CN109485093A - A kind of anatase titanium dioxide hollow ball shell and preparation method thereof that spherical shape is intact - Google Patents
A kind of anatase titanium dioxide hollow ball shell and preparation method thereof that spherical shape is intact Download PDFInfo
- Publication number
- CN109485093A CN109485093A CN201811408890.4A CN201811408890A CN109485093A CN 109485093 A CN109485093 A CN 109485093A CN 201811408890 A CN201811408890 A CN 201811408890A CN 109485093 A CN109485093 A CN 109485093A
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- intact
- liquid
- preparation
- hollow ball
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
- C01G23/08—Drying; Calcining ; After treatment of titanium oxide
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
-
- 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
-
- 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
Abstract
The present invention provides a kind of anatase titanium dioxide hollow ball shell and preparation method thereof that spherical shape is intact, includes the following steps: step 1, prepares PS Modified Adhesive body microballoon lotion using no soap lye polymerization；Step 2, TiO is wrapped up by mixed solvent method2Shell structurre obtains PS@TiO2Powder；Step 3, PS@TiO2Powder carries out calcination processing twice: primary calcining is to calcine 2h at 450-550 DEG C；Secondary clacining is to calcine 10min at 320-420 DEG C, obtains titanium dioxide hollow ball shell.Titanium dioxide produced by the present invention be Detitanium-ore-type, hollow shell structure, good sphericity, uniform particle diameter, diameter between 100-400nm, catalysis, battery, gas storage and separation etc. optical electro-chemistry application field have a wide range of applications.
Description
Technical field
The invention belongs to field of material technology, be related to a kind of anatase titanium dioxide hollow ball shell that spherical shape is intact and its
Preparation method.
Background technique
Core-shell structure is to be coated another nano material by chemical bond or other active forces by a kind of nano material
Ordered fabrication structure come the nanoscale formed.Core-shell structure incorporates inside and outside two kinds of materials due to its unique architectural characteristic
The property of material, and the respective deficiency that complements each other, catalysis, battery, gas storage and separation in terms of have a wide range of applications before
Scape.
Due to nano-TiO2Specific surface area it is larger, surface dead key is more, cause its preparation and application process in easily
Agglomeration occurs, so that catalytic efficiency is not high, excellent performance cannot be fully played.Therefore, it is with titanium dioxide
Attention of the research of the core-shell structured nanomaterials of base by numerous researchers.
Currently, titania-based core-shell structured nanomaterials restrict there are still the science and technical problem of more key
Its industrial application.The preparation cost of most of titania-based core-shell structured nanomaterials is high, complex process causes large-scale production
Difficulty reduces cost and simplification of flowsheet into top priority；Using which kind of material and titanium dioxide synthesis core shell structure
Performance is best, and its appropriate proportioning in core-shell structure etc. need to be considered.
Have researcher using nano carbon microsphere or glucose as core (for example, CN101905153A, CN101890350A and
CN101857267A), organic-titanium dioxide core shell structure is prepared by precursor liquid of butyl titanate, then removes organic core through calcining
Body obtains hollow TiO2Shell.But size due to nano carbon microsphere itself is not uniform enough, and sphericity is also not perfect, so packet
TiO obtained is calcined after wrapping up in2Shell structure is not of uniform size；In addition, the poor dispersion of nano carbon microsphere, is easy to reunite, before package
Long-time ultrasonic disperse is needed, serious adhesion occurs between no side shell, influences the functionalized application of material.In recent years, with
The colloid micro ball good dispersion degree that microemulsion method is prepared, particle diameter distribution is narrow, using colloid micro ball as core, wraps up TiO2Prepare hollow ball
The method of shell attempts (CN105502485A and CN101077792A) by everybody, but the control of the condition of gained core-shell structure is compared
Harshness, especially in the process of calcining, complete spherical shell structure by serious destruction, often result in collapsing, produce it is broken
Hemisphere.
So far, spherical intact Detitanium-ore-type TiO is largely prepared2Hollow ball shell does not have document report.
