CN105540657A - Nanosheet-assembling core-shell structure anatase titanium dioxide microsphere and preparation method thereof - Google Patents
Nanosheet-assembling core-shell structure anatase titanium dioxide microsphere and preparation method thereof Download PDFInfo
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- CN105540657A CN105540657A CN201610024981.2A CN201610024981A CN105540657A CN 105540657 A CN105540657 A CN 105540657A CN 201610024981 A CN201610024981 A CN 201610024981A CN 105540657 A CN105540657 A CN 105540657A
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- C—CHEMISTRY; METALLURGY
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- 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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- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- 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
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- 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
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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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
- C01P2004/50—Agglomerated particles
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- C—CHEMISTRY; METALLURGY
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- 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 nanosheet-assembling core-shell structure anatase titanium dioxide microsphere and a preparation method thereof. Titanium potassium oxalate serves as a titanium source, titanium potassium oxalate is hydrolyzed and redeposited in a hydrogen peroxide solution where nitric acid is dissolved, and a nanosheet-assembling core-shell structure microsphere is prepared at the low temperature of 40 DEG C close to the room temperature; then, the subsequent acid pickling and forging processes are conducted, and the nanosheet-assembling core-shell structure anatase titanium dioxide microsphere is obtained. The high-temperature high-pressure hydrothermal environment is not needed, and the nanosheet-assembling core-shell structure anatase titanium dioxide microsphere is obtained in one step at the low temperature. The preparation technology is simple and easy to implement, cost is low, the yield is high, and the nanosheet-assembling core-shell structure anatase titanium dioxide microsphere can be used in various fields such as photocatalysis, photoelectric catalysis, solar batteries, gas sensors, biological materials and lithium ion batteries.
Description
Technical field
The present invention relates to nucleocapsid structure anatase titania microballoon of a kind of nanometer sheet assembling and preparation method thereof, belong to metal oxide functional field of material technology.
Background technology
Titanium dioxide is that a few is in one of acidity or inorganic multifunctional material all highly stable in the basic conditions, owing to having excellent biocompatibility, and itself is nontoxic, resource is sufficient simultaneously, with low cost, day by day become a kind of critical material solving global environment and energy problem.Nucleocapsid structure, due to the structural advantage of its uniqueness, becomes the focus of concern in recent years, has broad application prospects in photochemical catalysis, lithium ion battery, gas sensing, the transport of medicine orientation etc.The existing method preparing titanium dioxide core shell structure needs to use template mostly, and production cost is high.Patent of invention CN104860348A discloses a kind of method preparing the titanium dioxide of core-shell structure that nanometer sheet is constructed, but the titanium source that the method uses is titanium alcohol source, facile hydrolysis, difficult control, and the method used is solvent-thermal method, needs high temperature and high pressure environment, energy consumption is large, environment friendly is poor, and there is larger potential safety hazard, industrialization cost is higher.Patent of invention CN101857267A discloses a kind of method preparing titanium dioxide of core-shell structure nano material, with trivalent titanium salt for titanium source, overcome the problem such as facile hydrolysis, instability, increase environmental pressure that other titanium sources exist, but the method used is still the solvent-thermal method of High Temperature High Pressure.
Summary of the invention
The object of this invention is to provide a kind of process nucleocapsid structure anatase titania microballoon that is simple, that assemble without the nanometer sheet of template, low cost and preparation method thereof.
The nucleocapsid structure anatase titania microballoon of nanometer sheet assembling of the present invention, the diameter of microballoon is 1.2 ~ 2.5 μm, microballoon is nucleocapsid structure, the diameter of kernel is 0.25 ~ 0.55 μm, and the thickness of shell is 0.30 ~ 0.65 μm, has cavity between kernel and shell, the nanometer sheet that shell is 10 ~ 20nm by thickness assembles, nanometer sheet is formed by connecting by particle, there is hole between particle, and the crystal formation of microballoon is Anatase.
The preparation method of the nucleocapsid structure anatase titania microballoon of nanometer sheet assembling 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) to step 1) nitric acid and hydrogen peroxide mixed solution in add titanium potassium oxalate(T.P.O.), make titanium potassium oxalate(T.P.O.) concentration in the solution be 300 ~ 500 mM/ls, sonic oscillation fully mixes, and then seals, at 40 ~ 80 DEG C be incubated 48 ~ 144 hours;
3) collected by centrifugation powder, first uses the pickling of 0.1MHCl solution, then uses deionized water wash, drying, then in atmosphere 450 DEG C calcining 1 hour.
