CN103073056A - Method for preparing titanium dioxide with hierarchical porous array structure - Google Patents
Method for preparing titanium dioxide with hierarchical porous array structure Download PDFInfo
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- CN103073056A CN103073056A CN2013100168239A CN201310016823A CN103073056A CN 103073056 A CN103073056 A CN 103073056A CN 2013100168239 A CN2013100168239 A CN 2013100168239A CN 201310016823 A CN201310016823 A CN 201310016823A CN 103073056 A CN103073056 A CN 103073056A
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Abstract
The invention relates to a method for preparing titanium dioxide (TiO2) with a hierarchical porous array structure. With adoption of a polystyrene (PS) template combining with a sol-gel method, the preparation method comprises the following steps: (1) pre-assembling the PS template onto a glass slide substrate to obtain a single-layer array template by utilizing a pulling method, and stripping the PS template from the glass slide by water; (2) transferring the PS template obtained in the step (1) from the water surface to another substrate; (3) using the PS template, which is loaded on the substrate and is obtained in the step (2), as a secondary carrier, and repeating the step (2) to obtain multiple layers of PS templates, of which the number of layers is controllable; (4) vertically soaking the templates obtained in the step (3) in a TiO2 sol for 2 min, pulling and separating the templates from the sol, and drying at room temperature; and (5) sintering. According to the method for preparing titanium dioxide with the hierarchical porous array structure, the hierarchical porous array TiO2 with controllable layer number and pore size can be prepared, and the method is further suitable for other materials prepared by the sol-gel method.
Description
Technical field
The present invention relates to field of nano material preparation, be specifically related to a kind of preparation method of hierarchy porous array titanium dioxide.
Background technology
The dimensional effect of nano material uniqueness and huge specific surface area make its performance than traditional material more excellent, and for different research purposes and Application Areas, the nano material that needs design to have ad hoc structure and pattern is given full play to its performance.For TiO
2, widespread use and business-like nano material are the P25 powder at present, however the size distribution of P25 is wider, specific surface area is limited (50 m only
2g
-1), its performance can not be given full play to, it uses the object of reference that also only is confined to be used as the precursor of synthetic advanced function material or is used as scientific research.Studies show that in recent years, TiO
2In air-sensitive, photochemical catalysis, dye sensitization solar battery and lithium ion battery field potential using value is arranged all, but it need to be designed to specific vesicular structure, its effect is when being to improve the material specific surface area, can satisfy the requirement of gas, photochemical catalysis target molecule or the quick infiltrating material of lithium-ion battery electrolytes and circulation.Porous material generally is divided three classes: mean pore size is less than the poromerics that is called of 2 nm, and the aperture is at the mesoporous material that is called of 2-50 nm scope, and mean pore size is greater than the large pore material that is called of 50 nm.Ordered porous nano-TiO
2Characteristics be duct size evenly, have large specific surface area, a high thermostability.TiO
2Be applied to above-mentioned field, it is designed to vesicular structure, one can increase specific surface area, and then increases the contact area of material and target molecule and electrolytic solution; Its two, pore structure is conducive to the conducting of ion and electronics, can improve the physical and chemical performance such as gas, light, electricity of material.Template is preparation porous nano TiO
2The most effective and the most practical method, the method can be prepared the porous material of novel structure, excellent performance usually in conjunction with other technology such as sol-gel method, electrochemical deposition method, TCD thermochemical deposition method and hydrothermal method etc.Template synthesis porous TiO
2Nano material not only can be carried out at low temperatures, and can effectively control the size in aperture and the spatial distribution in hole by the kind, shape and the size that change template according to investigator's wish, prepares highly active porous nano TiO
2, this is the previous important research direction of order, has also become an important core theory and technology in nano materials research field simultaneously.
Template synthesis porous nano TiO
2As template take the aggregate of surfactant molecule or nonsurfactant, take titanium salt as precursor, under the condition that solvent exists, free precursor is guided, by the reactive force between the non covalent bond (such as Coulomb's force, Van der Waals force, hydrophobic interaction, hydrogen bond, the stacking reactive force of π-π etc.), particle or the film of preparation ordered structure, then remove template by methods such as calcining, extractions, obtain required vesicular structure.Preparation porous nano TiO
2Template commonly used mainly comprises: surfactant templates, block copolymer template, emulsion template, monodisperse polymer particles etc.