Summary of the invention
Aiming at the problems existing in the prior art, it is hollow to provide a kind of anatase titanium dioxide that spherical shape is intact by the present invention
The titanium dioxide hollow ball shell spherical structure of spherical shell and preparation method thereof, preparation is complete, and size is uniform, and breakage significantly reduces.
The present invention is to be achieved through the following technical solutions:
A kind of preparation method for the anatase titanium dioxide hollow ball shell that spherical shape is intact, includes the following steps:
Step 1, it prepares PS Modified Adhesive body microballoon lotion: taking styrene, α-methacrylic acid and water, be uniformly mixed, in 75-
It is stirred to react 30-60min at 90 DEG C, is then injected into initiator potassium persulfate solution, 7-9h is reacted at 75-90 DEG C, is changed
Property PS colloid micro ball lotion；
Step 2, TiO is wrapped up2Shell structurre: gained PS Modified Adhesive body microballoon emulsion dispersion is in the mixed liquor of ethyl alcohol and acetonitrile
In, it is denoted as A liquid；Butyl titanate is dissolved in the mixed liquor of ethyl alcohol and acetonitrile, is denoted as B liquid；Under agitation, slowly by B liquid
It injects in A liquid, is stirred to react to obtain PS@TiO2The dispersion liquid of microballoon is ground into PS@TiO using washing, drying2Powder；
Step 3, PS@TiO2Powder carries out calcination processing twice: primary calcining is to calcine 2h at 450-550 DEG C；It is secondary
Calcining is to calcine 10min at 320-420 DEG C, obtains titanium dioxide hollow ball shell.
Preferably, in step 1, the ratio of styrene, α-methacrylic acid and water are as follows: (7-14) mL:(0.5-1) mL:
(90-180)mL。
Preferably, in step 1, the ratio of potassium peroxydisulfate and styrene is 17g:(7-14) mL.
Preferably, in step 1, styrene used is purified mistake, purification process are as follows: by styrene sodium hydroxide
Solution washing, then milli-Q water is used, until solution is in neutrality, solid water-free calcium chloride, removing water is added.
Preferably, in step 2, after B liquid injects A liquid, the ratio of PS Modified Adhesive body microballoon and butyl titanate is (3-6) g:
(0.5-3)mL。
Preferably, in step 2, after B liquid is slowly injected A liquid, 1-30h is reacted at 20-40 DEG C.
Preferably, in step 2, the drop speed control that B liquid slowly injects A liquid is controlled in drop speed in 30-60 drop/min, every dropwise addition
The interval 5mL 5-10min, is during which kept stirring, is during which kept stirring.
Preferably, in step 2, washing is specifically: detergent, ultrasonic disperse 20-30min, centrifugation is added；Centrifugal rotational speed is
7000-10000r/min, centrifugation time 20-30min.
Preferably, primary calcining is to be warming up to 480-520 DEG C in tube furnace with 1-5 DEG C/min of heating rate；It is secondary to forge
Burning is to be warming up to 320-420 DEG C in Muffle furnace with 1-5 DEG C/min of heating rate.
The intact anatase titanium dioxide hollow ball shell of the spherical shape that the preparation method is prepared.
Compared with prior art, the invention has the following beneficial technical effects:
The present invention first uses no soap lye polymerization, is raw material by styrene, and the modified enhancing parent of α-methacrylic acid is added
It is aqueous, initiator potassium persulfate is added, polystyrene (PS) colloid micro ball of uniform particle diameter is made；Pass through mixed solvent method reality again
Existing TiO2To the package of PS, core-shell structure is formed, is then calcined twice, PS is carbonized after primary calcining, and fold occurs in microballoon, secondary
After calcining, carbon is oxidized to carbon dioxide gas spilling, while shell is strutted, buckling phenomena be improved significantly, obtain
Extensive spherical intact anatase titanium dioxide nucleocapsid powder body material.It is rutile titania through titanium dioxide made from the method for the present invention
Mine type, hollow shell structure, good sphericity, uniform particle diameter, diameter in catalysis, battery, gas storage and divide between 100-400nm
From etc. optical electro-chemistry application field have a wide range of applications.Preparation method of the present invention is simple, and repeatability is strong, not only solves
Nano carbon microsphere is not of uniform size, and sphericity is not perfect, and TiO obtained is calcined after package2The non-uniform technical problem of shell structure, together
When solve the poor dispersion of carbon ball, be easy to reunite, long-time ultrasonic disperse needed before package, is occurred between shell serious
Adhesion influences the skills problem such as functionalized application of material.Present invention process operating process is simple and easy, stablizes repeatable.
