CN107344118B - TiO with controllable surface growth morphology for preparing porous resin microspheres2Method (2) - Google Patents
TiO with controllable surface growth morphology for preparing porous resin microspheres2Method (2) Download PDFInfo
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- CN107344118B CN107344118B CN201710637867.1A CN201710637867A CN107344118B CN 107344118 B CN107344118 B CN 107344118B CN 201710637867 A CN201710637867 A CN 201710637867A CN 107344118 B CN107344118 B CN 107344118B
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- 239000011347 resin Substances 0.000 title claims abstract description 50
- 229920005989 resin Polymers 0.000 title claims abstract description 50
- 239000004005 microsphere Substances 0.000 claims abstract description 91
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000013329 compounding Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 13
- 239000010936 titanium Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 16
- -1 polytetrafluoroethylene Polymers 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- 229910001220 stainless steel Inorganic materials 0.000 claims description 11
- 239000010935 stainless steel Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- SQKIRAVCIRJCFS-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.C=CC1=CC=CC=C1C=C SQKIRAVCIRJCFS-UHFFFAOYSA-N 0.000 claims 1
- OYJAVFDOALZIRF-UHFFFAOYSA-N 2-methylprop-2-enoic acid;2-(2-methylprop-2-enoyloxy)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(O)=O.CC(=C)C(=O)OCCOC(=O)C(C)=C OYJAVFDOALZIRF-UHFFFAOYSA-N 0.000 claims 1
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 12
- 239000011159 matrix material Substances 0.000 abstract description 7
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 5
- MOYYRJZUAMTDQI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;oxiran-2-ylmethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1CO1.C=CC1=CC=CC=C1C=C MOYYRJZUAMTDQI-UHFFFAOYSA-N 0.000 description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- BHHCZVFCISJWIX-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 2-methylprop-2-enoate;oxiran-2-ylmethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1CO1.CC(=C)C(=O)OCCOC(=O)C(C)=C BHHCZVFCISJWIX-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003094 microcapsule Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
- B01J35/33—Electric or magnetic 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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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
- 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
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention relates to a method for preparing porous resin microspheres and TiO with controllable surface growth morphology2The method takes porous resin microspheres as a matrix, and grows inorganic semiconductor TiO on the surface of the porous resin microspheres through a hydrothermal process2Preparing to obtain porous resin microsphere/TiO2And (3) compounding the microspheres. TiO on porous resin microsphere surface2The morphology can be effectively regulated and controlled by adjusting the pore structure of the resin, the dosage of the titanium source, the reaction time and the like. Porous resin microsphere/TiO2Composite microsphere with porous high specific surface area of resin microsphere matrix and TiO2The catalytic property, namely the adsorption and degradation advantages of the material are obvious, so the material has wide application prospect in the field of environmental science.
Description
Technical Field
The invention belongs to the technical field of new materials, and relates to a method for preparing porous resin microspheres and TiO with controllable surface growth morphology2The method specifically comprises the steps of taking porous resin microspheres as a matrix, and growing TiO with controllable morphology on the surface of the porous resin microspheres through a hydrothermal process2Thereby preparing porous resin microsphere/TiO2A method for compounding microspheres.