Tensio-active agent is divided into ionic and nonionic surface active agent two classes.Ionic is that tensio-active agent can ionize in water, mainly comprises cats product and anion surfactant.The reacting driving force of ionic template is with the electrostatic attraction effect between the tensio-active agent of xenogenesis electric charge and surface source material or the medium.Surfactant molecule is very active in the bicomponent system of water-tensio-active agent, and along with the increase of concentration, it can form different structure formation in solution, such as spherical, stratiform, six side's shape structures etc.The hydrophilic radical of nonionic surface active agent and hydrophobic group are all not charged, such as polyoxyethylene glycol (PEG).As template, the method by the self-assembly of sol-gel template can prepare nano-TiO with polyoxyethylene glycol (PEG)
2Porous membrane.The research discovery, the content of polyoxyethylene glycol and molecular weight are to TiO
2The microtexture on surface has a great impact, and hole area increases along with the increase of the content of polyoxyethylene glycol and molecular weight.Only depend on hydrogen bond action between nonionic surface active agent and the inorganics, so template is easy to remove with solvent-extracted method.As preparing mesoporous TiO with nonionogenic tenside TritonX-100 as template
2, template water and ethanol at room temperature clean and just can remove fully without calcining, and the material structure that obtains is stable.
Segmented copolymer also can self-assembly generation microphase-separated in solution, forms diversified Jie and sees mesomorphic phase.As template, can obviously improve the hydrothermal stability of porous material, the structure of Effective Regulation porous material and performance with the segmented copolymer that contains hydrophilic group and hydrophobic group.The porous TiO that utilizes block copolymer template to prepare
2Not only the aperture is adjustable, and form also can be controlled.Take segmented copolymer P123 (EO20 PO70EO20) as template, adopt evaporation to induce self-assembly method can prepare the mesoporous TiO of Detitanium-ore-type of 2D hexagonal configuration
2, sample has narrower pore size distribution, high specific surface area, and the wall in duct contains a large amount of anatase type nano crystals, still has thermostability up to 400 ℃ the time.With similar method then obtained having high-crystallinity at 550 ℃, bigger serface, leakless, pore size distribution is narrower and the three-dimensional meso-hole TiO of even particle distribution, compound with regular structure
2As structure directing agent, induce self-assembly and sol-gel method synthetic regular pore passage structure mesoporous TiO with evaporation with segmented copolymer F127 (EO106 PO70 EO106)
2Network.
The emulsion template technology refers generally to utilize the emulsion particle with regular homogeneous profile to be template, piles up, assembles again the required material of preparation at particulate, further template can be removed after the typing and stays regular pore structure.The reported first emulsions such as Stucky prepare mesoporous material as template.In titanium colloidal sol, mix cationic microemulsion, by control incorporation and pH value, prepare TiO
2Porous membrane, experimental result show, the porous membrane of preparing has stronger photo-catalysis capability.
Monodisperse polymer particles can prepare the macroporous structure of three-dimensional high-sequential as template.This method large I simple, quick, the aperture is regulated by the median size of monodisperse particles.1998, Wijndhoven synthesized TiO with the PS glue crystal template that centrifugal field forms first
2Three-dimensional ordered macroporous material.After this, Brain etc. also adopts PS glue crystal template to obtain closelypacked TiO
2Macroporous structure.Recently, take tetrabutyl titanate as presoma, with the good PS microballoon of monodispersity as template, be that the PS microballoon is immersed in the precursor solution repeatedly under 3 the condition at pH, then the PS template is removed in the temperature programming calcining, obtain three-dimensional Detitanium-ore-type macroporous titanium dioxide, and the duct is connected with each other.Along with the development of PS mould plate technique and deepening continuously of research, after the surface-functionalized modification of PS, can prepare structure uniqueness, the abundant TiO of pattern
2Material on the PS of pipe absocped with polyelectrolyte on surface template, is prepared ordered porous TiO by the liquid deposition reaction such as Lobmann
2Hollow ball, the people such as Ge then utilize the PS microballoon of sulfonating surface, obtain the ordered porous TiO of cage shape on the drop surface by liquid phase deposition
2Hollow ball.This shows, the PS template is at preparation porous TiO
2Demonstrate great superiority and operability on the material, be TiO
2Design on material structure and controlled preparation provide technical support and assurance.