The present invention achieves the low-temperature growth of the nucleocapsid structure anatase titania microballoon of nanometer sheet assembling first.Take titanium potassium oxalate(T.P.O.) as titanium source, utilize the hydrolysis of titanium potassium oxalate(T.P.O.) in the hydrogen peroxide solution being dissolved with nitric acid-deposition process again, prepare the nucleocapsid structure microballoon of nanometer sheet assembling under close to the low temperature of 40 DEG C of room temperature, be aided with follow-up pickling and calcination process, obtain the nucleocapsid structure anatase titania microballoon of nanometer sheet assembling.The present invention is without the need to the thermal and hydric environment of High Temperature High Pressure, the nucleocapsid structure anatase titania microballoon of next step acquisition nanometer sheet assembling of low temperature, preparation technology is simple and easy to do, cost is low, productive rate is high, and the nucleocapsid structure anatase titania microballoon of this nanometer sheet assembling 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 the nucleocapsid structure anatase titania microballoon of embodiment 1 nanometer sheet assembling;
Fig. 2 is the high power SEM photo of the nucleocapsid structure anatase titania microballoon of embodiment 1 nanometer sheet assembling;
Fig. 3 is the XRD figure spectrum of the nucleocapsid structure anatase titania microballoon of embodiment 1 nanometer sheet assembling;
Fig. 4 is the TEM photo of the nucleocapsid structure anatase titania microballoon of embodiment 1 nanometer sheet assembling;
Fig. 5 is HRTEM figure and the SAED Transformation Graphs of the nucleocapsid structure anatase titania microballoon of embodiment 1 nanometer sheet assembling; Wherein scheming a is HRTEM figure, and scheming b is SAED Transformation Graphs.
Fig. 6 is the nitrogen adsorption curve of the nucleocapsid structure anatase titania microballoon of embodiment 1 nanometer sheet assembling;
Fig. 7 is the SEM figure of the nucleocapsid structure anatase titania microballoon of embodiment 2 nanometer sheet assembling;
Fig. 8 is the SEM figure of the nucleocapsid structure anatase titania microballoon of embodiment 3 nanometer sheet assembling;
Fig. 9 is the SEM photo of the nucleocapsid structure anatase titania microballoon of embodiment 4 nanometer sheet assembling;
Figure 10 is the SEM photo of the nucleocapsid structure anatase titania microballoon of embodiment 5 nanometer sheet assembling.
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 3mL mass concentration be 63% nitric acid to join 50mL mass concentration be in the hydrogen peroxide solution of 10%;
2) in step 1) add titanium potassium oxalate(T.P.O.) in the solution that obtains, make titanium potassium oxalate(T.P.O.) concentration in the solution be 500 mM/ls, sonic oscillation fully mixes, and obtains garnet clear solution, is sealed by solution, is placed in 40 DEG C of baking ovens, is incubated 72 hours;
3) collected by centrifugation powder, with 0.1MHCl solution pickling 3 times, each 40 minutes, then use deionized water wash, drying, then 450 DEG C of calcinings 1 hour in atmosphere, obtained white powder, are the nucleocapsid structure anatase titania microballoon of nanometer sheet assembling.
As shown in Figure 1, 2, the diameter of microballoon is 1.2 ~ 2.5 μm to the nucleocapsid structure anatase titania microballoon of the nanometer sheet assembling that this example is obtained, and the diameter of kernel is 0.25 ~ 0.55 μm, and the generous of shell is 0.30 ~ 0.65 μm.The XRD results verification gained powder of Fig. 3 is the anatase structured titanium dioxide of well-crystallized.Fig. 4,5 TEM characterization result display, microballoon is made up of nucleocapsid structure, has hole between kernel and shell, and shell is assembled by nanometer sheet, and nanometer sheet is formed by connecting by particle, there is many holes between particle.The low temperature nitrogen adsorption curve of Fig. 6 shows, the sample specific surface area of preparation is 92.3m
2/ g, mean pore size is 16.9nm, and pore fraction is 0.3911cm
3/ g.
Example 2 step is with example 1, and difference is " being incubated 48 hours ", and the SEM figure obtaining the nucleocapsid structure anatase titania microballoon of nanometer sheet assembling under this condition is shown in Fig. 7, and the diameter of microballoon is 1.5 ~ 2.4 μm.
Example 3 step is with example 1, and difference is " being incubated 144 hours ", and the SEM figure obtaining the nucleocapsid structure anatase titania microballoon of nanometer sheet assembling under this experiment condition is shown in Fig. 8, and the diameter of microballoon is 1.3 ~ 2.2 μm.