Background
In recent years, TiO2TiO with the shapes of flaky, spherical, rod-shaped, hollow, mesoporous, cluster and the like which are frequently reported in the aspect of controlling preparation2The dye can be prepared by a synthesis method and regulation and control of process conditions, and the application research of the dye in the aspect of dye degradation is limited by the contradiction between high specific surface area and high-efficiency recovery efficiency. Researchers have found that in quartzTiO can be realized on glass (ZL201410346487.9), ITO or FTO conductive glass (ZL201210358379.4) and a ceramic substrate (ZL201310422337.7)2Guided growth of burrs or clusters of flowers, this high specific surface area supported TiO2The method has good effect in photoelectric conversion and dye degradation application. With the continuous development of material preparation technology and the continuous enrichment of material types, resin microspheres are taken as a matrix and TiO is taken as2Composite microspheres as modifiers are receiving more and more extensive attention. TiO is deposited or coated on the surface of the polymer microsphere at present2The method mainly comprises the steps of firstly synthesizing polymer microspheres or microcapsules, and then coating TiO on the surfaces of the polymer microspheres or microcapsules by a sol-gel method2(ZL201110150864.8, CN201110150864.8, CN 201611120277.3). TiO with controllable growth morphology on the surface of the porous polymer microsphere is not seen yet2(rod-like, sphere-like) related reports.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a method for preparing porous resin microspheres with controllable surface growth morphology TiO2The method takes porous resin microspheres as a matrix and adopts a hydrothermal method to realize TiO on the surface of the porous resin microspheres2Nanorod, TiO2Controllable growth of the microspheres to prepare the porous resin microspheres/TiO with different shapes2And (3) compounding the microspheres.
Technical scheme
TiO with controllable surface growth morphology for preparing porous resin microspheres2The method is characterized by comprising the following steps:
step 1: adding a titanium source solution into porous resin microspheres, ultrasonically dispersing, and transferring to a stainless steel hydrothermal reaction kettle with a polytetrafluoroethylene lining, wherein the mass ratio of the porous resin microspheres to the titanium source solution is 1: 10-15;
the titanium source solution is as follows: preparing a titanium source solution with the mass concentration of 50-200 g/L by using a hydrochloric acid solution with the concentration of 4-6 mol/L;
step 2: placing a stainless steel hot reaction kettle with a polytetrafluoroethylene lining in a high-temperature oven, slowly heating to 180-220 ℃, and reacting for 4-12 hours;
and step 3: after the reaction is finished, the stainless steel hydrothermal reaction kettle with the polytetrafluoroethylene lining is naturally cooled to room temperature, and the product is washed and centrifugally separated to obtain the porous resin microsphere/TiO2And (3) compounding the microspheres.
The titanium source is n-butyl titanate or tetraisopropyl titanate.
The porous resin microspheres are crosslinked styrene, acrylate or acrylonitrile porous polymer microspheres or porous magnetic composite microspheres.
The average pore diameter of the porous resin microspheres is more than 20 nm.
Advantageous effects
The invention provides a TiO with controllable surface growth morphology for preparing porous resin microspheres2The method takes porous resin microspheres as a matrix, and grows inorganic semiconductor TiO on the surface of the porous resin microspheres through a hydrothermal process2Preparing to obtain porous resin microsphere/TiO2And (3) compounding the microspheres. TiO on porous resin microsphere surface2The morphology can be effectively regulated and controlled by adjusting the pore structure of the resin, the dosage of the titanium source, the reaction time and the like. Porous resin microsphere/TiO2Composite microsphere with porous high specific surface area of resin microsphere matrix and TiO2The catalytic property, namely the adsorption and degradation advantages of the material are obvious, so the material has wide application prospect in the field of environmental science.
This surface-supported TiO compound2The magnetic composite microsphere has three obvious advantages in the aspect of photocatalytic degradation of organic pollutants in water: (1) TiO with bur or flower cluster shape on surface2The material has high specific surface area and good photoelectric conductivity; (2) the photocatalyst carrier microsphere has larger grain diameter, convenient and easy enrichment and reusability; (3) the porous polymer microsphere surface also has high adsorption capacity for pollutants and can exert a synergistic effect with a catalyst.