Summary of the invention
The objective of the invention is the deficiency for solving the problems of the technologies described above, a kind of preparation method of hierarchy porous array titanium dioxide is provided, can prepare the controlled hierarchy porous array TiO of the number of plies and aperture size
2
The present invention is the deficiency that solves the problems of the technologies described above, and the technical scheme that adopts is: the preparation method of hierarchy porous array titanium dioxide may further comprise the steps:
1), get slide glass and clean after, the use nitrogen atmosphere dries up, then slide glass is dipped vertically into mass concentration and is in 5% the PS aqueous solution and leave standstill 2～3min, then vertically pull out with the pull rate of 4cm/min, dry under the room temperature, obtain the monolayer array template, then slowly insert in water with 45 ° of angles of inclination the monolayer array template, the PS bead is automatically peeled off and again with regular being arranged on the water surface of form of single sheet, is obtained floating on the individual layer PS template of the water surface; PS is polystyrene.
2), get another substrate as carrier with tweezers, there is not the place of PS to insert the water with 45 ° of obliquitys from the water surface in carrier after cleaning up, then carrier is slowly moved to PS template below, slowly mention afterwards, PS can be assembled in the substrate again, substrate is placed 110 ℃ of dry 10min of vacuum drying oven, obtain being carried on the PS template of substrate;
3), choosing the particle diameter PS preparation quality concentration little than step 1) is 5% the PS aqueous solution, repeating step 1) operation preparation floats on the individual layer PS template of the water surface, and take step 2) the PS template that is carried on substrate that obtains is carrier, repeating step 2) operation, obtain two-layer PS template;
4), the two-layer PS template that makes take step 3) is as carrier, repeating step 3) operation steps obtain multilayer PS template;
5) the multilayer PS template that, step 4) is obtained vertically is immersed in TiO
2In the colloidal sol behind 2～3min, vertically lift with the pull rate of 4cm/min and to leave colloidal sol, then put at room temperature dryly, obtain the presintering sample, for subsequent use;
6), the dried presintering sample of step 5) is put into retort furnace and carry out sintering, speed with 5 ℃/min in retort furnace is warming up to 450 ℃ from room temperature, and cool to room temperature 450 ℃ of insulations with the furnace after 2～3 hours, namely obtain hierarchy porous array titanium dioxide.
Described step 1) and step 2) in purging method be specially: slide glass or the substrate that will need to clean are respectively carried out ultrasonic cleaning in 10 minutes with clear water, ethanol, acetone, deionized water as cleaning solution respectively.
Described step 2) in substrate be FTO conductive glass, metal titanium or metal platinum.
Described step 5) TiO
2Colloidal sol is that mol ratio is Ti (OBu)
4: EtOH: HCl: H
2O: CH
3COOH=1: 10: 7: 2: 0.6 colloidal sol.
Beneficial effect
The number of plies and the controlled hierarchy porous array TiO of aperture size can be prepared by present method
2, for design of material and preparation provide new feasible technology, enriched the content of field of material preparation.
Description of drawings
Fig. 1 is depicted as template group packing technique schematic diagram of the present invention;
Fig. 2 is depicted as the SEM photo of the embodiment of the invention 1 gained PS template;
Fig. 3 is depicted as the SEM photo of the PS template of the embodiment of the invention 2 gained;
Fig. 4 is depicted as the SEM photo of the PS template of the embodiment of the invention 2 gained;
Fig. 5 is depicted as the SEM photo of the PS template of the embodiment of the invention 3 gained;
Fig. 6 is depicted as the SEM photo of the PS template of the embodiment of the invention 3 gained;
Fig. 7 is depicted as the SEM photo of the PS template of the embodiment of the invention 3 gained;
Fig. 8 is depicted as the SEM photo of the PS template of the embodiment of the invention 4 gained;
Fig. 9 is depicted as the SEM photo of the embodiment of the invention 3 gained titanium dioxide;
Figure 10 is depicted as the SEM photo of the embodiment of the invention 4 gained titanium dioxide;
Figure 11 is depicted as the SEM photo of the embodiment of the invention 4 gained titanium dioxide.
