CN104843779A - Hollow spherical rutile titanium dioxide mesocrystal and preparation method thereof - Google Patents
Hollow spherical rutile titanium dioxide mesocrystal and preparation method thereof Download PDFInfo
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- CN104843779A CN104843779A CN201510210633.XA CN201510210633A CN104843779A CN 104843779 A CN104843779 A CN 104843779A CN 201510210633 A CN201510210633 A CN 201510210633A CN 104843779 A CN104843779 A CN 104843779A
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Abstract
The invention discloses hollow spherical rutile titanium dioxide mesocrystal which is of a hollow spherical structure assembled through rutile crystal nanorods, wherein the diameter of a hollow sphere is 3.0 to 6.0 microns, the length of every nanorod is 200 to 500 nanometers, and the width of every nanorod is 100 to 250 nanometers. A preparation method of the hollow spherical rutile titanium dioxide mesocrystal comprises the step of dissolving titanium potassium oxalate into the hydrogen peroxide reaction liquid for 48 to 72 hours of heat preservation under 80 DEG C, wherein nitric acid is added into the hydrogen peroxide reaction liquid. According to the hollow spherical rutile titanium dioxide mesocrystal and the preparation method thereof, the high temperature and high pressure hydrothermal environment is not required, the hollow spherical rutile titanium dioxide mesocrystal is obtained after the low temperature, the preparation route is simple and easy, the cost is low, the powder production rate is high, and the hollow spherical rutile titanium dioxide mesocrystal and the preparation method can be applied to the fields of light catalysis, lithium ion batteries and the like.
Description
Technical field
The present invention relates to a kind of hollow ball-shape rutile titanium dioxide mesomorphic and preparation method thereof, belong to the preparation field of metal oxide functional material.
Background technology
Titanium dioxide is that a few is in one of acidity or inorganic materials all highly stable in the basic conditions, owing to having excellent biocompatibility, and itself is nontoxic, resource is sufficient simultaneously, with low cost, have broad application prospects in photochemical catalysis, electrochromism, dye sensitization solar battery and lithium ion battery, day by day become a kind of critical material solving global environment and energy problem.Mesomorphic structure material has abundant mesoporous, its atomic arrangement orientation close to single crystal structure, thus its physicochemical property and monocrystalline similar, and specific surface area is significantly higher than monocrystalline, becomes one of Recent study focus.The preparation method of current titanium dioxide mesomorphic mainly contains the hot method of hydrothermal/solvent, and the topology transformation etc. of precursor.Wherein the hot method of hydrothermal/solvent needs high temperature and high pressure environment, and energy consumption is large, and environment friendly is poor, and there is larger potential safety hazard, industrialization cost is higher; And topological transformation method needs to prepare suitable precursor, obtain titanium dioxide mesomorphic by the subsequent processes of precursor.The pattern of the titanium dioxide crystal obtained at present has nanometer rod, nano flower hollow Nano brick, dumbbell shape and sheet structure, but does not also have low temperature directly to prepare by the stacking hollow ball-shape structure of rutile crystalline nanometer rod.
Summary of the invention
The object of this invention is to provide a kind of process hollow ball-shape rutile titanium dioxide mesomorphic that is simple, that prepare without the single stage method of template, low cost and preparation method thereof.
Hollow ball-shape rutile titanium dioxide mesomorphic of the present invention is the hollow ball-shape structure assembled by rutile crystalline nanometer rod, and the diameter of hollow ball is 3.0 ~ 6.0 μm, and the length of nanometer rod is 200 ~ 500nm, and width is 100 ~ 250nm.
The preparation method of hollow ball-shape rutile titanium dioxide mesomorphic of the present invention, its concrete steps are as follows:
1) joined by the nitric acid of mass concentration 63% in the hydrogen peroxide solution of mass concentration 10%, the volume ratio of nitric acid and hydrogen peroxide solution is 0.02-0.06;
2) in the nitric acid and hydrogen peroxide mixed solution of step 1), add titanium potassium oxalate(T.P.O.), make titanium potassium oxalate(T.P.O.) concentration in the solution be 100 ~ 200 mM/ls, sonic oscillation fully mixes, and then seals, 80
obe incubated 48 ~ 72 hours under C, through centrifugation, washing, drying, obtain hollow ball-shape rutile titanium dioxide mesomorphic.
The present invention achieves the low temperature preparation of hollow ball-shape structure rutile titanium dioxide mesomorphic first.Utilize titanium potassium oxalate(T.P.O.) for titanium source, utilize the titanium potassium oxalate(T.P.O.) hydrolysis-dissolving in the hydrogen peroxide solution being dissolved with nitric acid-deposition process again, 80
othe hollow ball-shape rutile titanium dioxide mesomorphic of high-crystallinity is prepared under the low temperature of C.This hollow ball-shape structure is the secondary structure that essentially consist unit assembles by nanometer rod, and the selected area electron diffraction of individual nanorod shows that synthesis of nano rod has the structure of single crystal-like, and in monocrystal nano rod, distribution is mesoporous.The hollow ball-shape titania mesomorphic of synthesis has a wide range of applications in various fields such as photochemical catalysis, photoelectrocatalysis, solar cell, gas sensor, biomaterial, lithium ion batteries.
