CN102976404A - Preparation method of three-dimensional ordered macroporous titanium dioxide material - Google Patents
Preparation method of three-dimensional ordered macroporous titanium dioxide material Download PDFInfo
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- CN102976404A CN102976404A CN2012105434756A CN201210543475A CN102976404A CN 102976404 A CN102976404 A CN 102976404A CN 2012105434756 A CN2012105434756 A CN 2012105434756A CN 201210543475 A CN201210543475 A CN 201210543475A CN 102976404 A CN102976404 A CN 102976404A
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Abstract
The invention discloses a preparation method of a three-dimensional ordered macroporous titanium dioxide material, and the preparation method comprises the following steps of: at a certain temperature, carrying out constant temperature evaporation and self-assembly on a binary-component mixed solution formed by monodisperse polystyrene microspheres emulsion and titanium dioxide sol to form a binary ordered material; and removing a template agent by roasting to form the three-dimensional ordered macroporous titanium dioxide material. In the three-dimensional ordered macroporous titanium dioxide material, titanium dioxide has anatase and a macroporous/ mesoporous double-pore structure; the average pore sizes of macropores and mesoporous are respectively 220-336nm and 3-6nm; and the specific surface area is 240-350m<2>/g. The aperture size of the three-dimensional ordered macroporous titanium dioxide material can be controlled and adjusted by the microsphere size of the template agent polystyrene.
Description
Technical field
The invention belongs to three-dimensional ordered macroporous material preparation field, particularly relate to the technology of preparing of three-dimensional ordered macroporous titanium dioxide.
Background technology
Three-dimensional ordered macroporous material have pore structure arrange periodically strong, pore size distribution is narrow, the even a series of characteristics such as the adjustable and three-dimensional long-range order of one-piece construction of hole dimension, can application and the aspects such as support of the catalyst, filtration and parting material, battery and thermal resistance material.
At present, three-dimensional ordered macroporous material generally adopts the brilliant masterplate legal system of glue standby, and its key step is: (1) preparation mono-dispersion microballoon, and be assembled into the brilliant masterplate of glue; (2) precursor of the three-dimensional ordered macroporous material of the required target of filling in the masterplate gap; (3) remove masterplate and obtain three-dimensional ordered macroporous material.This kind preparation method's advantage is that equipment is simple, easy to operate, and the three-dimensional ordered macroporous material degree of order that obtains is high.But, also there is following obvious deficiency: the one, to fill and remove the contraction that is easy to cause macropore in the masterplate process, the highest contraction can reach 40%; The 2nd, can not prepare adequate thickness and the material of high-sequential degree is arranged; The 3rd, preparation time is long, sometimes reaches the several months, has hindered the application of three-dimensional ordered macroporous material.
The bibliographical information that has fully mixes rear natural subsidence with mono-dispersion microballoon with the precursor nanoparticle, and in the mono-dispersion microballoon self-assembly, the precursor nanoparticle begins to pile up in the space.The three-dimensional ordered macroporous material of the method for codeposition preparation thus, shrinking percentage obviously is reduced.But, the material thickness of preparation efficiency and preparation still do not have be improved significantly.
Summary of the invention
The present invention is directed to that present three-dimensional ordered macroporous material preparation efficiency is low, material thickness and physical strength be not enough to reach the problem that material is used to be needed, the preparation method who invents a kind of three-dimensional ordered macroporous titanium dioxide.
The objective of the invention is to be achieved through the following technical solutions: the preparation method of a kind of three-dimensional ordered macroporous titanic oxide material of the present invention, as masterplate take monodisperse polystyrene microsphere, binary blending ingredients with polystyrene microsphere emulsion-TiO 2 sol formation, obtain binary codeposition product through the evaporation self-assembly, this binary codeposition product obtains three-dimensional ordered macroporous titanic oxide material after high-temperature roasting removes the polystyrene masterplate.
