlling the precursor, the polystyrene core as the template can be spontaneously dissolved after the shell layer is formed and crystallized, so that the hollow shell structure of the nano titanium dioxide can be directly obtained in the water phase. Compared with the traditional preparation method, the method has the advantages of simple process, strong operability, relatively low cost, suitability for batch preparation, industrial production possibility, and wide application prospect in aspects of environmental purification, drug transportation, photonic crystals and the like.
Description
Technical field
The present invention relates to the preparation method of nucleocapsid-ghost structural material, particularly the method for water one-step synthesis Detitanium-ore-type crystallizing titanium dioxide nano nuclear-shell or ghost structural material.
Background technology
Nucleocapsid and hollow shell structure nano material be in catalysis, chromatography, and the bioactive agents protection, wastewater treatment, the great application prospect in fields such as macromole slow-releasing system, controlled preparation nucleocapsid and hollow shell structure nano material become the emphasis of people's research just day by day.Nano titanium oxide nucleocapsid and hollow shell structure make it in environmental purification owing to photocatalytic activity, catalysis, and coating, fields such as opto-electronic conversion are with a wide range of applications; Moreover, because titanium dioxide is in the low absorption of visible and near-infrared region and high specific refractory power, make nucleocapsid and hollow shell structure nano titanium dioxide ball become preparation photonic crystal ideal material, thereby make that also preparation nucleocapsid and hollow shell structure nano titanium dioxide ball become the focus in the synthetic field of present nanometer.By sol-gel method at first at the surperficial encasement layer material of mould material (being generally polymer microsphere), remove template by sintering or dissolving again and obtain hollow shell structure, obtained using widely (1.Imhof as a kind of synthetic nucleocapsid of routine and the method for ghost structural material, A., Preparation andcharacterization of titania-coated polystyrene spheres and hollow titania shells.Langmuir 2001,17, (12), 3579～3585.2.Caruso, R.A.; Susha, A.; Caruso, F., Multilayered titania, silica, and Laponite nanoparticle coatings on polystyrenecolloidal templates and resulting inorganic hollow spheres.Chemistry of Materials2001,13, (2), 400～409.3.Wang, D.B.; Song, C.X.; Lin, Y.S.; Hu, Z.S., Preparation and characterization of TiO2 hollow spheres.Materials Letters 2006,60, (1), 77～80.).The nucleocapsid and the hollow shell structure semiconductor material that are different from other are synthetic, because the strong polarity of titanium ion, make its hydrolysis of control difficult relatively, therefore, report by sol-gel method water synthesis of titanium dioxide nucleocapsid and hollow shell structure is less relatively, alcoholysis then is widely used the organic compound that utilizes titanium as an alternative as presoma, but the defective of these class methods is outstanding equally, in order to obtain the titanium dioxide hollow shell structure of crystallization, high temperature sintering step or special hydrothermal reaction condition is absolutely necessary.Have numerous superiority by water miscible titanium precursor body material preparation titanium compound as titanium organic compound class presoma alternative, at first, from the angle of environment, water is synthetic can effectively to be reduced environmentally hazardous substance and uses and discharge; Secondly, water-soluble precursor can effectively reduce synthetic cost; At last, can show reduction titanium dioxide shell crystallization temperature by water is synthetic.
Summary of the invention
The object of the present invention is to provide a kind of simple and easy to controlly, respond well, be suitable for the water one-step synthesis Detitanium-ore-type crystallizing titanium dioxide nano nuclear-shell of large-scale commercial production or the method for ghost structural material.
The present invention utilize first the water-soluble titanium peroxide precursor by sol-gel method at polystyrene surface clad nano titanium oxide layer, shell titanium oxide (80～100 ℃) water direct crystallization under low relatively temperature be anatase octahedrite nano titanium oxide and need not sintering.Moreover, by control, can make shell after formation and crystallization, thereby spontaneous dissolving directly obtain the nano titanium oxide hollow shell structure at water as the polystyrene core of template to presoma pH.
Preparation method of the present invention at first disperses to obtain lotus positive electricity polystyrene milk sap with polystyrene spheres by cats product, thereby the water-soluble titanium peroxide presoma secondly by different pH values reacts with it and obtains final product.