Further, by controlling the additional amount of pre-reaction material butyl titanate, TiO is realized2Thickness of the shell controllable preparation.
TiO prepared by the present invention2In Detitanium-ore-type, hollow shell structure, good sphericity, spherical structure is complete, and size is uniform, breaks
Damage significantly reduces.Titanium dioxide (TiO2) it is a kind of with the semiconductor material that value is widely applied.Especially uniform complete shell
The TiO of structure2Nano material has better permeability, bigger specific surface area, smaller density, and the gap between shell makes
Obtaining light can reflect repeatedly, improve TiO2The light utilization ratio of material, these features promote TiO2Material photocatalysis,
The application in the modern science and technology fields such as macromolecular sustained release, solar battery, lithium ion battery.Prepare shell structure TiO2Nanometer material
Material has become the research hotspot received significant attention.
Detailed description of the invention
Fig. 1 is the XRD diagram of the resulting titanium dioxide powder of 1 secondary clacining of embodiment；
Fig. 2 is the SEM figure that embodiment 1 once calcines resulting titanium dioxide powder；
Fig. 3 and Fig. 4 is that the SEM of the resulting titanium dioxide powder of 1 secondary clacining of embodiment schemes；
Fig. 5 is that the SEM of the resulting titanium dioxide powder of 3 secondary clacining of embodiment schemes；
Fig. 6 is that the EDS of the resulting titanium dioxide powder of 3 secondary clacining of embodiment schemes；
Fig. 7 is that the two-dimensional surface of the resulting titanium dioxide powder of 3 secondary clacining of embodiment sweeps EDS figure.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
The preparation method of the intact anatase titanium dioxide hollow ball shell of spherical shape of the present invention, including following step
It is rapid:
1) styrene purifies, and α-methacrylic acid is added in three neck round bottom flask in the styrene solution after taking purification
And deionized water, magnetic agitation 30min or more mix solution, separately configure potassium persulfate solution；Styrene, Alpha-Methyl propylene
The ratio of acid and deionized water are as follows: (7-14) mL:(0.5-1) mL:(90-180) mL；The concentration of potassium persulfate solution is 1.7g/
mL。
2) preparation of PS colloid micro ball lotion: connection condensing unit is put into 80 DEG C of oil bath pans, magnetic agitation 30-
60min reacts in the potassium persulfate solution injection system of step 1) 7-9h under 75-90 DEG C of thermostatic effect, it is micro- to obtain PS colloid
Ball lotion；The ratio of potassium peroxydisulfate and styrene is 1.7g:(7-14) mL.
3) one third of gained PS colloid micro ball lotion is scattered in the mixed liquor of ethyl alcohol and acetonitrile, A liquid is denoted as, by titanium
Acid butyl ester (TBOT) is dissolved in the mixed liquor of ethyl alcohol and acetonitrile, is denoted as B liquid；In A liquid, PS colloid micro ball lotion, ethyl alcohol and acetonitrile
Ratio are as follows: 20mL:80mL:20mL；In B liquid, the ratio of butyl titanate, ethyl alcohol and acetonitrile are as follows: (0.5-3) mL:16mL:4mL.
4) mixed solvent method prepares core-shell structure PS@TiO2: B liquid is slowly injected in A liquid, make PS Modified Adhesive body microballoon with
The ratio of butyl titanate is (3-6) g:(0.5-3) mL, and quick magnetic agitation at 20-40 DEG C obtains PS@TiO after a period of time2
Dispersion liquid, using washing and ultrasonic disperse, drying be ground into PS@TiO2Powder.