Embodiment
A kind of preparation method of hierarchy porous array titanium dioxide may further comprise the steps:
1), get slide glass and clean after, the use nitrogen atmosphere dries up, then slide glass is dipped vertically into mass concentration and is in 5% the PS aqueous solution and leave standstill 2～3min, then vertically pull out with the pull rate of 4cm/min, dry under the room temperature, obtain the monolayer array template, then slowly insert in water with 45 ° of angles of inclination the monolayer array template, the PS bead is automatically peeled off and again with regular being arranged on the water surface of form of single sheet, is obtained floating on the individual layer PS template of the water surface; PS is polystyrene.
This step does not need to peel off fully, because pre-assembled template is not very regular, and also has packing phenomenon, and through peeling off this step two purposes are arranged: one can obtain arranging the PS template of regular and individual layer; It two can conveniently be transferred to this template in other substrate that needs.
Purging method is specially: slide glass or the substrate that will need to clean are respectively carried out ultrasonic cleaning in 10 minutes with clear water, ethanol, acetone, deionized water as cleaning solution respectively.
2), get another substrate as carrier with tweezers, there is not the place of PS to insert the water with 45 ° of obliquitys from the water surface in carrier after cleaning up, then carrier is slowly moved to PS template below, slowly mention afterwards, PS can be assembled in the substrate again, substrate is placed 110 ℃ of dry 10min of vacuum drying oven, obtain being carried on the PS template of substrate;
Concrete grammar is: getting another substrate that cleans up with tweezers does not have the place of PS to insert the water (water herein refers to the aqueous solution of the floating PS of the having single tier templates that makes in the step) with 45 ° of obliquitys from the water surface it, then substrate is slowly moved to PS template below, after PS template below is inserted in substrate, mobile substrate makes substrate parallel with horizontal plane, then slowly mention, PS can be assembled in the substrate again.
Purging method is specially: slide glass or the substrate that will need to clean are respectively carried out ultrasonic cleaning in 10 minutes with clear water, ethanol, acetone, deionized water as cleaning solution respectively.
Described substrate is FTO conductive glass, metal titanium or metal platinum.
3), choosing the particle diameter PS preparation quality concentration little than step 1) is 5% the PS aqueous solution, repeating step 1) operation preparation floats on the individual layer PS template of the water surface, and take step 2) the PS template that is carried on substrate that obtains is carrier, repeating step 2) operation, obtain two-layer PS template;
4), the two-layer PS template that makes take step 3) is as carrier, repeating step 3) operation steps obtain multilayer PS template;
The particle diameter of PS can be selected as required, if assemble double-deck hierarchy template, general particle diameter ratio r is large: r is little 〉=during 5:1 the template assembling comparatively desirable.
5) the multilayer PS template that, step 4) is obtained vertically is immersed in TiO
2In the colloidal sol behind 2～3min, vertically lift with the pull rate of 4cm/min and to leave colloidal sol, then put at room temperature dryly, obtain the presintering sample, for subsequent use;
TiO
2Colloidal sol is that mol ratio is Ti (OBu)
4: EtOH: HCl: H
2O: CH
3COOH=1: 10: 7: 2: 0.6 colloidal sol.
6), the dried presintering sample of step 5) is put into retort furnace and carry out sintering, speed with 5 ℃/min in retort furnace is warming up to 450 ℃ from room temperature, and cool to room temperature 450 ℃ of insulations with the furnace after 2～3 hours, namely obtain hierarchy porous array titanium dioxide.
Be illustrated in figure 1 as template group packing technique schematic diagram of the present invention.