Accompanying drawing explanation
Fig. 1 is the low power SEM photo of hollow ball-shape titania mesomorphic prepared by embodiment 1;
Fig. 2 is the high power SEM photo of hollow ball-shape titania mesomorphic prepared by embodiment 1;
Fig. 3 is the XRD figure spectrum of hollow ball-shape titania mesomorphic prepared by embodiment 1;
Fig. 4 is the TEM photo of the essentially consist unit nanometer rod of hollow ball-shape titania mesomorphic prepared by embodiment 1;
Fig. 5 is HRTEM figure and the FFT Transformation Graphs of the essentially consist unit nanometer rod of hollow ball-shape titania mesomorphic prepared by embodiment 1; Wherein scheming a is HRTEM figure, and scheming b is FFT Transformation Graphs.
Fig. 6 is the nitrogen adsorption curve of hollow ball-shape titania mesomorphic prepared by embodiment 1;
Fig. 7 is the SEM figure that embodiment 1 reacts 12 hours reaction product; Wherein scheming a is low power SEM photo, and figure b is high power SEM photo.
Fig. 8 is the SEM figure that embodiment 1 reacts 24 hours reaction product; Wherein scheming a is low power SEM photo, and figure b is high power SEM photo.
Fig. 9 is the SEM figure that embodiment 1 reacts 36 hours reaction product; Wherein scheming a is low power SEM photo, and figure b is high power SEM photo.
Figure 10 is the SEM figure that embodiment 1 reacts 48 hours reaction product; Wherein scheming a is low power SEM photo, and figure b is high power SEM photo.
Figure 11 is the SEM figure that embodiment 1 reacts 60 hours reaction product; Wherein scheming a is low power SEM photo, and figure b is high power SEM photo.
Figure 12 is 12 hours reaction product XRD figure spectrums;
Figure 13 is hollow ball-shape titania mesomorphic SEM photo prepared by embodiment 2;
Figure 14 is hollow ball-shape titania mesomorphic SEM photo prepared by embodiment 3.
Embodiment
Set forth the present invention further below in conjunction with embodiment, but the present invention is not only confined to following embodiment.
Embodiment 1
1) get 3 mL mass percents be 63% nitric acid to join 50 mL mass percents be in the hydrogen peroxide solution of 10%;
2) add titanium potassium oxalate(T.P.O.) in the solution obtained in step 1), make titanium potassium oxalate(T.P.O.) concentration in the solution be 100 mM/ls, sonic oscillation fully mixes, and obtains garnet clear solution;
3) by step 2) sealing of the garnet clear solution that obtains, be placed on 80
oin C baking oven, be incubated 72 hours, through centrifugation, washing, drying, obtain white powder, be hollow ball-shape rutile titanium dioxide mesomorphic.
As shown in Figure 1, 2, width about 100 ~ 250 nm of nanometer rod, length is about 200 ~ 500 nm to the hollow ball-shape rutile titanium dioxide mesomorphic that this example obtains, and the hollow ball diameter assembled by nanometer rod is 3.0 ~ 6.0 μm.The XRD results verification gained powder of Fig. 3 is well-crystallized's rutile structure titanium dioxide.Fig. 4,5 the display of TEM characterization result, the basic structural unit of composition hollow ball-shape is rutile titanium dioxide monocrystalline (i.e. mesomorphic) that distribution is mesoporous in it.The low temperature nitrogen adsorption curve of Fig. 6 shows, the sample specific surface area of preparation is 32.19 m
2/ g, mean pore size is 11.3 nm, confirms mesoporous existence further.
The time series test display of Fig. 7, be 12 hours when reacted, reaction product is the globe that set of nanowires is dressed up, known in conjunction with Figure 12, and this product is hydrogen metatitanic acid.Reaction times is 24 hours, and as shown in Figure 8, nano wire disappears, and occurs the solid sphere that club shaped structure is stacking.Along with the carrying out of reaction, formed gradually and assemble the hollow ball-shape structure formed, as shown in Fig. 9,10,11 by nanometer rod.
Embodiment 2
1) get 1 mL mass percent be 63% nitric acid to join 50 mL mass percents be in the hydrogen peroxide solution of 10%;
2) add titanium potassium oxalate(T.P.O.) in the solution obtained in step 1), make titanium potassium oxalate(T.P.O.) concentration in the solution be 100 mM/ls, sonic oscillation fully mixes, and obtains garnet clear solution;
3) by step 2) sealing of the garnet clear solution that obtains, be placed on 80
oin C baking oven, be incubated 72 hours, through centrifugation, washing, drying, obtain white powder.