5) high-temperature process: PS@TiO2Powder is calcined to obtain spherical intact Detitanium-ore-type TiO twice2Nucleocapsid powder material
Material.
In step 1), styrene purification, which refers to, washes twice the styrene of purchase with 10% sodium hydroxide solution, then
More than three times with milli-Q water, until solution is in neutrality, to remove polymerization inhibitor, a small amount of solid water-free calcium chloride is added, removes
Water is sealed in cold compartment of refrigerator, for use.The mixing speed of magnetic agitation is 400r/min.
In step 2), heating magnetic agitation rotating speed is 300r/min.
In step 4), during which the drop speed control slowly injected is kept in 60 drops/min, every dropwise addition 5mL interval 5min
Stirring；A period of time range is 1-30h；Quick magnetic agitation is 500r/min；Washing and ultrasound procedure refer to deionized water cleaning 3
It is secondary, washes of absolute alcohol 3 times, it is centrifuged gap ultrasonic disperse 20-30min, centrifugal rotational speed 7000-10000r/min in washing, from
Heart time 20-30min.
The calcining system calcined twice in step 5), which is respectively as follows: in tube furnace, calcines 2h at 480-520 DEG C, heating rate 1-
5℃/min；Then through 320-420 DEG C of calcining 10min, 1-5 DEG C of heating rate/min in Muffle furnace.
Embodiment 1
A kind of anatase titanium dioxide core-shell material that spherical shape is intact, comprising the following steps:
1) styrene purifies, and is washed twice with 10% sodium hydroxide solution, then more than three times with milli-Q water, until
Solution is in neutrality, and to remove polymerization inhibitor, a small amount of solid water-free calcium chloride is added, removes water, is sealed in cold compartment of refrigerator, takes
0.5mL α-methacrylic acid and 90mL deionized water is added in three neck round bottom flask in styrene solution after being purified with 7mL,
Magnetic agitation 30min under the conditions of revolving speed 400r/min is uniformly mixed solution, another to configure 1.7g/mL potassium persulfate solution 10mL；
2) preparation of PS colloid micro ball lotion: connection condensing unit is put into 75 DEG C of oil bath pans, 300r/min magnetic agitation
30min reacts 7h under 75 DEG C of thermostatic effects in the potassium persulfate solution injection system of step 1), obtains PS microballoon dispersion liquid,
Centrifuge washing；
3) one third of gained PS lotion is scattered in the mixed liquor of 80mL ethyl alcohol and 20mL acetonitrile, is denoted as A liquid, will
0.5mL butyl titanate (TBOT) is dissolved in the mixed liquor of 16mL ethyl alcohol and 4mL acetonitrile, is denoted as B liquid；
4) mixed solvent method prepares core-shell structure PS@TiO2: B liquid is slowly injected in A liquid, drip speed control 30 drip/
Min, every dropwise addition 5mL interval 5min, is during which kept stirring, and obtains PS@TiO after quick magnetic agitation 500r/min, 1h at 20 DEG C2
Dispersion liquid, then through deionized water clean 3 times, washes of absolute alcohol 3 times, washing be centrifuged gap ultrasonic disperse 20min, centrifugation
Revolving speed 7000r/min, centrifugation time 20min.Drying is ground into powder；
5) 2h, 1 DEG C/min of heating rate high-temperature process: are calcined in tube furnace at 480 DEG C；Then through 320 in Muffle furnace
DEG C calcining 10min, 1 DEG C/min of heating rate.Calcining twice obtains spherical intact Detitanium-ore-type TiO2Nucleocapsid powder body material.
