CN103613128A - Rapid preparation method of three-dimensional ordered macroporous titanium dioxide - Google Patents
Rapid preparation method of three-dimensional ordered macroporous titanium dioxide Download PDFInfo
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- CN103613128A CN103613128A CN201310508528.5A CN201310508528A CN103613128A CN 103613128 A CN103613128 A CN 103613128A CN 201310508528 A CN201310508528 A CN 201310508528A CN 103613128 A CN103613128 A CN 103613128A
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Abstract
The invention provides a rapid preparation method of three-dimensional ordered macroporous titanium dioxide by using a vacuum filling template method. The method is as below: filling a homogeneous transparent sol, formed by mixing anhydrous alcohol and tetrabutyl titanate, into template gaps in vacuum; then placing the template into a constant temperature and humidity chamber and controlling certain humidity and temperature for gelation; taking out the template and conducting natural air-drying for 24 h; and finally calcining the obtained sample under high temperature in a muffle furnace to remove the template, so as to obtain the three-dimensional ordered macroporous titanium dioxide with specific crystal form. Compared with a traditional method, the method provided by the invention is simple, practicable, and convenient for operation and has high efficiency, short filling time and few filling frequencies.
Description
Technical field
The present invention relates to a kind of method of the three-dimensional ordered macroporous titanium dioxide of preparation of filling in conjunction with vacuum filtration with sol-gel process, belong to new material technology field.
Background technology
It is a kind of wide bandgap semiconductor that titanium dioxide is done, and has non-toxic inexpensive, anti-photoetch, an advantage such as catalytic activity is high, oxidation capacity is strong, good stability, prepares specific surface area high, and the poriferous titanium dioxide that catalytic performance is good enjoys people's concern.With precursor liquid, colloidal crystal template being filled is to prepare poriferous titanium dioxide simple and efficient way, and its advantage is to utilize the colloidal crystal template of different size to synthesize the large pore material of different pore size size, and the large pore material of preparation connects mutually.But, with precursor liquid, fill colloidal crystal template method and prepare macroporous titanium dioxide material, be that material pattern or regularity etc. all have problems.Major cause, the one, precursor liquid is easily hydrolyzed, and is difficult to control its filling extent, and the 2nd, precursor liquid viscosity is larger, easily on macroporous titanium dioxide surface, forms tectum, causes material surface duct to be stopped up.If it is few to fill number of times, can cause and fill not exclusively, hole wall is very thin, causes hole wall collapse in calcination process; And fill number of times when more, and be easy at a large amount of titanium dioxide layer of colloidal crystal surface coverage, cause macropore capped, can not form the regular macroporous structure of mutual perforation.
Summary of the invention
The object of the invention is the deficiency existing for prior art, provide a kind of simple and effective, can prepare the fast preparation method of compound with regular structure, the intectate three-dimensional ordered macroporous titanic oxide material in surface.
For achieving the above object, the present invention has adopted following technical scheme:
A fast preparation method for three-dimensional ordered macroporous titanic oxide material, is characterized in that, comprises the following steps:
(1) by massfraction, be that the 5% monodisperse polystyrene microsphere aqueous solution (dispersion coefficient 0.005) is laid on clean slide glass, in humidity 40%, under temperature 60 C, evaporation 4h makes polystyrene colloid crystal film;
(2) by the colloidal crystal film preparing thermal treatment 30min at 100 ℃ of temperature, be chilled to after room temperature, on its surface, cover again one deck slide glass, and by two slide glass clip fixations, form two slide glasss of " sandwich " structure;
(3) tetrabutyl titanate is mixed with dehydrated alcohol, magnetic agitation 2 hours, obtains the precursor solution of homogeneous transparent;
(4) two slide glasss of " sandwich " structure are vertically put into precursor solution, under vacuum tightness-0.07MPa, keep taking out after vacuum 1min;
(5), by two slide glasss of populated " sandwich " structure, at temperature 60 C, humidity 40% time, allows precursor liquid fast hydrolyzing gelation in the middle of " sandwich " structure, seasoning 24h after taking out;
(6) slide glass is placed in to retort furnace, first with 3 ℃/min, is slowly warmed up to 300 ℃ of insulation 2h, then be warmed up to 500-800 ℃ of insulation 2h with 2 ℃/min, remove polystyrene colloid crystal template, obtain three-dimensional ordered macroporous titanic oxide material.
Further, the particle diameter of described polystyrene microsphere is 240nm～350nm.
Further, the volume ratio of described tetra-n-butyl titanate and dehydrated alcohol is 1:5～20.
Compared with prior art, tool of the present invention has the following advantages:
1. two slide glasss of " sandwich " of the present invention structure, when carrying out vacuum filling with precursor liquid p-poly-phenyl ethene colloidal crystal template, the thin force phenomenon of bistrichiasis of two slide glasss has promoted the filling of precursor liquid in masterplate gap, and surface covers without precursor liquid, the macroporous titanium dioxide material structure of preparation is regular, is accurately repeatedly making of colloidal crystal template.
