CN104692457B - The micro-nano hierarchy TiO of a kind of lichee shape 2crystal and synthetic method thereof - Google Patents
The micro-nano hierarchy TiO of a kind of lichee shape 2crystal and synthetic method thereof Download PDFInfo
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- CN104692457B CN104692457B CN201510035292.7A CN201510035292A CN104692457B CN 104692457 B CN104692457 B CN 104692457B CN 201510035292 A CN201510035292 A CN 201510035292A CN 104692457 B CN104692457 B CN 104692457B
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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
- 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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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Abstract
The present invention relates to the micro-nano hierarchy TiO of a kind of lichee shape
2crystal and synthetic method thereof.First prepare homodisperse spherical unformed presoma TiO
2, then by presoma TiO
2the TiO of the micro-nano hierarchy of lichee shape is obtained with solvent crystallization in thermal and hydric environment
2crystal.Obtained TiO
2crystal is spherical, and diameter is 500-700nm, and spherical surface is evenly distributed with the ball bumps that diameter is 10-20nm.This TiO
2crystal has anatase structured, in solar cell, photochemical catalysis, automatically cleaning etc., have important application.Simultaneously the method is that the surperficial classification of other particle is modified and provided a kind of new thinking.
Description
Technical field
The present invention relates to a kind of TiO
2micro Nano material, the micro-nano hierarchy TiO of especially a kind of lichee shape
2crystal and synthetic method thereof
Technical background
Titanium dioxide (TiO
2) there is excellent photoelectric properties and physical property, have a wide range of applications in fields such as chromatographic separation, lithium ion battery, dye sensitization solar battery, gas sensor, catalysis, its with low cost and environment friendly also receives the favor of investigator, is therefore the study hotspot of information and power and environmentally conscious materials always.
Pile up because spherical morphology has uniform close, the characteristic that surface curvature, mobility etc. are adjustable, monodisperse spherical TiO
2material has demonstrated many real and emerging application.Utilize liquid phase method, synthesize the TiO of different morphologies
2powder granule, as adopted sol-gel traditional technology mating surface promoting agent synthesizing spherical TiO
2particle, utilizes polystyrene spheres, SiO
2the synthesizing porous TiO of prefab-form such as ball, C ball, PMMA ball
2ball.But above-mentioned preparation technology mostly is the single dispersing TiO of synthesizing micron-grade
2ball, still there is pattern and dispersed uncontrollable, the shortcoming such as technique is more complicated in the monodisperse sphere for Nano grade.
The microtexture of material and the arrangement mode in space thereof produce material impact by the performance of material, the nanostructure field that the is prepared in dominate of low-dimensional nano structure material, and the compound with secondary nanostructure makes it may will have more novel character in optical, electrical, magnetic etc. because of the structure of its novelty and unique chemical physical property and pattern and the extreme influence of size to character.Therefore, to TiO
2the research of the secondary structure of granule-morphology is also more and more extensive, and its Application Areas is also provided with more wide prospect.
The present invention is based on the principle of process simplification, by first synthesizing micron-grade single dispersing persursor material, then in the liquid phase environment of gentleness the secondary microtexture of decorative material, synthesized the TiO with new meaning pattern
2powder granule, expects to be more widely used.
Summary of the invention
The invention provides the micro-nano hierarchy TiO of a kind of lichee shape
2crystal and synthetic method thereof, is characterized in that, the micro-nano hierarchy TiO of described lichee shape
2crystal is spherical, and spherical surface is distributed with the ball bumps of small particle size, and crystal formation is Detitanium-ore-type;
The micro-nano hierarchy TiO of described lichee shape
2spherical diameter is 500-700nm, and the diameter of described ball bumps is 10-20nm.
Preferably, the micro-nano hierarchy TiO of lichee shape
2crystal preparation step is as follows:
(1), under room temperature condition, be that the PVP of 1.5-2:25:75, water and n-propyl alcohol make mixed liquor A, by Ti (SO by W/V/V
4)
2solution is slowly poured in mixed liquor A, and after stirring, 70 DEG C of heating in water bath 3h-6h obtain mixed liquid B, after mixed liquid B is cooled to room temperature, centrifugal, washing, be 60 DEG C of ageing 12h in 1-2mol/LKOH solution in volumetric molar concentration, centrifugal, washing, dry after obtain presoma TiO
2powder C;
(2) mixed by precursor powder C and solvent D, precursor powder C and solvent D mass volume ratio W/V is 0.4:20, inserts water heating kettle and heat 2h at 180 DEG C, centrifugal, washing, dry after obtain the micro-nano hierarchy TiO of lichee shape
2crystal powder.