The preparation method of a kind of three-dimensional ordered macroporous titanic oxide material of the present invention is as follows:
(1) in the polystyrene microsphere emulsion of single dispersion (dispersion coefficient 0.0030), add TiO 2 sol, sonic oscillation mixes, and obtains the binary composition mixed solution;
(2) binary composition mixed solution obtained above is placed glassware, under 40～80 ℃ of conditions of temperature, evaporation at constant temperature 4～8h obtains binary codeposition solid;
(3) with above-mentioned binary codeposition solid under 450～550 ℃, after roasting 2～4h, obtain three-dimensional ordered macroporous titanic oxide material behind the Slow cooling.
Polystyrene microsphere of the present invention is to use dispersion copolymerization method, or emulsion polymerization, or the standby dispersion coefficient of emulsifier-free emulsion polymerization legal system is 0.0030, the uniform microsphere of particle diameter between 240～380nm.
TiO 2 sol of the present invention is the stabilize water dispersion liquid of nano-titanium dioxide powder, titanium dioxide median size 10～20nm, content 20～25wt%.
The volume ratio of components of binary composition mixed solution of the present invention is: polystyrene emulsion: TiO 2 sol=30: 3.Wherein, the solid content of polystyrene emulsion is 7.0%, and solvent is isopyknic alcohol-water.
Beneficial effect of the present invention: select titanium dioxide nano-particle as the space of the brilliant masterplate of precursor filling glue, avoid using the titanium alkoxide, can overcome the unmanageable disadvantage of titanium alkoxide sol process conditional; Adopt evaporation at constant temperature method p-poly-phenyl vac emulsion-TiO 2 sol efficiently to assemble, it is the forced assembly under gravity, buoyancy and capillary force acting in conjunction, thereby accelerates assembling speed, and built-up time shortens to several hours; By regulating the concentration ratio of polystyrene emulsion-TiO 2 sol, can obtain the three-dimensional ordered macroporous titanic oxide material that thickness reaches centimetre-sized.
Description of drawings
Fig. 1 is the stereoscan photograph of the three-dimensional ordered macroporous titanic oxide material of embodiment 2 preparations.Can find out clearly that from photo this three-dimensional ordered macroporous titanic oxide material is the regular arrangement of three-dimensional order, the pore size distribution homogeneous is about 235nm, compares with masterplate agent polystyrene particle diameter, and shrinking percentage is 6%, interpenetrates by fenestella between duct and the duct.Form open three-dimensional order network structure.
Fig. 2 is the pore structure analysis result of the three-dimensional ordered macroporous titanic oxide material of embodiment 2 preparations.The result shows that this three-dimensional ordered macroporous titanic oxide material has meso-hole structure, and its mesoporous aperture is about 5nm, and specific surface area is long-pending to be 280m
2/ g.
Fig. 3 is the XRD analysis result of the three-dimensional ordered macroporous titanic oxide material of embodiment 3 preparations.Analytical results shows that this three-dimensional ordered macroporous titanic oxide material has the Anatase structure.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment.
Embodiment 1: in polystyrene microsphere (particle diameter 340nm) emulsion of the single dispersion of 30mL (dispersion coefficient 0.0030), add 3mL TiO 2 sol (particle diameter 12nm), sonic oscillation mixes, and obtains the binary composition mixed solution; Binary composition mixed solution obtained above is placed glassware, and under 40 ℃ of conditions of temperature, evaporation at constant temperature 5h obtains binary codeposition solid; Above-mentioned binary codeposition solid at 480 ℃, after the roasting 3h, is obtained three-dimensional ordered macroporous titanic oxide material behind the Slow cooling.
Embodiment 2: in polystyrene microsphere (particle diameter 250nm) emulsion of the single dispersion of 30mL (dispersion coefficient 0.0030), add 3mL TiO 2 sol (particle diameter 16nm), sonic oscillation mixes, and obtains the binary composition mixed solution; Binary composition mixed solution obtained above is placed glassware, and under the temperature 60 C condition, evaporation at constant temperature 5h obtains binary codeposition solid; Above-mentioned binary codeposition solid under 500 ℃, after the roasting 4h, is obtained titanium dioxide/heteropolyacid composite photo-catalyst behind the Slow cooling.Fig. 1 is this three-dimensional ordered macroporous titanic oxide material stereoscan photograph.Fig. 2 is the pore structure analysis of three-dimensional ordered macroporous titanic oxide material.