2. the preparation method of a kind of three-dimensional ordered macroporous titanic oxide material of the present invention, " sandwich " features simple structure is effective, only needs vacuum filling once, has greatly shortened the time of preparing macroporous titanium dioxide material.
3. the preparation method of a kind of three-dimensional ordered macroporous titanic oxide material of the present invention, changes the size of polystyrene microsphere, can make the three-dimensional ordered macroporous titanium dioxide of different size.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the three-dimensional ordered macroporous titanic oxide material of embodiment 1 preparation.From photo, can find out clearly, this three-dimensional ordered macroporous titanic oxide material is the regular arrangement of three-dimensional order, between pore size distribution homogeneous duct and duct, by fenestella, interpenetrates.Form open three-dimensional order network structure.
Fig. 2 is the low temperature nitrogen adsorption-desorption graphic representation of the three-dimensional ordered macroporous titanic oxide material that makes of embodiment 2.Illustrate that the three-dimensional ordered macroporous titanic oxide material making has meso-hole structure.
Fig. 3 is the X-ray diffraction result that three-dimensional ordered macroporous titanic oxide material roasting under differing temps that embodiment 3 makes obtains.500～600 ℃ of roastings, mainly obtain anatase titanium dioxide, when temperature, bring up to 700 ℃ and when above, occur the titanium dioxide of sharp red stone crystal formation.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.But this should be interpreted as to the scope of the above-mentioned theme of the present invention only limits to following embodiment.
Embodiment 1:
(1) by massfraction, be that the 5% monodisperse polystyrene microsphere aqueous solution (particle diameter 265nm, dispersion coefficient 0.005) is laid on clean slide glass, in humidity 40%, under temperature 60 C, evaporation 4h makes polystyrene colloid crystal film;
(2) by the colloidal crystal film preparing thermal treatment 30min at 100 ℃ of temperature, be chilled to after room temperature, on its surface, cover again one deck slide glass, and by two slide glass clip fixations, form two slide glasss of " sandwich " structure;
(3) by tetrabutyl titanate and dehydrated alcohol by volume 1:5 mix, magnetic agitation 2 hours, obtains the precursor solution of homogeneous transparent;
(4) two slide glasss of " sandwich " structure are vertically put into precursor solution, under vacuum tightness-0.07MPa, keep taking out after vacuum 1min;
(5), by two slide glasss of populated " sandwich " structure, at temperature 60 C, humidity 40% time, allows precursor liquid fast hydrolyzing gelation in the middle of " sandwich " structure, seasoning 24h after taking out;
(6) slide glass is placed in to retort furnace, first with 3 ℃/min, is slowly warmed up to 300 ℃ of insulation 2h, then be warmed up to 600 ℃ of insulation 2h with 2 ℃/min, remove polystyrene colloid crystal template, obtain three-dimensional ordered macroporous titanic oxide material.
Fig. 1 is the surface of three-dimensional ordered macroporous titanic oxide material and the SEM in the cross section figure that embodiment 1 makes.
Embodiment 2:
(1) by massfraction, be that the 5% monodisperse polystyrene microsphere aqueous solution (particle diameter 310nm, dispersion coefficient 0.005) is laid on clean slide glass, in humidity 40%, under temperature 60 C, evaporation 4h makes polystyrene colloid crystal film;
(2) by the colloidal crystal film preparing thermal treatment 30min at 100 ℃ of temperature, be chilled to after room temperature, on its surface, cover again one deck slide glass, and by two slide glass clip fixations, form two slide glasss of " sandwich " structure;
(3) by tetrabutyl titanate and dehydrated alcohol by volume 1:10 mix, magnetic agitation 2 hours, obtains the precursor solution of homogeneous transparent;
(4) two slide glasss of " sandwich " structure are vertically put into precursor solution, under vacuum tightness-0.07MPa, keep taking out after vacuum 1min;
(5), by two slide glasss of populated " sandwich " structure, at temperature 60 C, humidity 40% time, allows precursor liquid fast hydrolyzing gelation in the middle of " sandwich " structure, seasoning 24h after taking out;
(6) slide glass is placed in to retort furnace, first with 3 ℃/min, is slowly warmed up to 300 ℃ of insulation 2h, then be warmed up to 700 ℃ of insulation 2h with 2 ℃/min, remove polystyrene colloid crystal template, obtain three-dimensional ordered macroporous titanic oxide material.
Fig. 2 is the low temperature nitrogen adsorption-desorption graphic representation of the three-dimensional ordered macroporous titanic oxide material that makes of embodiment 2.Illustrate that the three-dimensional ordered macroporous titanic oxide material making has meso-hole structure.