Embodiment 4
1) get 1mL mass concentration be 63% nitric acid to join 50mL mass concentration be in the hydrogen peroxide solution of 10%;
2) in step 1) add titanium potassium oxalate(T.P.O.) in the solution that obtains, make titanium potassium oxalate(T.P.O.) concentration in the solution be 300 mM/ls, sonic oscillation fully mixes, and obtains garnet clear solution, is sealed by solution, is placed in 80 DEG C of baking ovens, is incubated 72 hours;
3) collected by centrifugation powder, with 0.1MHCl solution pickling 3 times, each 40 minutes, then use deionized water wash, drying, then 450 DEG C of calcinings 1 hour in atmosphere, obtained white powder, are the nucleocapsid structure anatase titania microballoon of nanometer sheet assembling.
The SEM pattern display of reaction result: Fig. 9, obtain the nucleocapsid structure anatase titania microballoon of nanometer sheet assembling under this condition, the diameter of microballoon is 3.0 ~ 8.0 μm, and the width forming the nanometer sheet of shell is 2.0 ~ 5.0 μm.
Embodiment 5
1) get 3mL mass concentration be 63% nitric acid to join 50mL mass concentration be in the hydrogen peroxide solution of 10%;
2) in step 1) add titanium potassium oxalate(T.P.O.) in the solution that obtains, make titanium potassium oxalate(T.P.O.) concentration in the solution be 400 mM/ls, sonic oscillation fully mixes, and obtains garnet clear solution, is sealed by solution, is placed in 80 DEG C of baking ovens, is incubated 72 hours;
3) collected by centrifugation powder, with 0.1MHCl solution pickling 3 times, each 40 minutes, then use deionized water wash, drying, then 450 DEG C of calcinings 1 hour in atmosphere, obtained white powder, are the nucleocapsid structure anatase titania microballoon of nanometer sheet assembling.
The SEM pattern display of reaction result: Figure 10, obtain the nucleocapsid structure anatase titania microballoon of nanometer sheet assembling under this condition, the diameter of microballoon is 1.5 ~ 2.2 μm, and the width forming the nanometer sheet of shell is being 0.5 ~ 1.5 μm.
Claims (2)
1. the nucleocapsid structure anatase titania microballoon of a nanometer sheet assembling, it is characterized in that, the diameter of microballoon is 1.2 ~ 2.5 μm, and microballoon is nucleocapsid structure, and the diameter of kernel is 0.25 ~ 0.55 μm, the thickness of shell is 0.30 ~ 0.65 μm, have cavity between kernel and shell, the nanometer sheet that shell is 10 ~ 20nm by thickness assembles, and nanometer sheet is formed by connecting by particle, there is hole between particle, the crystal formation of microballoon is Anatase.
2., by the preparation method of the nucleocapsid structure anatase titania microballoon of nanometer sheet assembling according to claim 1, its step is 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) to step 1) nitric acid and hydrogen peroxide mixed solution in add titanium potassium oxalate(T.P.O.), make titanium potassium oxalate(T.P.O.) concentration in the solution be 300 ~ 500 mM/ls, sonic oscillation fully mixes, and then seals, at 40 ~ 80 DEG C be incubated 48 ~ 144 hours;
3) collected by centrifugation powder, first uses the pickling of 0.1MHCl solution, then uses deionized water wash, drying, then in atmosphere 450 DEG C calcining 1 hour.
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Cited By (4)
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| CN106252607A (en) * | 2016-08-11 | 2016-12-21 | 郑州大学 | Hemicentrotus seu Strongylocentrotus shape nanometer Tixsn1 xo2the preparation method of/Graphene three-dimensional composite material and the application on lithium ion battery negative thereof |
| 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 |
| CN111874944A (en) * | 2020-07-28 | 2020-11-03 | 盐城工学院 | Hydrothermal synthesis method of biphase titanium dioxide |
| CN112939072A (en) * | 2021-04-22 | 2021-06-11 | 泉州师范学院 | Preparation method of high-dispersion rutile titanium dioxide microspheres |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106252607A (en) * | 2016-08-11 | 2016-12-21 | 郑州大学 | Hemicentrotus seu Strongylocentrotus shape nanometer Tixsn1 xo2the preparation method of/Graphene three-dimensional composite material and the application on lithium ion battery negative thereof |
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| 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 |
| CN111874944A (en) * | 2020-07-28 | 2020-11-03 | 盐城工学院 | Hydrothermal synthesis method of biphase titanium dioxide |
| CN111874944B (en) * | 2020-07-28 | 2022-09-23 | 盐城工学院 | Hydrothermal synthesis method of biphase titanium dioxide |
| CN112939072A (en) * | 2021-04-22 | 2021-06-11 | 泉州师范学院 | Preparation method of high-dispersion rutile titanium dioxide microspheres |
| CN112939072B (en) * | 2021-04-22 | 2022-09-16 | 泉州师范学院 | Preparation method of high-dispersion rutile titanium dioxide microspheres |
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