Embodiment 2
A kind of anatase titanium dioxide core-shell material that spherical shape is intact, comprising the following steps:
1) styrene purifies, and is washed twice with 10% sodium hydroxide solution, then more than three times with milli-Q water, until
Solution is in neutrality, and to remove polymerization inhibitor, a small amount of solid water-free calcium chloride is added, removes water, is sealed in cold compartment of refrigerator, takes
Styrene solution after being purified with 11mL is in three neck round bottom flask, addition 0.8mL α-methacrylic acid, 120mL deionized water,
400r/min magnetic agitation 30min, mixes solution, another to configure 1.7g/mL potassium persulfate solution 10mL；
2) preparation of PS colloid micro ball lotion: connection condensing unit is put into 80 DEG C of oil bath pans, 300r/min magnetic agitation
40min reacts 8h under 80 DEG C of thermostatic effects in the potassium persulfate solution injection system of step 1), obtains PS microballoon dispersion liquid,
Centrifuge washing；
3) one third of gained PS lotion is scattered in the mixed liquor of 80mL ethyl alcohol and 20mL acetonitrile, is denoted as A liquid, will
2mL butyl titanate (TBOT) is dissolved in the mixed liquor of 16mL ethyl alcohol and 4mL acetonitrile, is denoted as B liquid；
4) mixed solvent method prepares core-shell structure PS@TiO2: B liquid is slowly injected in A liquid, drip speed control 40 drip/
Min, every dropwise addition 5mL interval 8min, is during which kept stirring, and obtains PS@TiO after quick magnetic agitation 500r/min, 5h at 30 DEG C2
Dispersion liquid, then through deionized water clean 3 times, washes of absolute alcohol 3 times, washing be centrifuged gap ultrasonic disperse 25min, centrifugation
Revolving speed 8000r/min, centrifugation time 25min.Drying is ground into powder；
5) 2h, 2 DEG C/min of heating rate high-temperature process: are calcined in tube furnace at 500 DEG C；Then through 370 in Muffle furnace
DEG C calcining 10min, 2 DEG C/min of heating rate.Calcining twice obtains spherical intact Detitanium-ore-type TiO2Nucleocapsid powder body material.
Embodiment 3
A kind of anatase titanium dioxide core-shell material that spherical shape is intact, comprising the following steps:
1) styrene purifies, and is washed twice with 10% sodium hydroxide solution, then more than three times with milli-Q water, until
Solution is in neutrality, and to remove polymerization inhibitor, a small amount of solid water-free calcium chloride is added, removes water, is sealed in cold compartment of refrigerator, takes
Styrene solution after being purified with 14mL is in three neck round bottom flask, addition 1.0mL α-methacrylic acid, 180mL deionized water,
400r/min magnetic agitation 30min, mixes solution, another to configure 1.7g/mL potassium persulfate solution 10mL；
2) preparation of PS colloid micro ball lotion: connection condensing unit is put into 90 DEG C of oil bath pans, 300r/min magnetic agitation
60min reacts 9h under 90 DEG C of thermostatic effects in the potassium persulfate solution injection system of step 1), obtains PS microballoon dispersion liquid,
Centrifuge washing；
3) one third of gained PS lotion is scattered in the mixed liquor of 80mL ethyl alcohol and 20mL acetonitrile, is denoted as A liquid, will
3mL butyl titanate (TBOT) is dissolved in the mixed liquor of 16mL ethyl alcohol and 4mL acetonitrile, is denoted as B liquid；
4) mixed solvent method prepares core-shell structure PS@TiO2: B liquid is slowly injected in A liquid, drip speed control 60 drip/
Min, every dropwise addition 5mL interval 10min, is during which kept stirring, and obtains PS@after quick magnetic agitation 500r/min, 5h at 40 DEG C
TiO2Dispersion liquid, then through deionized water clean 3 times, washes of absolute alcohol 3 times, washing be centrifuged gap ultrasonic disperse 30min,
Centrifugal rotational speed 10000r/min, centrifugation time 30min.Drying is ground into powder；
5) 2h, 5 DEG C/min of heating rate high-temperature process: are calcined in tube furnace at 520 DEG C；Then through 420 in Muffle furnace
DEG C calcining 10min, 5 DEG C/min of heating rate.Calcining twice obtains spherical intact Detitanium-ore-type TiO2Nucleocapsid powder body material.