Drawings
FIG. 1 shows porous resin microspheres/TiO prepared at different growth times2Compounding the microspheres: 4h (A); 6h (B); 8h (C); 10h (D); 12h (E);
FIG. 2 shows porous magnetic resin microspheres/TiO prepared with different amounts of titanium source2The composite microspheres respectively comprise the following tetrabutyl titanate: 2g (a); 3g (B); 4g (C); 5g (D); 6g (E)
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
example 1: porous resin microsphere/TiO2Preparation of composite microspheres
Preparing a butyl titanate solution with the mass concentration of 100g/L, wherein the solvent is a hydrochloric acid solution with the concentration of 5 mol/L; 3.0g of porous poly (styrene-divinylbenzene) microspheres were added to 30g of the above n-butyl titanate solution and dispersed by ultrasound. Transferring the dispersed solution into a stainless steel hydrothermal reaction kettle with a polytetrafluoroethylene lining, placing the hydrothermal reaction kettle in a high-temperature oven, slowly heating to 180 ℃, reacting for 12 hours, naturally cooling to room temperature, washing the product with water, and performing centrifugal separation to obtain the porous poly (styrene-divinylbenzene) microspheres/TiO2And (3) compounding the microspheres.
Example 2: porous resin microsphere/TiO2Preparation of composite microspheres
Preparing tetraisopropyl titanate solution with the mass concentration of 100g/L, wherein the solvent is hydrochloric acid solution with the concentration of 5 mol/L; 2.5g of porous poly (glycidyl methacrylate-divinylbenzene) microspheres were added to 30g of the above tetraisopropyl titanate solution and dispersed ultrasonically. Transferring the dispersed solution into a stainless steel hydrothermal reaction kettle with a polytetrafluoroethylene lining, placing the hydrothermal reaction kettle into a high-temperature oven, slowly heating to 200 ℃, reacting for 6 hours, naturally cooling to room temperature, washing the product with water, and performing centrifugal separation to obtain the porous poly (glycidyl methacrylate-divinylbenzene) microspheres/TiO2And (3) compounding the microspheres.
Example 3: porous resin microsphere/TiO2Preparation of composite microspheres
Preparing a butyl titanate solution with the mass concentration of 100g/L, wherein the solvent is a hydrochloric acid solution with the concentration of 4 mol/L; 3.0g of porous poly (glycidyl methacrylate-divinylbenzene) microspheres were added to 30g of the above-mentioned n-butyl titanate solution and dispersed by ultrasound. Transferring the dispersed solution to a stainless steel hydrothermal reaction kettle with a polytetrafluoroethylene liningThen placing the hydrothermal reaction kettle in a high-temperature oven, slowly heating to 220 ℃, reacting for 9 hours, naturally cooling to room temperature, washing the product with water, and performing centrifugal separation to obtain the porous poly (glycidyl methacrylate-divinylbenzene) microspheres/TiO2And (3) compounding the microspheres.
Example 4: porous resin microsphere/TiO2Preparation of composite microspheres
Preparing a butyl titanate solution with the mass concentration of 100g/L, wherein the solvent is a hydrochloric acid solution with the concentration of 6 mol/L; 2.5g of porous poly (styrene-divinylbenzene) microspheres were added to 30g of the above n-butyl titanate solution and dispersed by ultrasound. Transferring the dispersed solution into a stainless steel hydrothermal reaction kettle with a polytetrafluoroethylene lining, placing the hydrothermal reaction kettle into a high-temperature oven, slowly heating to 220 ℃, reacting for 4 hours, naturally cooling to room temperature, washing the product with water, and performing centrifugal separation to obtain the porous poly (styrene-divinylbenzene) microspheres/TiO2And (3) compounding the microspheres.
Example 5: porous resin microsphere/TiO2Preparation of composite microspheres
Preparing tetraisopropyl titanate solution with the mass concentration of 100g/L, wherein the solvent is hydrochloric acid solution with the concentration of 4 mol/L; 2.2g of porous poly (glycidyl methacrylate-ethylene glycol dimethacrylate) microspheres were added to 33g of the above tetraisopropyl titanate solution and ultrasonically dispersed. Transferring the dispersed solution into a stainless steel hydrothermal reaction kettle with a polytetrafluoroethylene lining, placing the hydrothermal reaction kettle into a high-temperature oven, slowly heating to 200 ℃, reacting for 10 hours, naturally cooling to room temperature, washing the product with water, and performing centrifugal separation to obtain the porous poly (glycidyl methacrylate-ethylene glycol dimethacrylate) microspheres/TiO2And (3) compounding the microspheres.