Preferably, in described step (1), Ti (SO
4)
2solution volumetric molar concentration is 0.8mol/L, Ti (SO
4)
2described in solution and this step, mixed solution A volume ratio V/V is 1:2.
Preferably, in described step (2), solvent D is ethylene glycol, the 0.01g/mL cetyl trimethylammonium bromide aqueous solution or volume ratio V/V are one in the DMF/ aqueous solution of 1:1.
Major advantage of the present invention is as follows:
(1) the obtained micro-nano hierarchy TiO of lichee shape
2the spherical diameter of crystal is 500-700nm, belongs to micro/nano level, and large particle diameter makes TiO
2crystal is easy to when being used as catalyzer reclaim.
(2) lichee shape hierarchy is that final product remains the pattern of presoma by obtaining the finishing of presoma, and defines secondary microtexture, is conducive to the specific surface area improving material, improves its photocatalysis characteristic further.
Accompanying drawing explanation
Fig. 1 is presoma TiO in embodiment 1
2scanning electron microscope diagram;
Fig. 2 is the micro-nano hierarchy TiO of lichee shape in embodiment 1
2the scanning electron microscope diagram of crystal;
Fig. 3 is presoma TiO in embodiment 1
2and the micro-nano hierarchy TiO of lichee shape
2xRD figure;
Fig. 4 is the micro-nano hierarchy TiO of lichee shape in embodiment 2
2the scanning electron microscope diagram of crystal;
Fig. 5 is the micro-nano hierarchy TiO of lichee shape in embodiment 3
2the scanning electron microscope diagram of crystal;
Fig. 6 is presoma TiO in embodiment 5
2scanning electron microscope diagram;
Fig. 7 is presoma TiO in embodiment 6
2scanning electron microscope diagram;
Fig. 8 is the test result of degradation of methylene blue in embodiment 7.
Embodiment
Embodiment 1
(1) 2gPVP, 25mL water and 75mL n-propyl alcohol are mixed with mixed liquor A, by the Ti (SO of 50mL0.8mol/L
4)
2the aqueous solution is slowly poured in mixed liquor A, and after stirring, 70 DEG C of heating in water bath 3h-6h obtain mixed liquid B, after mixed liquid B is cooled to room temperature, centrifugal, washing, 60 DEG C of ageing 12h in 1mol/LKOH solution, centrifugal, washing, dry after obtain TiO
2precursor powder C;
(2) 0.4g precursor powder C being joined 20mL volume ratio is mix in the DMF/ aqueous solution of 1:1, and the water heating kettle pouring 25mL into heats 2h at 180 DEG C, centrifugal, washing, dry after obtain the micro-nano hierarchy TiO of lichee shape
2crystal powder.
Fig. 1 is presoma TiO in the present embodiment
2the scanning electron microscope diagram of powder, can find out presoma TiO
2for equally distributed spherical, diameter is about 700nm.
Fig. 2 is the micro-nano hierarchy TiO of lichee shape that the present embodiment obtains
2the scanning electron microscope diagram of crystal, can find out, this TiO
2crystal entirety is spherical, and diameter is about 700nm, and spherical surface is evenly distributed with the ball bumps that diameter is about 20nm.
Fig. 3 is the present embodiment presoma TiO
2and the micro-nano hierarchy TiO of lichee shape
2the XRD figure of crystal, can find out, presoma TiO
2xRD spectra substantially do not go out peak, presoma TiO is described
2do not form crystallization, belong to unformed shape.The micro-nano hierarchy TiO of lichee shape
2crystal is Detitanium-ore-type, does not have dephasign, and show that crystalline structure is complete, peak shape is broadening slightly, shows have nanostructure to generate.
Embodiment 2
(1) 2.0gPVP, 25mL water and 75mL n-propyl alcohol are mixed with mixed liquor A, by the Ti (SO of 50mL0.8mol/L
4)
2the aqueous solution is slowly poured in mixed liquor A, and after stirring, 70 DEG C of heating in water bath 3h-6h obtain mixed liquid B, after mixed liquid B is cooled to room temperature, centrifugal, washing, 60 DEG C of ageing 12h in 1.0mol/LKOH solution, centrifugal, washing, dry after obtain TiO
2precursor powder C;
(2) 4g precursor powder C being joined 20mL volume is mix in the ethylene glycol solution of 20mL, and the water heating kettle pouring 25mL into heats 2h at 180 DEG C, centrifugal, washing, dry after obtain the micro-nano hierarchy TiO of lichee shape
2crystal powder.
The micro-nano hierarchy TiO of the lichee shape obtained
2the scanning electron microscope diagram of crystal as shown in Figure 4.Can find out, this TiO
2crystal entirety is spherical, and diameter is about 500nm, and spherical surface is evenly distributed with the ball bumps that diameter is about 10nm.