Embodiment 3:
(1) by massfraction, be that the 5% monodisperse polystyrene microsphere aqueous solution (particle diameter 345nm, dispersion coefficient 0.005) is laid on clean slide glass, in humidity 40%, under temperature 60 C, evaporation 4h makes polystyrene colloid crystal film;
(2) by the colloidal crystal film preparing thermal treatment 30min at 100 ℃ of temperature, be chilled to after room temperature, on its surface, cover again one deck slide glass, and by two slide glass clip fixations, form two slide glasss of " sandwich " structure;
(3) by tetrabutyl titanate and dehydrated alcohol by volume 1:15 mix, magnetic agitation 2 hours, obtains the precursor solution of homogeneous transparent;
(4) two slide glasss of " sandwich " structure are vertically put into precursor solution, under vacuum tightness-0.07MPa, keep taking out after vacuum 1min;
(5), by two slide glasss of populated " sandwich " structure, at temperature 60 C, humidity 40% time, allows precursor liquid fast hydrolyzing gelation in the middle of " sandwich " structure, seasoning 24h after taking out;
(6) slide glass is placed in to retort furnace, first with 3 ℃/min, is slowly warmed up to 300 ℃ of insulation 2h, then be warmed up to 500-800 ℃ of insulation 2h with 2 ℃/min, remove polystyrene colloid crystal template, obtain three-dimensional ordered macroporous titanic oxide material.
Fig. 3 is the X-ray diffraction result that three-dimensional ordered macroporous titanic oxide material roasting under differing temps that embodiment 3 makes obtains.
Claims (3)
1. a fast preparation method for three-dimensional ordered macroporous titanic oxide material, is characterized in that, comprises the following steps:
(1) by massfraction, be that the 5% monodisperse polystyrene microsphere aqueous solution (dispersion coefficient 0.005) is laid on clean slide glass, in humidity 40%, under temperature 60 C, evaporation 4h makes polystyrene colloid crystal film;
(2) by the colloidal crystal film preparing thermal treatment 30min at 100 ℃ of temperature, be chilled to after room temperature, on its surface, cover again one deck slide glass, and by two slide glass clip fixations, form two slide glasss of " sandwich " structure;
(3) tetrabutyl titanate is mixed with dehydrated alcohol, magnetic agitation 2 hours, obtains the precursor solution of homogeneous transparent;
(4) two slide glasss of " sandwich " structure are vertically put into precursor solution, under vacuum tightness-0.07MPa, keep taking out after vacuum 1min;
(5), by two slide glasss of populated " sandwich " structure, at temperature 60 C, humidity 40% time, allows precursor liquid fast hydrolyzing gelation in the middle of " sandwich " structure, seasoning 24h after taking out; (6) slide glass is placed in to retort furnace, first with 3 ℃/min, is slowly warmed up to 300 ℃ of insulation 2h, then be warmed up to 500-800 ℃ of insulation 2h with 2 ℃/min, remove polystyrene colloid crystal template, obtain three-dimensional ordered macroporous titanic oxide material.
2. according to claim 1, the particle diameter of described polystyrene microsphere is 240nm～350nm.
3. according to claim 1, described tetra-n-butyl titanate and the volume ratio of dehydrated alcohol are 1:5～20.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104383966A (en) * | 2014-12-03 | 2015-03-04 | 中国石油大学(华东) | Preparation method of 3D ordered macroporous polyaniline (OM PANI)/TiO2 composite photocatalytic material and application thereof |
| CN106350004A (en) * | 2016-08-25 | 2017-01-25 | 华东理工大学 | Sandwich structure type hollow compound wave absorption material and preparation method thereof |
| 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 |
| 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 |
| CN108993466A (en) * | 2018-08-07 | 2018-12-14 | 中国科学院地球环境研究所 | A kind of three-dimensional ordered macroporous titanate and its sacrifice preparation method certainly in situ |
| CN112759951A (en) * | 2020-12-25 | 2021-05-07 | 中建材蚌埠玻璃工业设计研究院有限公司 | Preparation method of ordered macroporous silicon dioxide coating |
-
2013
- 2013-10-23 CN CN201310508528.5A patent/CN103613128A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| ZHONGYU CAI ET AL.: "Fabrication of TiO2 Binary Inverse Opals without Overlayers via the Sandwich-Vacuum Infiltration of Precursor", 《LANGMUIR》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104383966A (en) * | 2014-12-03 | 2015-03-04 | 中国石油大学(华东) | Preparation method of 3D ordered macroporous polyaniline (OM PANI)/TiO2 composite photocatalytic material and application thereof |
| 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 |
| CN106350004A (en) * | 2016-08-25 | 2017-01-25 | 华东理工大学 | Sandwich structure type hollow compound wave absorption material and preparation method thereof |
| CN106350004B (en) * | 2016-08-25 | 2018-04-17 | 华东理工大学 | A kind of hollow composite wave-suction material of sandwich structure type and preparation method thereof |
| 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 |
| CN108993466A (en) * | 2018-08-07 | 2018-12-14 | 中国科学院地球环境研究所 | A kind of three-dimensional ordered macroporous titanate and its sacrifice preparation method certainly in situ |
| CN112759951A (en) * | 2020-12-25 | 2021-05-07 | 中建材蚌埠玻璃工业设计研究院有限公司 | Preparation method of ordered macroporous silicon dioxide coating |
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Application publication date: 20140305 |