Embodiment 3: in single polystyrene microsphere (particle diameter 380nm) emulsion of disperseing (dispersion coefficient 0.0030) of 30mL, add 3mL TiO 2 sol (particle diameter 20nm) and, the sonic oscillation mixing obtains the binary composition mixed solution; Binary composition mixed solution obtained above is placed glassware, and under the temperature 60 C condition, evaporation at constant temperature 6h obtains binary codeposition solid; Above-mentioned binary codeposition solid under 520 ℃, after the roasting 3h, is obtained three-dimensional ordered macroporous titanic oxide material behind the Slow cooling.Fig. 3 is the X-ray diagram of this three-dimensional ordered macroporous titanic oxide material.
Embodiment 4: in polystyrene microsphere (particle diameter 290nm) emulsion of the single dispersion of 30mL (dispersion coefficient 0.0030), add 3mL TiO 2 sol (particle diameter 15nm), sonic oscillation mixes, and obtains the binary composition mixed solution; Binary composition mixed solution obtained above is placed glassware, and under the temperature 50 C condition, evaporation at constant temperature 5h obtains binary codeposition solid; Above-mentioned binary codeposition solid under 470 ℃, after the roasting 2h, is obtained three-dimensional ordered macroporous titanic oxide material behind the Slow cooling.
Claims (4)
1. the preparation method of a three-dimensional ordered macroporous titanic oxide material is characterized in that the preparation method is as follows:
(1) in the polystyrene microsphere emulsion of single dispersion (dispersion coefficient 0.0030), add TiO 2 sol, sonic oscillation mixes, and obtains the binary composition mixed solution;
(2) binary composition mixed solution obtained above is placed glassware, under 40～80 ℃ of conditions of temperature, evaporation at constant temperature 4～8h obtains binary codeposition solid;
(3) with above-mentioned binary codeposition solid under 500～600 ℃, after roasting 2～4h, obtain three-dimensional ordered macroporous titanic oxide material behind the Slow cooling.
2. a kind of preparation method of three-dimensional ordered macroporous titanic oxide material as claimed in claim 1, it is characterized in that: described monodisperse polystyrene microsphere is to use dispersion copolymerization method, or emulsion polymerization, or the standby dispersion coefficient of emulsifier-free emulsion polymerization legal system is 0.0030, the uniform microsphere of particle diameter between 240～380nm.
3. a kind of preparation method of three-dimensional ordered macroporous titanic oxide material as claimed in claim 1, it is characterized in that: described TiO 2 sol is the stabilize water dispersion liquid of nano-titanium dioxide powder, titanium dioxide median size 10～20nm, content 20～25wt%.
4. a kind of preparation method of three-dimensional ordered macroporous titanic oxide material as claimed in claim 1, it is characterized in that: the volume ratio of components of the described binary composition mixed solution of step (1) is: polystyrene emulsion: TiO 2 sol=30: 3.Wherein, the solid content of polystyrene emulsion is 7.0%, and solvent is isopyknic alcohol-water.
