CN107986328A - A kind of preparation method of nano titania bowl array - Google Patents
A kind of preparation method of nano titania bowl array Download PDFInfo
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- CN107986328A CN107986328A CN201711427032.XA CN201711427032A CN107986328A CN 107986328 A CN107986328 A CN 107986328A CN 201711427032 A CN201711427032 A CN 201711427032A CN 107986328 A CN107986328 A CN 107986328A
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- microballoon
- lotion
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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Abstract
The present invention proposes a kind of method that titanium dioxide two-dimensional nano bowl array is prepared on substrate using three-dimensional one step of colloidal crystal self assembly, and this method specifically comprises the steps of：(1) two (2 hydracrylic acid) two hydroxide diammonium is closed into titanium (TiBALDH) and ethanol mixes, add certain density hydrochloric acid afterwards, the volume ratio according to TiBALDH, ethanol and 0.1M HCl is 1:4:2 configuration TiO 2 precursor solution；(2) 1.2% 9% TiO 2 precursor solution of microballoon lotion volume is added in the microballoon lotion for doing vertical self assembly, is sufficiently mixed it using ultrasonic wave；(3) microballoon lotion is positioned in container, substrate is inserted vertically into wherein, container is positioned in baking oven, after solvent volatilization, substrate surface forms two-dimentional nano titania bowl array.
Description
Technical field
The invention belongs to inorganic material to synthesize field, is related to a kind of two-dimensional nano bowl array and preparation method thereof.
Background technology
Nano bowl array has important application prospect in nano impression, high density magnetic storage and Microfluidics etc., separately
Outer nano bowl array forms unique optical property, in antireflective and the preparation of photonic crystal due to its regular arrangement
Also it is widely used.Titanic oxide material is also widely used in photocatalysis field, and the bowl-shape array of nanometer can reduce light
Reflection so as to lifting light utilization efficiency in photocatalytic process.
The preparation of nano bowl array at present is usually to be self-assembly of individual layer glue first with gas-liquid interface progress microballoon
Body crystal, and it is filled by the methods of chemical method, magnetron sputtering using it as template, finally remove microballoon and obtain dioxy
Change titanium nano bowl array.Cai etc. (J.Mater.Chem.A, 2014,2,545), which reports to prepare using the method assembled altogether, to be had
The three-dimensional titanium dioxide inverse opal of photo-catalysis function, but their report is only limitted to the preparation of three-dimensional structure, is not directed to
The preparation of two-dimensional nano bowl array.
The content of the invention
The present invention proposes that one kind prepares titanium dioxide two-dimensional nano using three-dimensional one step of colloidal crystal self assembly on substrate
The method of bowl array, this method specifically comprise the steps of：
(1) two (2 hydroxy propanoic acid) two hydroxide diammonium is closed into titanium (TiBALDH) and ethanol mixes, added afterwards certain dense
The hydrochloric acid of degree, the volume ratio according to TiBALDH, ethanol and 0.1M HCl are 1:4:2 configuration TiO 2 precursor solution；
(2) before adding microballoon lotion volume 1.2%-9% titanium dioxide in the microballoon lotion for doing vertical self assembly
Liquid solution is driven, is sufficiently mixed it using ultrasonic wave；
(3) microballoon lotion is positioned in container, substrate is inserted vertically into wherein, container is positioned in baking oven, solvent
After volatilization, substrate surface forms two-dimentional nano titania bowl array.
In this method, in microballoon self assembling process, while being formed on substrate, titanium dioxide not only deposits colloidal crystal
Between microballoon, the surface of colloidal crystal also is deposited upon, the titanium dioxide water content that initial stage is formed is bigger, can be with dry
Carry out and syneresis.Since most of volume is occupied by microballoon in colloidal crystal, the contraction phase of the titanium dioxide between microballoon
To limited, and the titanium dioxide layer shrinkage amplitude on colloidal crystal surface is accordingly much greater, therefore, if superficial silicon dioxide titanium layer
If having larger thickness, its shrinkage tensions can make whole colloidal crystal film depart from substrate, package be formed, so that in substrate table
Face leaves two-dimensional nano bowl array.Therefore, in preparation process, it shall be guaranteed that the amount of TiO 2 precursor will be enough to be full of certainly
The gap of the colloidal crystal formed is assembled, and thicker layer of titanium dioxide layer is formed on its surface.Thus, the present invention
In, the addition of TiO 2 precursor solution is the 1.2%-9% of microballoon lotion volume, if less than 1.2%, in Colloidal crystals
There is no the thinner thickness of titanium dioxide deposition or deposition on body film, cannot all form enough shrinkage tensions takes off colloidal crystal
From substrate, so that nano bowl array can not be made.Be different from herein Cai etc. document (J.Mater.Chem.A, 2014,2,
545), in its document, TiO 2 precursor dosage is less, thus in self assembling process, be filled only with microballoon gap it
Between, so that for preparing three-dimensional counter opal structure.
In step 2, the lotion of selection is usually polymer microballoon lotion, and the preferred self-polystyrene of polymer microballoon (PS) is micro-
Ball, crosslinked PS microballoons, polymethyl methacrylate (PMMA) microballoon, polyethyl methacrylate (PEMA) microballoon；Microballoon
Particle diameter is 80nm-2000nm, and the dispersed phase for forming lotion is generally water or ethanol, and the concentration of microballoon lotion is 0.02-0.3%
(percent by volume).
In step 3, if the dispersed phase of lotion is water, container can be positioned over to 50-80 DEG C of progress self assembly in baking oven,
If dispersed phase is ethanol, room temperature can be placed in, allows ethanol to volatilize naturally.
Brief description of the drawings
Fig. 1 is the stereoscan photograph of the obtained nano titania bowl array of embodiment 1.
Embodiment
Experimental method used in embodiment described below is conventional method unless otherwise specified.
Raw material, reagent used in embodiment described below etc., are to purchase from commercial channels unless otherwise specified
.
Embodiment 1, a diameter of 280nm nano titania bowl array preparation.
By TiBALDH, ethanol and 0.1M HCl according to volume ratio 1:4:2 prepare TiO 2 precursor solution.
280nm PS microballoon aqueous emulsions are prepared using emulsifier-free emulsion polymerization, and are 0.1% by its concentration dilution with ultra-pure water
(percent by volume), takes 10ml lotions to be put among 15mL beakers, and adds 400 μ L TiO 2 precursor solution, super to it
Sound is sufficiently mixed it；
The sheet glass of 1cm × 2cm is placed in Piranha solution (98% concentrated sulfuric acid and the dioxygen that mass percentage concentration is 30%
Water aqueous solution by volume 3:1 mixed solution prepared；The solution has strong oxidizing property, and explosion may be triggered by meeting solvent,
Rigorous concentration safety is answered in use) in, 90 DEG C of heating 30min, are then cleaned with deionized water, and are dried up with nitrogen, it
It is put into vertically afterwards the above equipped with PS microballoon lotions beaker in, beaker is inserted in 60 DEG C of baking ovens, 48 it is small when after, sheet glass
Surface forms two-dimensional nano bowl array, its scanning electron microscope (SEM) photograph is shown in attached drawing 1.Further, since colloidal crystal superficial silicon dioxide titanium film is received
The colloidal crystal volume for contracting and being formed also remains in glass sheet surface, is impacted by high pressure draught, can roll up colloidal crystal and blow off
Glass sheet surface.
Embodiment 2, a diameter of 690nm nano titania bowl array preparation.