The XRD analysis of 1 gained sample of embodiment is as shown in Figure 1, TiO2For anatase crystal, and in addition to TiO2Characteristic peak
Except, no miscellaneous peak occurs, and shows pure using sample prepared by this method.
The scanning electron microscope (SEM) photograph of the primary calcined sample of embodiment 1 is as shown in Fig. 2, it can be seen from the figure that spherical shell surface
Coarse, fold is uneven, and poly- phenomenon is serious, and nucleome PS is reduced to carbon at this time.Anatase made from 1 secondary clacining of embodiment
Type TiO2Powder sample is as shown in Figure 3 and Figure 4, and shell thickness is about 10nm, is clear that hollow ball shell, structure is presented in it
It is uniform complete, it is broken seldom.Illustrate after the secondary low temperature calcination of Muffle furnace, carbon is oxidized to carbon dioxide gas spilling, together
When shell is strutted, buckling phenomena be improved significantly.
Embodiment 3 increases the ratio of precursor liquid butyl titanate and PS microballoon, obtained Detitanium-ore-type TiO2Powder sample is such as
Shown in Fig. 5, shell thickness is about 20nm.It is clear that hollow ball shell is presented in it, structure is uniform complete, broken seldom.
Shell structurre TiO prepared by embodiment 32EDS energy spectrum diagram as shown in fig. 6, the presence of a small amount of C element illustrates PS core
There is remaining fabricated in situ carbon after body vacuum calcining, Ti and O element proves TiO2Appearance.Fig. 7 is that two-dimensional surface sweeps EDS energy spectrum diagram,
It can be seen that apparent hollow TiO2Structure, the large area distribution reason of C are the interference effect of carbon film on copper mesh.
Claims (10)
1. a kind of preparation method for the anatase titanium dioxide hollow ball shell that spherical shape is intact, which is characterized in that including walking as follows
It is rapid:
Step 1, it prepares PS Modified Adhesive body microballoon lotion: taking styrene, α-methacrylic acid and water, be uniformly mixed, at 75-90 DEG C
Under be stirred to react 30-60min, be then injected into initiator potassium persulfate solution, react 7-9h at 75-90 DEG C, obtain modified PS
Colloid micro ball lotion；
Step 2, TiO is wrapped up2Shell structurre: gained PS Modified Adhesive body microballoon emulsion dispersion is in the mixed liquor of ethyl alcohol and acetonitrile, note
For A liquid；Butyl titanate is dissolved in the mixed liquor of ethyl alcohol and acetonitrile, is denoted as B liquid；Under agitation, B liquid is slowly injected into A
In liquid, it is stirred to react to obtain PS@TiO2The dispersion liquid of microballoon is ground into PS@TiO using washing, drying2Powder；
Step 3, PS@TiO2Powder carries out calcination processing twice: primary calcining is to calcine 2h at 450-550 DEG C；Secondary clacining is
10min is calcined at 320-420 DEG C, obtains titanium dioxide hollow ball shell.
2. the preparation method of the intact anatase titanium dioxide hollow ball shell of spherical shape according to claim 1, feature
It is, in step 1, the ratio of styrene, α-methacrylic acid and water are as follows: (7-14) mL:(0.5-1) mL:(90-180) mL.
3. the preparation method of the intact anatase titanium dioxide hollow ball shell of spherical shape according to claim 1, feature
It is, in step 1, the ratio of potassium peroxydisulfate and styrene is 17g:(7-14) mL.
4. the preparation method of the intact anatase titanium dioxide hollow ball shell of spherical shape according to claim 1, feature
It is, in step 1, styrene used is purified mistake, purification process are as follows: styrene is washed with sodium hydroxide solution,
Milli-Q water is used again, and until solution is in neutrality, addition solid water-free calcium chloride removes water.
5. the preparation method of the intact anatase titanium dioxide hollow ball shell of spherical shape according to claim 1, feature
It is, in step 2, after B liquid injects A liquid, the ratio of PS Modified Adhesive body microballoon and butyl titanate is (3-6) g:(0.5-3) mL.