Below be specific embodiments of the invention
A kind of preparation method of hierarchy porous array titanium dioxide may further comprise the steps:
1), get slide glass and clean after, the use nitrogen atmosphere dries up, then slide glass is dipped vertically into mass concentration and is in 5% the PS aqueous solution and leave standstill 2～3min, PS particle diameter in the PS aqueous solution is selected 2.5 μ m, then vertically pull out with the pull rate of 4cm/min, dry under the room temperature, obtain the monolayer array template, then slowly insert in water with 45 ° of angles of inclination the monolayer array template, the PS bead is automatically peeled off and again with regular being arranged on the water surface of form of single sheet, is obtained floating on the individual layer PS template of the water surface;
Purging method is specially: slide glass or the substrate that will need to clean are respectively carried out ultrasonic cleaning in 10 minutes with clear water, ethanol, acetone, deionized water as cleaning solution respectively.
2), get the FTO conductive glass as carrier with tweezers, do not have the place of PS to insert the water with 45 ° of obliquitys from the water surface in carrier after cleaning up, then carrier is slowly moved to PS template below, slowly mention afterwards, PS can be assembled in the substrate again, obtains being carried on the PS template of substrate;
Purging method is specially: slide glass or the substrate that will need to clean are respectively carried out ultrasonic cleaning in 10 minutes with clear water, ethanol, acetone, deionized water as cleaning solution respectively.
3), with step 2) the PS template that is carried on substrate that obtains vertically is immersed in TiO
2In the colloidal sol behind 2～3min, vertically lift with the pull rate of 4cm/min and to leave colloidal sol, then put at room temperature dryly, obtain the presintering sample, for subsequent use;
TiO
2Colloidal sol is that mol ratio is Ti (OBu)
4: EtOH: HCl: H
2O: CH
3COOH=1: 10: 7: 2: 0.6 colloidal sol.
4), the dried presintering sample of step 3) is put into retort furnace and carry out sintering, speed with 5 ℃/min in retort furnace is warming up to 450 ℃ from room temperature, and cool to room temperature 450 ℃ of insulations with the furnace after 3 hours, namely obtain hierarchy porous array titanium dioxide.
A kind of preparation method of hierarchy porous array titanium dioxide may further comprise the steps:
1), get slide glass and clean after, the use nitrogen atmosphere dries up, then slide glass is dipped vertically into mass concentration and is in 5% the PS aqueous solution and leave standstill 2～3min, PS particle diameter in the PS aqueous solution is selected 700nm, then vertically pull out with the pull rate of 4cm/min, dry under the room temperature, obtain the monolayer array template, then slowly insert in water with 45 ° of angles of inclination the monolayer array template, the PS bead is automatically peeled off and again with regular being arranged on the water surface of form of single sheet, is obtained floating on the individual layer PS template of the water surface;
Purging method is specially: slide glass or the substrate that will need to clean are respectively carried out ultrasonic cleaning in 10 minutes with clear water, ethanol, acetone, deionized water as cleaning solution respectively.
2), get FTO conductive glass (substrate) as carrier with tweezers, there is not the place of PS to insert the water with 45 ° of obliquitys from the water surface in carrier after cleaning up, then carrier is slowly moved to PS template below, slowly mention afterwards, PS can be assembled in the substrate again, obtains being carried on the PS template of substrate;
Purging method is specially: slide glass or the substrate that will need to clean are respectively carried out ultrasonic cleaning in 10 minutes with clear water, ethanol, acetone, deionized water as cleaning solution respectively.
3), with step 2) the PS template that is carried on substrate that obtains vertically is immersed in TiO
2In the colloidal sol behind 2～3min, vertically lift with the pull rate of 4cm/min and to leave colloidal sol, then put at room temperature dryly, obtain the presintering sample, for subsequent use;
TiO
2Colloidal sol is that mol ratio is Ti (OBu)
4: EtOH: HCl: H
2O: CH
3COOH=1: 10: 7: 2: 0.6 colloidal sol.
4), the dried presintering sample of step 3) is put into retort furnace and carry out sintering, speed with 5 ℃/min in retort furnace is warming up to 450 ℃ from room temperature, and cool to room temperature 450 ℃ of insulations with the furnace after 3 hours, namely obtain hierarchy porous array titanium dioxide.