Example 6: porous resin microsphere/TiO2Preparation of composite microspheres
Preparing a tetraisopropyl titanate solution with the mass concentration of 50g/L, wherein a solvent is a hydrochloric acid solution with the concentration of 6 mol/L; 3.0g of porous poly (styrene-divinylbenzene) microspheres were added to 33g of the above tetraisopropyl titanate solution and ultrasonically dispersed. Transferring the dispersed solution to a teflon linerPlacing the hydrothermal reaction kettle in a high-temperature oven, slowly heating to 200 deg.C, reacting for 8 hr, naturally cooling to room temperature, washing with water, and centrifuging to obtain porous poly (styrene-divinylbenzene) microsphere/TiO2And (3) compounding the microspheres.
Claims (1)
1. TiO with controllable surface growth morphology for preparing porous resin microspheres2The method is characterized by comprising the following steps:
step 1: adding a titanium source solution into porous resin microspheres, ultrasonically dispersing, and transferring to a stainless steel hydrothermal reaction kettle with a polytetrafluoroethylene lining, wherein the mass ratio of the porous resin microspheres to the titanium source solution is 1: 10-15;
the titanium source solution is as follows: preparing a titanium source solution with the mass concentration of 50-200 g/L by using a hydrochloric acid solution with the concentration of 4-6 mol/L;
step 2: placing a stainless steel hot reaction kettle with a polytetrafluoroethylene lining in a high-temperature oven, slowly heating to 180-220 ℃, and reacting for 4-12 hours;
and step 3: after the reaction is finished, the stainless steel hydrothermal reaction kettle with the polytetrafluoroethylene lining is naturally cooled to room temperature, and the product is washed and centrifugally separated to obtain the porous resin microsphere/TiO2Compounding the microspheres;
the average pore diameter of the porous resin microspheres is more than 20 nm;
the titanium source is n-butyl titanate or tetraisopropyl titanate;
the porous resin microspheres are polystyrene-divinylbenzene porous resin microspheres, polyglycidyl methacrylate-divinylbenzene porous resin microspheres or polyglycidyl methacrylate-ethylene glycol dimethacrylate porous resin microspheres;
the TiO with controllable appearance2The appearance of the material is in a burr shape or a flower cluster shape.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549204A (en) * | 2014-12-23 | 2015-04-29 | 中国科学院宁波材料技术与工程研究所 | Preparing method and application of titanium dioxide/carbon nano-micro spherical powder |
| CN104815637A (en) * | 2015-04-02 | 2015-08-05 | 西北师范大学 | Method for hydrothermal method preparation of graphene-loaded flower-type titanium dioxide composite material |
| CN105129849A (en) * | 2015-09-17 | 2015-12-09 | 上海大学 | Flowerlike nano-sized titanium dioxide material and template-free preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549204A (en) * | 2014-12-23 | 2015-04-29 | 中国科学院宁波材料技术与工程研究所 | Preparing method and application of titanium dioxide/carbon nano-micro spherical powder |
| CN104815637A (en) * | 2015-04-02 | 2015-08-05 | 西北师范大学 | Method for hydrothermal method preparation of graphene-loaded flower-type titanium dioxide composite material |
| CN105129849A (en) * | 2015-09-17 | 2015-12-09 | 上海大学 | Flowerlike nano-sized titanium dioxide material and template-free preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Preparation of PS/TiO2 core-shell microspheres and TiO2 hollow shells;JILIANG YIN etal.;《JOURNAL OF MATERIALS SCIENCE》;20031231;第4911–4916页 * |
| 二氧化钛/聚合物复合微球的制备及聚合物表面性质的影响研究;王宽等;《化工技术与开发》;20080531;第8-11页 * |
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