The method of water one-step synthesis Detitanium-ore-type crystallizing titanium dioxide nano nuclear-shell of the present invention or ghost structural material may further comprise the steps:
(1). the positive electrical treating of polystyrene microsphere surface lotus
Utilize cats product in pure water, to disperse to obtain surperficial lotus positive electricity polystyrene microsphere emulsion again the powder polystyrene microsphere; Wherein, the mass percent of powder polystyrene microsphere and cationic surface agent alive is 0.001～10% in the emulsion, and polystyrene microsphere and pure water mass percent are 0.001～30%; The agent alive of described cationic surface is the derivative of organic amine;
(2). the preparation of water-soluble titanium presoma
Dissolve positive metatitanic acid with superoxol and obtain titanium peroxide solution, wherein, the molecule mole ratio of hydrogen peroxide and titanium ion is 50～1; The pH value of regulating titanium peroxide solution with ammoniacal liquor and hydrochloric acid is 0～10; Wherein, the mass percentage concentration of hydrogen peroxide is 1～30%, and the mass percentage concentration of ammoniacal liquor is 1～25%, and the concentration mass percentage concentration of hydrochloric acid is 1～37.2%;
(3) nucleocapsid structure product preparation
The titanium peroxide solution of pH=5～10 that step (2) is prepared and the surperficial lotus positive electricity polystyrene microsphere emulsion that step (1) obtains are (wherein, titanium peroxide solution and polystyrene microsphere emulsion volume volume ratio are to mix in 10: 1～1: 1, in temperature is 80～100 ℃ of following stirring reactions, the stirring reaction time is 0.1～12 hour, and obtaining with the crystallization anatase-type nanometer titanium dioxide is shell and polystyrene is the nucleocapsid structure product of nuclear; Or
The titanium peroxide solution of pH=0～5 that step (2) is prepared and the surperficial lotus positive electricity polystyrene microsphere emulsion that step (1) obtains are (wherein, titanium peroxide solution is 10: 1～1: 1 with polystyrene microsphere emulsion volume percent) mix, in temperature is 80～100 ℃ of following stirring reactions, the stirring reaction time is 0.1～12 hour, and obtaining with the crystallization anatase-type nanometer titanium dioxide is the hollow shell structure product of shell;
(4) purification of products
With the product centrifugation that step (3) prepares, centrifugation again after resulting precipitation is disperseed again with the pure water washing is also ultrasonic repeats above washing step three times; Then resulting precipitation is disperseed again with absolute ethanol washing is also ultrasonic, centrifugation, vacuum-drying obtain Detitanium-ore-type crystallizing titanium dioxide nano nuclear-shell or ghost structural material.
The used polystyrene microsphere of present method can be commercially available or utilize vinylbenzene to prepare for polymerizable raw material that particle diameter is 0.1～100 μ m.
The derivative of described organic amine is uncle's ammonium, secondary ammonium, tertiary amine, quaternary amines salt compound or their any mixture.
Described uncle's ammonium salt compounds has following structure R-NH
2HX; Described secondary ammonium salt compounds has following structure R-NHCH
3HX; Described tertiary amine salt compounds has following structure R-N (CH
3)
2HX; Described quaternary ammonium compound has following structure R-N (CH
3)
3X;
Wherein: R is C
5～C
16Alkyl chain, X is a halogen, as Br, Cl.
Present method can be regulated the radius of the nuclear of nucleocapsid structure by changing the polystyrene microsphere particle diameter.
The present invention compares with the traditional preparation process method, and method flow of the present invention is simple, and is workable, relative cost is cheap simultaneously, is applicable to batch preparations, possesses the possibility of suitability for industrialized production, in environmental purification, medicament transport, aspects such as photonic crystal are with a wide range of applications.
Description of drawings
Figure 1A. the Detitanium-ore-type crystallizing titanium dioxide nano nuclear-shell structure product transmission electron microscope picture that the embodiment of the invention 1 is prepared.
Figure 1B. the Detitanium-ore-type crystallizing titanium dioxide nano nuclear-shell structure product sem photograph that the embodiment of the invention 1 is prepared.
The Detitanium-ore-type crystallizing titanium dioxide nano hollow shell structure product transmission electron microscope picture that Fig. 2 A. embodiment of the invention 2 is prepared.
The Detitanium-ore-type crystallizing titanium dioxide nano hollow shell structure product sem photograph that Fig. 2 B. embodiment of the invention 2 is prepared.
The Detitanium-ore-type crystallizing titanium dioxide nano hollow shell structure product sem photograph that Fig. 2 C. embodiment of the invention 2 is prepared.
Fig. 3. the Detitanium-ore-type crystallizing titanium dioxide nano hollow shell structure product X RD spectrogram that the embodiment of the invention 1,2 is prepared.