6. the preparation method of the intact anatase titanium dioxide hollow ball shell of spherical shape according to claim 1, feature
It is, in step 2, after B liquid is slowly injected A liquid, reacts 1-30h at 20-40 DEG C.
7. the preparation method of the intact anatase titanium dioxide hollow ball shell of spherical shape according to claim 1, feature
It is, in step 2, the drop speed control that B liquid slowly injects A liquid is controlled in drop speed in 30-60 drop/min, every dropwise addition 5mL interval 5-
During which 10min is kept stirring, be during which kept stirring.
8. the preparation method of the intact anatase titanium dioxide hollow ball shell of spherical shape according to claim 1, feature
It is, in step 2, washing is specifically: detergent, ultrasonic disperse 20-30min, centrifugation is added；Centrifugal rotational speed is 7000-
10000r/min, centrifugation time 20-30min.
9. the preparation method of the intact anatase titanium dioxide hollow ball shell of spherical shape according to claim 1, feature
It is, primary calcining is to be warming up to 480-520 DEG C in tube furnace with 1-5 DEG C/min of heating rate；Secondary clacining is in Muffle
320-420 DEG C is warming up in furnace with 1-5 DEG C/min of heating rate.
10. the intact anatase titanium dioxide of the spherical shape that the described in any item preparation methods of claim 1-9 are prepared is empty
Bulbus cordis shell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811408890.4A CN109485093B (en) | 2018-11-23 | 2018-11-23 | Anatase type titanium dioxide hollow spherical shell with good spherical shape and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811408890.4A CN109485093B (en) | 2018-11-23 | 2018-11-23 | Anatase type titanium dioxide hollow spherical shell with good spherical shape and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109485093A true CN109485093A (en) | 2019-03-19 |
| CN109485093B CN109485093B (en) | 2021-04-30 |
Family
ID=65696609
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811408890.4A Active CN109485093B (en) | 2018-11-23 | 2018-11-23 | Anatase type titanium dioxide hollow spherical shell with good spherical shape and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109485093B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112225247A (en) * | 2020-10-20 | 2021-01-15 | 桂林理工大学 | Nano titanium dioxide open hollow sphere and preparation method thereof |
| CN113415824A (en) * | 2021-06-24 | 2021-09-21 | 宁波航天米瑞科技有限公司 | Titanium dioxide particle and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007024917A2 (en) * | 2005-08-23 | 2007-03-01 | Altairnano, Inc. | HIGHLY PHOTOCATALYTIC PHOSPHORUS-DOPED ANATASE-TiO2 COMPOSITION AND RELATED MANUFACTURING METHODS |
| CN102730753A (en) * | 2011-04-02 | 2012-10-17 | 中国科学院金属研究所 | Method for preparing anatase porous TiO2 spheres, core-shell structure and hollow spheres |
| CN103803645A (en) * | 2014-02-19 | 2014-05-21 | 陕西科技大学 | Method for preparing anatase TiO2 nanometer hollow sphere |
| CN106082317A (en) * | 2016-05-31 | 2016-11-09 | 陕西科技大学 | A kind of preparation method of hollow hemisphere titanium dioxide |
| CN106745225A (en) * | 2016-11-24 | 2017-05-31 | 陕西盛迈石油有限公司 | Nanoscale TiO2The preparation method of hollow ball |
-
2018
- 2018-11-23 CN CN201811408890.4A patent/CN109485093B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007024917A2 (en) * | 2005-08-23 | 2007-03-01 | Altairnano, Inc. | HIGHLY PHOTOCATALYTIC PHOSPHORUS-DOPED ANATASE-TiO2 COMPOSITION AND RELATED MANUFACTURING METHODS |
| CN102730753A (en) * | 2011-04-02 | 2012-10-17 | 中国科学院金属研究所 | Method for preparing anatase porous TiO2 spheres, core-shell structure and hollow spheres |
| CN103803645A (en) * | 2014-02-19 | 2014-05-21 | 陕西科技大学 | Method for preparing anatase TiO2 nanometer hollow sphere |