By Fig. 2,3 and 4 as can be known, the PS template of present technique assembling is more smooth in the big area scope, even, and the PS template is monolayer array and arranges.In addition, the particle diameter of PS is controlled, and diameter is respectively 2.5 μ m and 700 nm, and particle size distribution is narrow, and the present invention has realized the technological breakthrough with floating-transfer method assembling individual layer PS template.
Embodiment 3
A kind of preparation method of hierarchy porous array titanium dioxide may further comprise the steps:
1), get slide glass and clean after, the use nitrogen atmosphere dries up, then slide glass is dipped vertically into mass concentration and is in 5% the PS aqueous solution and leave standstill 2～3min, PS particle diameter in the PS aqueous solution is selected 2.5 μ m, then vertically pull out with the pull rate of 4cm/min, dry under the room temperature, obtain the monolayer array template, then slowly insert in water with 45 ° of angles of inclination the monolayer array template, the PS bead is automatically peeled off and again with regular being arranged on the water surface of form of single sheet, is obtained floating on the individual layer PS template of the water surface;
Purging method is specially: slide glass or the substrate that will need to clean are respectively carried out ultrasonic cleaning in 10 minutes with clear water, ethanol, acetone, deionized water as cleaning solution respectively.
2), get metal titanium (substrate) as carrier with tweezers, there is not the place of PS to insert the water with 45 ° of obliquitys from the water surface in carrier after cleaning up, then carrier is slowly moved to PS template below, slowly mention afterwards, PS can be assembled in the substrate again, substrate is placed 110 ℃ of dry 10min of vacuum drying oven, obtain being carried on the PS template of substrate;
Purging method is specially: slide glass or the substrate that will need to clean are respectively carried out ultrasonic cleaning in 10 minutes with clear water, ethanol, acetone, deionized water as cleaning solution respectively.
3), choosing particle diameter is that the PS preparation quality concentration of 500nm is 5% the PS aqueous solution, repeating step 1) operation preparation floats on the individual layer PS template of the water surface, and take step 2) the PS template that is carried on substrate that obtains is carrier, repeating step 2) operation, obtain two-layer PS template, two-layer PS template is placed 110 ℃ of dry 10min of vacuum drying oven;
4) the two-layer PS template that, step 3) is obtained vertically is immersed in TiO
2In the colloidal sol behind 2～3min, vertically lift with the pull rate of 4cm/min and to leave colloidal sol, then put at room temperature dryly, obtain the presintering sample, for subsequent use;
TiO
2Colloidal sol is that mol ratio is Ti (OBu)
4: EtOH: HCl: H
2O: CH
3COOH=1: 10: 7: 2: 0.6 colloidal sol.
5), the dried presintering sample of step 4) is put into retort furnace and carry out sintering, speed with 5 ℃/min in retort furnace is warming up to 450 ℃ from room temperature, and cool to room temperature 450 ℃ of insulations with the furnace after 2～3 hours, namely obtain hierarchy porous array titanium dioxide.
By Fig. 5,6 and 7 as can be known, the PS(500 nm that grain size is little) template covers the large PS(2.5 μ m of grain size in mode even, individual layer) template surface, thereby form the PS/PS array mould plate with hierarchy, provide technical guarantee for preparing classifying porous array titanium dioxide.
As shown in Figure 9, the hierarchy titanium dioxide that adopts PS/PS array masterplate can obtain having the convex surface porous, lower floor is TiO2 macropore array, the upper strata is the porous array arch caping that covers on each macropore.
Embodiment 4
A kind of preparation method of hierarchy porous array titanium dioxide may further comprise the steps:
1), get slide glass and clean after, the use nitrogen atmosphere dries up, then slide glass is dipped vertically into mass concentration and is in 5% the PS aqueous solution and leave standstill 2～3min, PS particle diameter in the PS aqueous solution is selected 2.5 μ m, then vertically pull out with the pull rate of 4cm/min, dry under the room temperature, obtain the monolayer array template, then slowly insert in water with 45 ° of angles of inclination the monolayer array template, the PS bead is automatically peeled off and again with regular being arranged on the water surface of form of single sheet, is obtained floating on the individual layer PS template of the water surface;
Purging method is specially: slide glass or the substrate that will need to clean are respectively carried out ultrasonic cleaning in 10 minutes with clear water, ethanol, acetone, deionized water as cleaning solution respectively.