The SEM photo of the hollow ball-shape rutile titanium dioxide mesomorphic that this example is obtained is as Figure 13, and the length of its structural unit nanometer rod is 150 ~ 250 nm, and width is 70 ~ 150 nm.
Embodiment 3
1) get 3 mL mass percents be 63% nitric acid to join 50 mL mass percents be in the hydrogen peroxide solution of 10%;
2) add titanium potassium oxalate(T.P.O.) in the solution obtained in step 1), make titanium potassium oxalate(T.P.O.) concentration in the solution be 200 mM/ls, sonic oscillation fully mixes, and obtains garnet clear solution;
3) by step 2) sealing of the garnet clear solution that obtains, be placed on 80
oin C baking oven, be incubated 72 hours, through centrifugation, washing, drying, obtain white powder.
The SEM photo of the hollow ball-shape rutile titanium dioxide mesomorphic that this example is obtained is as Figure 14, and the length of its structural unit nanometer rod is about 150 ~ 200 nm, and width is about 50 ~ 100 nm.
Claims (2)
1. a hollow ball-shape rutile titanium dioxide mesomorphic, it is characterized in that the hollow ball-shape structure assembled by rutile crystalline nanometer rod, and the diameter of hollow ball is 3.0 ~ 6.0 μm, and the length of nanometer rod is 200 ~ 500nm, and width is 100 ~ 250nm.
2. prepare the method for hollow ball-shape rutile titanium dioxide mesomorphic according to claim 1, comprise step as follows:
1) joined by the nitric acid of mass concentration 63% in the hydrogen peroxide solution of mass concentration 10%, the volume ratio of nitric acid and hydrogen peroxide solution is 0.02-0.06;
2) in the nitric acid and hydrogen peroxide mixed solution of step 1), add titanium potassium oxalate(T.P.O.), make titanium potassium oxalate(T.P.O.) concentration in the solution be 100 ~ 200 mM/ls, sonic oscillation fully mixes, and then seals, 80
obe incubated 48 ~ 72 hours under C, through centrifugation, washing, drying, obtain hollow ball-shape rutile titanium dioxide mesomorphic.
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Cited By (6)
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| CN105540657A (en) * | 2016-01-14 | 2016-05-04 | 浙江大学 | Nanosheet-assembling core-shell structure anatase titanium dioxide microsphere and preparation method thereof |
| CN105600822A (en) * | 2016-03-31 | 2016-05-25 | 天津城建大学 | Preparation method of litchi-like hierarchical-structure {001}-surface-exposed TiO2 powder |
| CN106238097A (en) * | 2016-07-28 | 2016-12-21 | 安徽师范大学 | The TiO that a kind of butoxy is modified2single crystal hollow four directions nanocone materials, preparation method and applications |
| CN106370858A (en) * | 2016-08-20 | 2017-02-01 | 福建师范大学 | Potential addressing mode-based double tumor marker photoelectric detection method |
| CN106466604A (en) * | 2016-11-22 | 2017-03-01 | 安徽理工大学 | A kind of Cu2O/TiO2Composite photocatalyst material and preparation method thereof |
| CN112266242A (en) * | 2020-11-19 | 2021-01-26 | 张希君 | Method for preparing spherical rutile particles by using rutile with size less than 200 meshes as main raw material |
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| CN102583525A (en) * | 2012-01-31 | 2012-07-18 | 桂林理工大学 | Preparation method of rutile titanium dioxide mesomorphic crystal |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105540657A (en) * | 2016-01-14 | 2016-05-04 | 浙江大学 | Nanosheet-assembling core-shell structure anatase titanium dioxide microsphere and preparation method thereof |
| CN105600822A (en) * | 2016-03-31 | 2016-05-25 | 天津城建大学 | Preparation method of litchi-like hierarchical-structure {001}-surface-exposed TiO2 powder |
| CN106238097A (en) * | 2016-07-28 | 2016-12-21 | 安徽师范大学 | The TiO that a kind of butoxy is modified2single crystal hollow four directions nanocone materials, preparation method and applications |
| CN106238097B (en) * | 2016-07-28 | 2018-10-16 | 安徽师范大学 | A kind of TiO of butoxy modification2Single crystal hollow four directions nanocone materials, preparation method and applications |
| CN106370858A (en) * | 2016-08-20 | 2017-02-01 | 福建师范大学 | Potential addressing mode-based double tumor marker photoelectric detection method |
| CN106370858B (en) * | 2016-08-20 | 2017-11-07 | 福建师范大学 | A kind of photoelectric detecting method of double tumor markerses based on current potential addressing mode |
| CN106466604A (en) * | 2016-11-22 | 2017-03-01 | 安徽理工大学 | A kind of Cu2O/TiO2Composite photocatalyst material and preparation method thereof |
| CN112266242A (en) * | 2020-11-19 | 2021-01-26 | 张希君 | Method for preparing spherical rutile particles by using rutile with size less than 200 meshes as main raw material |
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