Embodiment
Embodiment 1:
Get commercially available 5g particle diameter and be about 200nm polystyrene microsphere powder, add the 0.25g cetyl trimethylammonium bromide as the dispersion agent ultra-sonic dispersion in the 1000ml pure water; Titanic Acid precipitation mass percentage concentration be 30% aqueous hydrogen peroxide solution (with the ratio of titanium ion mole molecule number be 4) dissolving, with mass percentage concentration is the pH=7 that 2.5% ammoniacal liquor is reconciled solution, this solution of 200ml is added in the above-mentioned polystyrene emulsion, in temperature is under 80～100 ℃, intense mechanical stirring and refluxing reaction 1 hour, the centrifugal product that obtains of 2500rpm speed, resulting product with pure water washing three times and ultrasonic disperse again after centrifugation again, again with absolute ethanol washing and ultrasonic dispersion again, centrifugation, drying obtain the nucleocapsid structure product.
The products therefrom pattern utilizes transmission electron microscope (referring to Figure 1A) and scanning electron microscope (referring to Figure 1B) to characterize.The products therefrom crystal structure analysis adopts the X ray electron diffraction instrument to characterize, and the result is referring to Fig. 3.
Embodiment 2:
Get commercially available 5g particle diameter and be about 200nm polystyrene microsphere powder, add the 0.25g palmityl trimethyl ammonium chloride as the dispersion agent ultra-sonic dispersion in the 1000ml pure water; Titanic Acid precipitation mass percentage concentration be 30% aqueous hydrogen peroxide solution (with the ratio of titanium ion mole molecule number be 4) dissolving, with mass percentage concentration is the pH=3 that 2.5% ammoniacal liquor is reconciled solution, this solution of 200ml is added in the above-mentioned polystyrene emulsion, in temperature is under 80～100 ℃, intense mechanical stirring and refluxing reaction 1 hour, the centrifugal product that obtains of 2500rpm speed, resulting product with pure water washing three times and ultrasonic disperse again after centrifugation again, again with absolute ethanol washing and ultrasonic dispersion again, centrifugation, drying obtain the hollow shell structure product.
The products therefrom pattern utilizes transmission electron microscope (referring to Fig. 2 A) and scanning electron microscope (referring to Fig. 2 B, 2C) to characterize.The products therefrom crystal structure analysis adopts the X ray electron diffraction instrument to characterize, and the result is referring to Fig. 3.
Embodiment 3:
Get commercially available 5g particle diameter and be about 500nm polystyrene microsphere powder, add 0.15g Trimethyllaurylammonium bromide and 0.15g Dodecyl trimethyl ammonium chloride as the dispersion agent ultra-sonic dispersion in the 1000ml pure water; Titanic Acid precipitation mass percentage concentration be 30% aqueous hydrogen peroxide solution (with the ratio of titanium ion mole molecule number be 4) dissolving, with mass percentage concentration is the pH=7 that 2.5% ammoniacal liquor is reconciled solution, this solution of 200ml is added in the above-mentioned polystyrene emulsion, in temperature is under 80～100 ℃, intense mechanical stirring and refluxing reaction 1 hour, the centrifugal product that obtains of 2500rpm speed, resulting product with pure water washing three times and ultrasonic disperse again after centrifugation again, again with absolute ethanol washing and ultrasonic dispersion again, centrifugation, drying obtain the nucleocapsid structure product.
Embodiment 4:
Get commercially available 5g particle diameter and be about 1 μ m polystyrene microsphere powder, add 0.15g dodecyl dimethyl brometo de amonio and 0.15g dodecyl methyl ammonium chloride as the dispersion agent ultra-sonic dispersion in the 1000ml pure water; Titanic Acid precipitation mass percentage concentration be 30% aqueous hydrogen peroxide solution (with the ratio of titanium ion mole molecule number be 4) dissolving, with mass percentage concentration is the pH=3 that 2.5% ammoniacal liquor is reconciled solution, this solution of 200ml is added in the above-mentioned polystyrene emulsion, in temperature is under 80～100 ℃, intense mechanical stirring and refluxing reaction 1 hour, the centrifugal product that obtains of 2500rpm speed, resulting product with pure water washing three times and ultrasonic disperse again after centrifugation again, again with absolute ethanol washing and ultrasonic dispersion again, centrifugation, drying obtain the hollow shell structure product.
Claims (6)
1. the method for water one-step synthesis Detitanium-ore-type crystallizing titanium dioxide nano nuclear-shell or ghost structural material is characterized in that this method may further comprise the steps:
(1). the positive electrical treating of polystyrene microsphere surface lotus
Utilize cats product in pure water, to disperse to obtain surperficial lotus positive electricity polystyrene microsphere emulsion again the powder polystyrene microsphere; Wherein, the mass percent of powder polystyrene microsphere and cationic surface agent alive is 0.001～10% in the emulsion, and polystyrene microsphere and pure water mass percent are 0.001～30%;
The agent alive of described cationic surface is the derivative of organic amine;
(2). the preparation of water-soluble titanium presoma
Dissolve positive metatitanic acid with superoxol and obtain titanium peroxide solution, wherein, the molecule mole ratio of hydrogen peroxide and titanium ion is 50～1; The pH value of regulating titanium peroxide solution with ammoniacal liquor and hydrochloric acid is 0～10;
(3) nucleocapsid structure product preparation
The titanium peroxide solution of pH=5～10 that step (2) is prepared mixes with the surperficial lotus positive electricity polystyrene microsphere emulsion that step (1) obtains, and wherein, the volume ratio of titanium peroxide solution and polystyrene microsphere emulsion is 10: 1～1: 1; In temperature is 80～100 ℃ of following stirring reactions, and obtaining with the crystallization anatase-type nanometer titanium dioxide is shell and polystyrene is the nucleocapsid structure product of nuclear; Or
The titanium peroxide solution of pH=0～5 that step (2) is prepared mixes with the surperficial lotus positive electricity polystyrene microsphere emulsion that step (1) obtains, and wherein, titanium peroxide solution and polystyrene microsphere emulsion volume percent are 10: 1～1: 1; In temperature is 80～100 ℃ of following stirring reactions, and obtaining with the crystallization anatase-type nanometer titanium dioxide is the hollow shell structure product of shell;
(4) purification of products
With the product centrifugation that step (3) prepares, washing, vacuum-drying obtains Detitanium-ore-type crystallizing titanium dioxide nano nuclear-shell or ghost structural material.
2. method according to claim 1 is characterized in that: the mass percentage concentration of hydrogen peroxide is 1～30% in the described step (2), and the mass percentage concentration of ammoniacal liquor is 1～25%, and the concentration mass percentage concentration of hydrochloric acid is 1～37.2%.
3. method according to claim 1 is characterized in that: the stirring reaction time described in the step (3) is 0.1～12 hour.
4. method according to claim 1 is characterized in that: the particle diameter of described polystyrene microsphere is 0.1～100 μ m.
5. method according to claim 1 is characterized in that: the derivative of described organic amine is uncle's ammonium, secondary ammonium, tertiary amine, quarternary ammonium salt compound or their any mixture.
6. method according to claim 1 is characterized in that: described uncle's ammonium salt compound has following structure R-NH
2HX; Described secondary ammonium salt compound has following structure R-NHCH
3HX; Described tertiary amine salt compound has following structure R-N (CH
3)
2HX; Described quarternary ammonium salt compound has following structure R-N (CH
3)
3X;
Wherein: R is C
5～C
16Alkyl chain, X are Br or Cl.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101879441A (en) * | 2010-07-12 | 2010-11-10 | 北京航空航天大学 | Microsphere TiO2 photocatalyst and preparation method thereof |
| CN101927164A (en) * | 2010-07-12 | 2010-12-29 | 北京航空航天大学 | Metallic ion-doping modification microsphere TiO2 photocatalyst and method for preparing same |
| CN102100926A (en) * | 2010-06-21 | 2011-06-22 | 浙江工业大学 | Medical titanium or titanium alloy surface activation modifying method |
| CN101659773B (en) * | 2009-09-28 | 2011-08-31 | 浙江理工大学 | Nano TiO2-polystyrene microsphere compound and preparation method and application thereof |
| CN101497067B (en) * | 2009-01-16 | 2011-11-09 | 北京航空航天大学 | Preparation method for assembling large-area ordered microsphere template by liquid level swirl method |
| CN101629031B (en) * | 2009-08-17 | 2012-07-04 | 湖北大学 | Photocatalytic functional coating and preparation method thereof |
| WO2013029203A1 (en) | 2011-08-31 | 2013-03-07 | 上海世展化工科技有限公司 | Inorganic non-metal mineral composite material carrying titanium dioxide layer, and preparation process and use thereof |
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| CN1194935C (en) * | 2003-07-31 | 2005-03-30 | 中国石油化工股份有限公司 | Core-shell structure nano titanium serial composition and its preparing method |
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