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| CN103730259A (en) * | 2013-12-27 | 2014-04-16 | 沈阳工业大学 | Nanocrystalline titanium dioxide film of two-specification pore structure and manufacturing method of nanocrystalline titanium dioxide film |
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| CN104773756A (en) * | 2015-03-30 | 2015-07-15 | 华东理工大学 | Titanium dioxide microsphere with hierarchical porous structure, and preparation method and application thereof |
| CN105304886A (en) * | 2015-09-23 | 2016-02-03 | 东莞市迈科科技有限公司 | Ordered macroporous titanium dioxide and preparation method thereof |
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| CN105502488A (en) * | 2016-02-01 | 2016-04-20 | 北京交通大学 | Preparation method for TiOx three-dimensionally ordered macroporous material |
| CN106158387A (en) * | 2015-04-17 | 2016-11-23 | 北京纳米能源与系统研究所 | Three-dimensional ordered macroporous structure titanium dioxide that nanoparticle is piled up and thin film and their preparation method and application |
| CN106747561A (en) * | 2016-12-06 | 2017-05-31 | 浙江大学 | The preparation method of macropore mayenite block |
| CN107347912A (en) * | 2016-05-10 | 2017-11-17 | 合肥杰事杰新材料股份有限公司 | A kind of preparation method of macroporous titanium dioxide carrying nano silver Antibacterial accessory ingredient |
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| CN103730259B (en) * | 2013-12-27 | 2016-08-17 | 沈阳工业大学 | A kind of nanocrystalline titanium dioxide film of two-specification pore structure and manufacturing method of nanocrystalline titanium dioxide film and preparation method thereof |
| CN103730259A (en) * | 2013-12-27 | 2014-04-16 | 沈阳工业大学 | Nanocrystalline titanium dioxide film of two-specification pore structure and manufacturing method of nanocrystalline titanium dioxide film |
| CN103981537A (en) * | 2014-05-06 | 2014-08-13 | 同济大学 | Preparation method and application of Pd/3DOM TiO2/BDD electrode used for photoelectrocatalytic reduction treatment of organic pollutants |
| CN103981537B (en) * | 2014-05-06 | 2016-06-15 | 同济大学 | The preparation method of the Pd/3DOM TiO2/BDD electrode of a kind of photoelectrocatalysis reduction treatment organic pollution and application thereof |
| CN104773756A (en) * | 2015-03-30 | 2015-07-15 | 华东理工大学 | Titanium dioxide microsphere with hierarchical porous structure, and preparation method and application thereof |
| CN106158387A (en) * | 2015-04-17 | 2016-11-23 | 北京纳米能源与系统研究所 | Three-dimensional ordered macroporous structure titanium dioxide that nanoparticle is piled up and thin film and their preparation method and application |
| CN105304886A (en) * | 2015-09-23 | 2016-02-03 | 东莞市迈科科技有限公司 | Ordered macroporous titanium dioxide and preparation method thereof |
| CN105295572A (en) * | 2015-12-04 | 2016-02-03 | 常熟市福达金属制件有限公司 | Novel iron hoop |
| CN105502488A (en) * | 2016-02-01 | 2016-04-20 | 北京交通大学 | Preparation method for TiOx three-dimensionally ordered macroporous material |
| CN105502488B (en) * | 2016-02-01 | 2017-03-15 | 北京交通大学 | A kind of TiOxThe preparation method of There-dimensional ordered macroporous materials |
| CN107347912A (en) * | 2016-05-10 | 2017-11-17 | 合肥杰事杰新材料股份有限公司 | A kind of preparation method of macroporous titanium dioxide carrying nano silver Antibacterial accessory ingredient |
| CN106747561A (en) * | 2016-12-06 | 2017-05-31 | 浙江大学 | The preparation method of macropore mayenite block |
| CN106747561B (en) * | 2016-12-06 | 2019-11-15 | 浙江大学 | The preparation method of macropore mayenite block |
| CN107973339A (en) * | 2017-11-24 | 2018-05-01 | 武汉理工大学 | The three-dimensional ordered macroporous calcium titanate photonic crystal and its synthetic method that a kind of porous nano-sheet is constructed |
| CN107973339B (en) * | 2017-11-24 | 2020-04-21 | 武汉理工大学 | Three-dimensional ordered macroporous calcium titanate photonic crystal constructed by porous nanosheets and synthetic method thereof |
| CN112030186A (en) * | 2020-08-13 | 2020-12-04 | 沧州信联化工有限公司 | Anode for preparing tetramethyl ammonium hydroxide by electrolysis |
| CN112030186B (en) * | 2020-08-13 | 2021-08-13 | 沧州信联化工有限公司 | Anode for preparing tetramethyl ammonium hydroxide by electrolysis |
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Application publication date: 20130320 |