2), get metal platinum (substrate) as carrier with tweezers, there is not the place of PS to insert the water with 45 ° of obliquitys from the water surface in carrier after cleaning up, then carrier is slowly moved to PS template below, slowly mention afterwards, PS can be assembled in the substrate again, substrate is placed 110 ℃ of dry 10min of vacuum drying oven, obtain being carried on the PS template of substrate;
Purging method is specially: slide glass or the substrate that will need to clean are respectively carried out ultrasonic cleaning in 10 minutes with clear water, ethanol, acetone, deionized water as cleaning solution respectively.
3), with step 2) the PS template that obtains vertically is immersed in TiO
2In the colloidal sol behind 2～3min, vertically lift with the pull rate of 4cm/min and to leave colloidal sol, then put at room temperature dryly, obtain the presintering sample, for subsequent use;
TiO
2Colloidal sol is that mol ratio is Ti (OBu)
4: EtOH: HCl: H
2O: CH
3COOH=1: 10: 7: 2: 0.6 colloidal sol.
4), the dried presintering sample of step 3) put into retort furnace carry out sintering, the speed with 5 ℃/min in retort furnace is warming up to 450 ℃ from room temperature, and cools to room temperature 450 ℃ of insulations with the furnace after 2～3 hours.
5), choosing particle diameter is that the PS preparation quality concentration of 700nm is 5% the PS aqueous solution, repeating step 1) operation preparation floats on the individual layer PS template of the water surface, and the sintered products that obtains take above-mentioned step 4) is as carrier, repeating step 2) operation, obtain two-layer PS template, two-layer PS template is placed 110 ℃ of dry 10min of vacuum drying oven;
6) the two-layer PS template that, step 5) is obtained vertically is immersed in TiO
2In the colloidal sol behind 2～3min, vertically lift with the pull rate of 4cm/min and to leave colloidal sol, then put at room temperature dryly, obtain the presintering sample, for subsequent use;
TiO
2Colloidal sol is that mol ratio is Ti (OBu)
4: EtOH: HCl: H
2O: CH
3COOH=1: 10: 7: 2: 0.6 colloidal sol.
7), the dried presintering sample of step 6) put into retort furnace carry out sintering, the speed with 5 ℃/min in retort furnace is warming up to 450 ℃ from room temperature, and cools to room temperature 450 ℃ of insulations with the furnace after 2～3 hours.
As shown in Figure 8, the PS template not only can be transferred to the PS surface, can also transfer to TiO 2 porous array surface, forms the porous array that macropore holds individual layer PS bead/PS secondary template.
By Figure 10,11 as can be known: then can obtain the hierarchy titanium dioxide that the macropore inwall covers the porous array film take porous array/PS as secondary template.In addition, the porous material of homogeneity and heterogeneous hierarchy can also be prepared respectively by present method, also is applicable to other material with the sol-gel method preparation.