| CN106082317A (en) * | 2016-05-31 | 2016-11-09 | 陕西科技大学 | A kind of preparation method of hollow hemisphere titanium dioxide |
| CN106745225A (en) * | 2016-11-24 | 2017-05-31 | 陕西盛迈石油有限公司 | Nanoscale TiO2The preparation method of hollow ball |
Non-Patent Citations (2)
| Title |
|---|
| JIABAI CAI ET AL.: "Influence of TiO2 hollow sphere size on its photo-reduction activity for toxic Cr(VI) removal", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| 李桂村 等: "二氧化钛空心微球的制备及表征", 《功能材料》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112225247A (en) * | 2020-10-20 | 2021-01-15 | 桂林理工大学 | Nano titanium dioxide open hollow sphere and preparation method thereof |
| CN113415824A (en) * | 2021-06-24 | 2021-09-21 | 宁波航天米瑞科技有限公司 | Titanium dioxide particle and preparation method and application thereof |
| CN113415824B (en) * | 2021-06-24 | 2022-05-03 | 宁波航天米瑞科技有限公司 | Titanium dioxide particle and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109485093B (en) | 2021-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106082317B (en) | A kind of preparation method of hollow hemisphere titanium dioxide | |
| CN106732818B (en) | Double layer hollow material based on titanium dioxide and preparation method thereof and the application in hydrogen sulfide photocatalysis treatment | |
| CN100348499C (en) | Prepn. process of mesic hole hollow ball-shape titania powder | |
| CN105056929A (en) | Graphene/titanium dioxide composite adopting hollow microspherical structure and preparation method of composite | |
| CN106430295B (en) | A kind of micro-nano hierarchy BaTiO3Crystal and preparation method thereof | |
| CN102786083A (en) | Preparation method of titanium dioxide nano hollow ball | |
| CN102674451A (en) | Preparation method of {001} face exposed titanium dioxide nanocrystals | |
| CN108609649A (en) | A kind of preparation method of sea urchin shape magnetic hollow microsphere | |
| CN106430308B (en) | A kind of method that hydro-thermal method prepares vanadic anhydride solid microsphere | |
| CN103111274B (en) | Preparation method of graphene/TiO2 fiber | |
| CN103771485A (en) | Controllable preparation method for three-dimensional nano self-assembly of copper oxide | |
| CN109485093A (en) | A kind of anatase titanium dioxide hollow ball shell and preparation method thereof that spherical shape is intact | |
| CN103342991A (en) | Composite nanocapsule phase-change material and preparation method thereof | |
| CN102199004A (en) | Preparation method of hollow glass microspheres with directional titanium dioxide nano-rods growths on surface | |
| CN103880073A (en) | Method for preparing nano titanium dioxide by applying precipitation process and adopting microreactor | |
| CN104193862A (en) | Preparation method of polystyrene/silver/titanium dioxide composite material | |
| CN104772136A (en) | Pucherite as well as preparation method and application of pucherite | |
| CN110201655A (en) | A kind of one-step method prepares hollow TiO2The method and application of nanosphere | |
| CN104310466A (en) | Hollow titanium dioxide microsphere based on gel sphere precursor and preparation method of hollow titanium dioxide microsphere | |
| CN102020283A (en) | Preparation method of silicon dioxide nano hollow sphere with adjustable inner diameter | |
| CN108033485A (en) | A kind of one-step synthesis method TiO2The efficient hydrogen manufacturing of microballoon and the method for degradation of contaminant | |
| CN103130266A (en) | Preparation method of titanium dioxide hollow ball constructed by nano slices | |
| CN102286804A (en) | Preparation method of titanium dioxide fibers with photocatalysis function and polycrystalline nanostructure | |
| CN101857267B (en) | Preparation method of titanium dioxide nano material with core-shell structure | |
| CN108298579A (en) | A kind of preparation method of hollow octahedra anatase titania |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |