CN106800309A - A kind of method for preparing Detitanium-ore-type micro-nano hierarchy titanium dioxide microballoon sphere - Google Patents
A kind of method for preparing Detitanium-ore-type micro-nano hierarchy titanium dioxide microballoon sphere Download PDFInfo
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- CN106800309A CN106800309A CN201710007236.1A CN201710007236A CN106800309A CN 106800309 A CN106800309 A CN 106800309A CN 201710007236 A CN201710007236 A CN 201710007236A CN 106800309 A CN106800309 A CN 106800309A
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- titanium dioxide
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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
- C01G23/0536—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing chloride-containing salts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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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
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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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
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Abstract
The invention discloses a kind of method for preparing Detitanium-ore-type micro-nano hierarchy titanium dioxide microballoon sphere, belong to micro-nano material field, prior art preparation technology is complicated, time-consuming, repeatable low, the problem that microballoon is irregular, crystallinity is poor for solving.Comprise the following steps：First under the conditions of 0 DEG C of ice-water bath, titanium tetrachloride is poured into dichloromethane, stirred；Then the CTAB aqueous solution of 0.8mol/L is mixed with the solution that the first step is obtained again, stirs 1min；Finally mixed liquor is poured into reactor and reacts 3h at a temperature of 150 200 DEG C, reactor is opened after Temperature fall, centrifuging and taking lower sediment is cleaned through deionized water and ethanol, dried, that is, obtain the titanium dioxide microballoon sphere of micro-nano structure.The technical scheme preparation process is simple of present invention offer, time-consuming short, repeatable high, microballoon are regular, good crystallinity.
Description
Technical field
It is that one kind prepares Detitanium-ore-type micro-nano hierarchy dioxy specifically the invention belongs to micro-nano material field
The method for changing titanium microballoon.
Background technology
Nano material is caused due to its skin effect, small-size effect, quantum size effect, macro quanta tunnel effect
The features such as unusual mechanics, magnetics, calorifics, optics and chemism not available for conventional material, make it in national defence, electronics, core
There is important application value in technology, metallurgy, aviation, light industry, medicine and other fields.But find to receive in actual use
Ground rice body there is also problems, although such as nano-powder material activity is high, specific surface area is big, its structural instability, easily
Reunite, so as to cause the reduction of performance, and be difficult to separate and recover after usage, especially in liquid-phase catalysis reaction.And
The material structure of micron-scale is just stablized relatively, and is easily isolated recovery, but its activity is relatively low.It would therefore be desirable to have the whole of effect
Close the advantage of nano material and micro materials.And micro-nano grading structure material is a kind of ordered aggregation of nano material, micro-
Seeing has nano unit in structure, the characteristic of nano material, i.e. high-specific surface area and high reaction activity etc. are maintained, macroscopically
Yardstick reaches micron dimension, overcomes that nanometer material structure is unstable, easy reunion deficiency, as current field of nanometer material technology
Important development direction.
Nano titanium oxide has most valuable optical property, is all shown in auto industry and numerous areas fine
Development prospect.Nano titanium oxide also has chemical stability very high, heat endurance, nontoxicity, Superhydrophilic, non-migrating
Property, and being contacted with food completely, thus be widely used in anti-ultraviolet material, weaving, photocatalysis catalyst, glass with clean,
In suncream, coating, ink, packaging material for food, paper industry, aerospace industry, in lithium battery.
It is that ilmenite is dissolved in into the concentrated sulfuric acid generally industrially to prepare titanium dioxide nanoparticle, the titanium dioxide that will then obtain
Titanyl hydrate is dehydrated, and the titanium dioxide nanoparticle specific surface energy that this method is obtained is big, and particle is easily reunited, and particle is generally not
Regular shape, particle diameter distribution is wide, therefore limits their range of application.And the narrow microballoon of good dispersion, particle diameter distribution can be with
Widen the application of titanium oxide.For example, there are some researches show, when a diameter of visible ray half of titanium dioxide granule or so (about 200~
When 500nm), with good whiteness, refractive index high can be carried effectively used in industries such as coating, plastics, papermaking, chemical fibre, ink
High yield quality, improvement properties of product.
The nanometer rods of one-dimentional structure can be taken into account into the advantage of microballoon and nanometer rods by being self-assembly of microballoon：Both possesses sky
Between three-dimensional structure, nanometer rods can provide more faster than nano particle electron transport ability in microscopic fields simultaneously, but with compared with
Specific surface area high, therefore the range of application of titanium oxide has been promoted significantly.Photocatalysis is for example used it for, reaction is easy to after terminating
Reclaim and separate；For the anode material of DSSC, be conducive to the quick transmission of light induced electron；For dyestuff
The scattering layer of sensitization solar battery, can improve the light capture ability of battery.
Patent document CN104326507B, the applying date 20141030, discloses a kind of preparation of hollow titanium dioxide microballoon
Method, by first carrying out the preparation of silica dioxide granule precast body, then introduces TiO 2 sol and is covered in silicon dioxide meter
Face, forms the core shell structure of silica-titania, then removes silica nuclear structure by sodium hydroxide solution, and leads to
Persalt removes the impure structure of microballoon, and constitutionally stable titanium dioxide hollow microballoon is finally given through calcining.The method technique is answered
Miscellaneous, preparation time is long, repeatable microballoon not high, preparing is not regular enough.
Patent document CN103771506B, the applying date 20131224, discloses a kind of micro-/hierarchy titanium dioxide of receiving micro-
The preparation method of ball, comprises the following steps：1) first by titanium sulfate, urea, disodium ethylene diamine tetraacetate, ammonium fluoride in molar ratio
1：4-8：1-2：2-4 is put into polytetrafluoroethylene (PTFE) autoclave inner bag；Deionized water to inner bag compactedness 30-60% is subsequently adding,
Stirring 2-4h obtains white " milky " liquid；2) microwave heating system and then by autoclave is put into, reaction temperature is 180 DEG C, during insulation
Between 5-30min；3) question response is finished, and after autoclave natural cooling, takes out product, with deionized water and absolute ethyl alcohol repeatedly
Product, in neutrality, is finally put into baking oven and dries 2-10h at 70 DEG C by washing to the aqueous solution, obtains final product final product by nanometer rods group
Into it is micro-/receive hierarchy titanium dioxide microballoon sphere.It is uniform to be stirred that the technique needs the long period, and time-consuming；And prepare
A diameter of 100nm of titanium dioxide microballoon sphere rod for going out or so, microsphere diameter are 2-5 microns, the diameter of rod in Nano microsphere
Greatly, microballoon is not regular enough.
The content of the invention
The present invention seeks to aim to provide short a kind of preparation process is simple, preparation process time, repeatable height, microballoon
Regular, good crystallinity the method for preparing Detitanium-ore-type micro-nano hierarchy titanium dioxide microballoon sphere.
To realize above-mentioned technical purpose, the technical solution adopted by the present invention is as follows：
A kind of method for preparing Detitanium-ore-type micro-nano hierarchy titanium dioxide microballoon sphere, comprises the following steps：
The first step, under the conditions of 0 DEG C of ice-water bath, titanium tetrachloride is poured into dichloromethane, is stirred；
Second step, the aqueous solution of CTAB is mixed with the solution that the first step is obtained, and stirs 1min；
3rd step, mixed liquor is poured into and reacts 3h in reactor at a temperature of 150-200 DEG C, and reaction is opened after Temperature fall
Kettle, centrifuging and taking lower sediment is cleaned through deionized water and ethanol, is dried, that is, obtain the titanium dioxide microballoon sphere of micro-nano structure；
Wherein, the mol ratio of titanium tetrachloride, dichloromethane and CTAB is 1-2：5.14-6.99：0.00084-0.00092.
Using the invention of above-mentioned technical proposal, water is nano titanium oxide with the mutual exclusive two kinds of liquid of dichloromethane
Self assembly provides a kind of flexible interface.And Surfactant CTAB is adsorbed in the particular crystal plane of titanium dioxide crystal, from
And the surface energy of these crystal faces is reduced, and reduce the speed of growth of these crystal faces so that titanium dioxide grows towards nano bar-shape,
So as to play structure directing agent.Therefore this method is processed without the template in later stage, and the microballoon knot that the nanometer rods for obtaining are assembled
Structure is complete, and pattern is unique, homogeneous.Whole preparation process can be obtained by the complete titanium dioxide of micro-sphere structure by one-step method,
And only needing three kinds of raw materials being easy to get can be prepared by, low cost, repetitive rate are high.
Further limit, the concentration of the CTAB is 0.8mmol/L.
Further limit, precipitation is cleaned 3-5 times through deionized water and ethanol in the 3rd step.
Further limit, in the 3rd step at a temperature of 40-60 DEG C, dry 30min-2h.
Further limit, the titanium dioxide microballoon sphere obtained in the 3rd step is self-assembled into by nanometer rods, the microballoon
It is a diameter of 3-6 microns, a diameter of 15-20 nanometers of the nanometer rods.
Two for can be obtained by that good crystallinity, microballoon are regular using one-step method in the present invention, being self-assembled into by nanometer rods
Titania microsphere, without subsequent treatment, preparation process is simple, and whole course of reaction only needs to 3h, and preparation time is short, cost
It is low, and repetitive rate is high, is adapted to industry and goes into operation.
Brief description of the drawings
The nonlimiting examples that the present invention can be given by accompanying drawing are further illustrated；
Fig. 1 is the scanning electron microscope (SEM) photograph of the titanium dioxide microballoon sphere obtained by the embodiment of the present invention 1；
Fig. 2 is the XRD of the titanium dioxide microballoon sphere obtained by the embodiment of the present invention 1；
Fig. 3 is the photoelectron energy collection of illustrative plates of the titanium dioxide microballoon sphere obtained by the embodiment of the present invention 1；
Specific embodiment
In order that those skilled in the art may be better understood the present invention, with reference to the accompanying drawings and examples to this hair
Bright technical scheme is further illustrated.
Embodiment 1
Detitanium-ore-type micro-nano hierarchy titanium dioxide microballoon sphere is prepared, is comprised the following steps：The first step will be in 0 DEG C of ice-water bath
Under the conditions of, 1.5 milliliters of titanium tetrachlorides are poured into 3.5 milliliters of dichloromethane, stir；Second step, 10 milliliters are contained
The aqueous solution of 0.8mmol/L CTAB mixes with first step solution, stirs 1min, and the 3rd step pours into 20mL reactors mixed liquor
150-200 DEG C of reaction 3h, opens reactor after Temperature fall, centrifuging and taking lower sediment is cleaned 3 times through deionized water and ethanol,
1h is dried at a temperature of 40 DEG C, that is, obtains the titanium dioxide microballoon sphere of micro-nano structure.
1st, electron microscope scanning test.
Obtained titanium dioxide microballoon sphere scanning of scanning electron microscope in embodiment 1 is obtained into scanning electricity as shown in Figure 1
Mirror picture.
A and b can be seen that products obtained therefrom for micron spheroid in Fig. 1, and the diameter of microballoon is about 3-6 microns, regular appearance, nothing
Other patterns (such as particle, sheet or bar-shaped), c and d display spheroids are assembled by many nanometer rods, a diameter of 15- of rod
20nm。
2nd, purity test.
Obtained titanium dioxide microballoon sphere X-ray diffractometer test obtains XRD spectra, and and standard card in A, embodiment 1
Piece JCPDS 21-1272 are contrasted, and obtain the X-ray powder diffraction figure of micro-nano hierarchy titanium dioxide microballoon sphere as shown in Figure 2.
Figure it is seen that obtained sample is anatase titania.And do not find other dephasign diffraction
Peak, this just illustrates that products therefrom is simple anatase crystal well.
B, Fig. 3 are respectively the photoelectron energy collection of illustrative plates of obtained titanium dioxide microballoon sphere in embodiment 1.
A in Fig. 3 proves there was only Ti and O elements (calibration value of each element when wherein C 1s are test) in product, in Fig. 3
B is Ti 2p tear seams, and peak position corresponds respectively to Ti 2p1/2 and Ti 2p3/2, illustrates to be Ti4 positioned at 464.2eV and 458.5eV
+.C is that O 1s photoelectron spectroscopies display combination can be located at 529.6eV and 532eV in Fig. 3, and Ti-O-Ti and Ti-OH is corresponded to respectively,
This detection also demonstrates that sample is pure titanium dioxide.
Two for can be obtained by that good crystallinity, microballoon are regular using one-step method in the present invention, being self-assembled into by nanometer rods
Titania microsphere, without subsequent treatment, preparation process is simple, and whole course of reaction only needs to 3h, and preparation time is short, cost
It is low, and repetitive rate is high, is adapted to industry and goes into operation.
A kind of method for preparing Detitanium-ore-type micro-nano hierarchy titanium dioxide microballoon sphere that the present invention is provided is carried out above
It is discussed in detail.The explanation of specific embodiment is only intended to help and understands the method for the present invention and its core concept.It should be pointed out that
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be entered
The some improvement of row and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
Claims (5)
1. a kind of method for preparing Detitanium-ore-type micro-nano hierarchy titanium dioxide microballoon sphere, it is characterised in that comprise the following steps：
The first step, under the conditions of 0 DEG C of ice-water bath, titanium tetrachloride is poured into dichloromethane, is stirred；
Second step, the aqueous solution of CTAB is mixed with the solution that the first step is obtained, and stirs 1min；
3rd step, mixed liquor is poured into and reacts 3h in reactor at a temperature of 150-200 DEG C, and reactor is opened after Temperature fall,
Centrifuging and taking lower sediment, cleans through deionized water and ethanol, dries, that is, obtain the titanium dioxide microballoon sphere of micro-nano structure；
Wherein, the mol ratio of titanium tetrachloride, dichloromethane and CTAB is 1-2：5.14-6.99：0.00084-0.00092.
2. a kind of method for preparing Detitanium-ore-type micro-nano hierarchy titanium dioxide microballoon sphere according to claim 1, it is special
Levy and be, the concentration of the CTAB is 0.8mmol/L.
3. a kind of method for preparing Detitanium-ore-type micro-nano hierarchy titanium dioxide microballoon sphere according to claim 1 and 2, its
It is characterised by, precipitation is cleaned 3-5 times through deionized water and ethanol in the 3rd step.
4. a kind of method for preparing Detitanium-ore-type micro-nano hierarchy titanium dioxide microballoon sphere according to claim 3, it is special
Levy and be, under being spent at 40-60 DEG C in the 3rd step, dry 30min-2h.
5. a kind of side for preparing Detitanium-ore-type micro-nano hierarchy titanium dioxide microballoon sphere according to claim 1 or 2 or 4
Method, it is characterised in that the titanium dioxide microballoon sphere obtained in the 3rd step is self-assembled into by nanometer rods, the microballoon it is a diameter of
3-6 microns, a diameter of 15-20 nanometers of the nanometer rods.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111957305A (en) * | 2020-08-11 | 2020-11-20 | 上海锐朗光电材料有限公司 | Titanium dioxide microsphere photocatalyst and preparation method thereof |
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| US20050233146A1 (en) * | 2002-02-12 | 2005-10-20 | Ralph Nonninger | Nanoscale rutile or nanoscale oxide and method for producing the same |
| CN102583530A (en) * | 2012-04-07 | 2012-07-18 | 河南工业大学 | Preparation method of nanometer titanium dioxide with ultralarge specific surface area |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050233146A1 (en) * | 2002-02-12 | 2005-10-20 | Ralph Nonninger | Nanoscale rutile or nanoscale oxide and method for producing the same |
| CN102583530A (en) * | 2012-04-07 | 2012-07-18 | 河南工业大学 | Preparation method of nanometer titanium dioxide with ultralarge specific surface area |
Non-Patent Citations (1)
| Title |
|---|
| CHANGHUA WANG ET AL.: ""Water-Dichloromethane Interface Controlled Synthesis of Hierarchical Rutile TiO2 Superstructures and Their Photocatalytic Properties"", 《INORG. CHEM.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111957305A (en) * | 2020-08-11 | 2020-11-20 | 上海锐朗光电材料有限公司 | Titanium dioxide microsphere photocatalyst and preparation method thereof |
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