By TiBALDH, ethanol and 0.1M HCl according to volume ratio 1:4:2 prepare TiO 2 precursor solution；
690nm PS microballoon aqueous phase emulsions are bought from the market, and are 0.05% (body by its concentration dilution with deionized water
Product percentage), take 10ml to be put among 15mL beakers, and 300 μ L TiO 2 precursor solution are added, fill it its ultrasound
Divide mixing；
A piece of 1cm × 2cm sheet glass that surface hydrophilic is treated with Piranha solution is put into above beaker vertically, will
Beaker is inserted in 60 DEG C of baking ovens, 48 it is small when after, glass sheet surface formed titanium dioxide two-dimensional nano bowl array.Further, since glue
The colloidal crystal volume that body plane of crystal titanium dioxide film shrinks and formed also remains in glass sheet surface, is rushed by high pressure draught
Hit, colloidal crystal can be rolled up its surface of blowing off.
Claims (5)
1. the present invention proposes that one kind prepares nano titania bowl array using three-dimensional one step of colloidal crystal self assembly on substrate
Method, this method specifically comprises the steps of：
(1) two (2 hydroxy propanoic acid) two hydroxide diammonium is closed into titanium (TiBALDH) and ethanol mixes, added afterwards certain density
Hydrochloric acid, the volume ratio according to TiBALDH, ethanol and 0.1M HCl are 1:4:2 configuration TiO 2 precursor solution；
(2) microballoon lotion volume 1.2%-9% TiO 2 precursors are added in the microballoon lotion for doing vertical self assembly
Solution, is sufficiently mixed it using ultrasonic wave；
(3) microballoon lotion is positioned in container, substrate is inserted vertically into wherein, container is positioned in baking oven, waves solvent
Hair, substrate surface form two-dimentional nano titania bowl array.
2. preparation method according to claim 1, it is characterised in that the TiO 2 precursor added in step 2, micro-
In ball self assembling process, not only it is filled in colloidal crystal, and titanium dioxide layer is formed on its surface, this layer, which is shunk, causes glue
Body crystal crimps and titanium dioxide two-dimensional nano bowl array is formed on substrate.
3. preparation method according to claim 1, it is characterised in that in step 2, the lotion of selection is that polymer microballoon is micro-
Ball lotion, the preferred self-polystyrene of polymer microballoon (PS) microballoon, crosslinked PS microballoons, polymethyl methacrylate (PMMA) are micro-
Ball, polyethyl methacrylate (PEMA) microballoon；The particle diameter of microballoon is 80nm-2000nm, formed the dispersed phase of lotion for water or
Person's ethanol.
4. preparation method according to claim 1, it is characterised in that the concentration of microballoon lotion is 0.02-0.3% (volumes
Percentage).
5. preparation method according to claim 1, it is characterised in that, can if the dispersed phase of lotion is water in step 3
Container is positioned over 50-80 DEG C of progress self assembly in baking oven；If dispersed phase is ethanol, room temperature self assembly can be placed in.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103143379A (en) * | 2013-03-06 | 2013-06-12 | 北京化工大学 | Method for preparing nitrogen-doped titanium dioxide inverse opal thin-film photocatalyst by using one-step method |
| CN104593864A (en) * | 2014-12-22 | 2015-05-06 | 江南大学 | Titanium dioxide inverse opals and preparation method thereof |
| CN107163268A (en) * | 2017-06-13 | 2017-09-15 | 中国科学院宁波材料技术与工程研究所 | A kind of hollow bowl-shape nano silicon two-dimensional array structure and its preparation and application |
-
2017
- 2017-12-26 CN CN201711427032.XA patent/CN107986328B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103143379A (en) * | 2013-03-06 | 2013-06-12 | 北京化工大学 | Method for preparing nitrogen-doped titanium dioxide inverse opal thin-film photocatalyst by using one-step method |
| CN104593864A (en) * | 2014-12-22 | 2015-05-06 | 江南大学 | Titanium dioxide inverse opals and preparation method thereof |
| CN107163268A (en) * | 2017-06-13 | 2017-09-15 | 中国科学院宁波材料技术与工程研究所 | A kind of hollow bowl-shape nano silicon two-dimensional array structure and its preparation and application |
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