Claims (4)
1. the preparation method of hierarchy porous array titanium dioxide is characterized in that: may further comprise the steps:
1), get slide glass and clean after, the use nitrogen atmosphere dries up, then slide glass is dipped vertically into mass concentration and is in 5% the PS aqueous solution and leave standstill 2～3min, then vertically pull out with the pull rate of 4cm/min, dry under the room temperature, obtain the monolayer array template, then slowly insert in water with 45 ° of angles of inclination the monolayer array template, the PS bead is automatically peeled off and again with regular being arranged on the water surface of form of single sheet, is obtained floating on the individual layer PS template of the water surface;
2), get another substrate as carrier with tweezers, there is not the place of PS to insert the water with 45 ° of obliquitys from the water surface in carrier after cleaning up, then carrier is slowly moved to individual layer PS template below, slowly mention afterwards, PS can be assembled in the substrate again, substrate is placed 110 ℃ of dry 10min of vacuum drying oven, obtain being carried on the PS template of substrate;
3), choosing the particle diameter PS preparation quality concentration little than step 1) is 5% the PS aqueous solution, repeating step 1) operation preparation floats on the individual layer PS template of the water surface, and take step 2) the PS template that is carried on substrate that obtains is carrier, repeating step 2) operation, obtain two-layer PS template;
4), the two-layer PS template that makes take step 3) is as carrier, repeating step 3) operation steps obtain multilayer PS template;
5) the multilayer PS template that, step 4) is obtained vertically is immersed in TiO
2In the colloidal sol behind 2～3min, vertically lift with the pull rate of 4cm/min and to leave colloidal sol, then put at room temperature dryly, obtain the presintering sample, for subsequent use;
6), the dried presintering sample of step 5) is put into retort furnace and carry out sintering, speed with 5 ℃/min in retort furnace is warming up to 450 ℃ from room temperature, and cool to room temperature 450 ℃ of insulations with the furnace after 2～3 hours, namely obtain hierarchy porous array titanium dioxide.
2. the preparation method of hierarchy porous array titanium dioxide as claimed in claim 1 is characterized in that: step 1) and step 2) in purging method be specially: slide glass and the substrate that will need to clean are respectively carried out ultrasonic cleaning in 10 minutes with clear water, ethanol, acetone, deionized water as cleaning solution respectively.
3. the preparation method of hierarchy porous array titanium dioxide as claimed in claim 1 is characterized in that: described step 2) substrate be FTO conductive glass, metal titanium or metal platinum.
4. the preparation method of hierarchy porous array titanium dioxide as claimed in claim 1 is characterized in that: described step 5) TiO
2Colloidal sol is that mol ratio is Ti (OBu)
4: EtOH: HCl: H
2O: CH
3COOH=1: 10: 7: 2: 0.6 colloidal sol.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103545549A (en) * | 2013-10-28 | 2014-01-29 | 北京理工大学 | Lithium secondary battery ionic gel electrolyte and preparation method thereof |
| CN105540654A (en) * | 2015-12-10 | 2016-05-04 | 西安电子科技大学 | Preparation method for multilayer TiO2 nanostructured array material |
| CN104829265B (en) * | 2015-04-09 | 2016-08-17 | 河北工业大学 | A kind of preparation method of inorganic hierarchical porous structure material |
| CN106058234A (en) * | 2016-08-19 | 2016-10-26 | 武汉理工大学 | TiO2 microsphere material having graded porous core-shell structure, preparation method and applications thereof |
| 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 |
Citations (1)
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| CN101323504A (en) * | 2008-06-13 | 2008-12-17 | 天津大学 | Preparation of macroporous-mesoporous nanocrystalline titania film |
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| CN101323504A (en) * | 2008-06-13 | 2008-12-17 | 天津大学 | Preparation of macroporous-mesoporous nanocrystalline titania film |
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| 雷建飞等: "多孔阵列TiO2/Ti的光电催化性能", 《物理化学学报》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103545549A (en) * | 2013-10-28 | 2014-01-29 | 北京理工大学 | Lithium secondary battery ionic gel electrolyte and preparation method thereof |
| CN103545549B (en) * | 2013-10-28 | 2015-07-22 | 北京理工大学 | Lithium secondary battery ionic gel electrolyte and preparation method thereof |
| CN104829265B (en) * | 2015-04-09 | 2016-08-17 | 河北工业大学 | A kind of preparation method of inorganic hierarchical porous structure material |
| CN105540654A (en) * | 2015-12-10 | 2016-05-04 | 西安电子科技大学 | Preparation method for multilayer TiO2 nanostructured array material |
| CN106058234A (en) * | 2016-08-19 | 2016-10-26 | 武汉理工大学 | TiO2 microsphere material having graded porous core-shell structure, preparation method and applications thereof |
| CN106058234B (en) * | 2016-08-19 | 2018-10-23 | 武汉理工大学 | A kind of TiO of classifying porous nucleocapsid2Sphere material and its preparation method and application |
| 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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