Embodiment 3
(1) 2gPVP, 25mL water and 75mL n-propyl alcohol are mixed with mixed liquor A, by the Ti (SO of 50mL0.8mol/L
4)
2the aqueous solution is slowly poured in mixed liquor A, and after stirring, 70 DEG C of heating in water bath 3h-6h obtain mixed liquid B, after mixed liquid B is cooled to room temperature, centrifugal, washing, 60 DEG C of ageing 12h in 1mol/LKOH solution, centrifugal, washing, dry after obtain TiO
2precursor powder C;
(2) joined in the 20mL0.01g/mL cetyl trimethylammonium bromide aqueous solution by 0.4g precursor powder C and mix, the water heating kettle pouring 25mL into heats 2h at 180 DEG C, centrifugal, washing, dry after obtain the micro-nano hierarchy TiO of lichee shape
2crystal powder.
The micro-nano hierarchy TiO of the lichee shape obtained
2the scanning electron microscope diagram of crystal as shown in Figure 5.Can find out, this TiO
2crystal entirety is spherical, and diameter is about 600nm, and spherical surface is evenly distributed with the ball bumps that diameter is about 10nm.
Embodiment 4
(1) 200gPVP, 2500mL water and 7500mL n-propyl alcohol are mixed with mixed liquor A, by the Ti (SO of 5000mL0.8mol/L
4)
2the aqueous solution is slowly poured in mixed liquor A, and after stirring, 70 DEG C of heating in water bath 3h-6h obtain mixed liquid B, after mixed liquid B is cooled to room temperature, centrifugal, washing, 60 DEG C of ageing 12h in 1mol/LKOH solution, centrifugal, washing, dry after obtain TiO
2precursor powder C;
(2) 40g precursor powder C being joined 2000mL volume ratio is mix in the DMF/ aqueous solution of 1:1, and the water heating kettle pouring 2500mL into heats 2h at 180 DEG C, centrifugal, washing, dry after obtain the micro-nano hierarchy TiO of lichee shape
2crystal powder.
The presoma TiO that the present embodiment obtains
2the micro-nano hierarchy TiO of the scanning electron microscope diagram of powder, lichee shape
2the scanning electron microscope diagram of crystal and presoma TiO
2and the micro-nano hierarchy TiO of lichee shape
2the XRD figure of crystal is with Fig. 1-Fig. 3 in embodiment 1.
Embodiment 5
The present embodiment is embodiment as a comparison, detects PVP addition to the micro-nano hierarchy TiO of lichee shape
2the impact of crystal, PVP add-on is 1.5g, all the other conditions with embodiment 1, the presoma TiO obtained
2scanning electron microscope diagram as shown in Figure 6, can find out, this presoma TiO
2there is agglomeration, reason is that surfactant concentration is not high, sterically hindered DeGrain.
Embodiment 6
The present embodiment is embodiment as a comparison, and during detection ageing, in step (1), KOH adds concentration to the micro-nano hierarchy TiO of lichee shape during ageing
2the impact of crystal, it is 2mol/L that KOH adds concentration, and all the other conditions are with embodiment 1.The presoma TiO obtained
2scanning electron microscope diagram as shown in Figure 7, can find out, this presoma TiO
2pattern is uneven, spheroid has small-particle or pit exist.Reason is that KOH concentration is excessive, has corrosive nature to presoma.
Embodiment 7
Embodiment 1-3 is carried out degradation of methylene blue experiment: the methylene blue solution of 50mg composite photocatalyst for degrading 30mL, 20mg/L, take ultraviolet lamp as light source irradiation, sampling in every 15 minutes once, centrifugal rear survey absorbancy (first stirs 30min sampling under dark condition, using the solution absorbance after adsorbing in the dark as blank), sample 6 times altogether.As shown in Figure 8,3 embodiment samples all can be degradable by methylene blue solution in 60min, and degradation effect, it is preferred that embodiment 1, is namely degraded at 45min completely for result.
Embodiment group 1-3 has the efficiency of good photocatalytic degradation methylene blue, and reason is that the adsorptivity of embodiment 1-3 sample is very large, and in light-catalyzed reaction, surface adsorption ability has a great impact catalytic activity, the TiO of stronger adsorptive power
2light-catalyzed reaction speed can be increased, and the micro-nano hierarchy TiO of lichee shape
2crystal surface structure then adds surface-area, improves photocatalytic speed.
Claims (3)
1. the micro-nano hierarchy TiO of lichee shape
2the preparation method of crystal, is characterized in that, preparation process is as follows:
(1) under room temperature condition, PVP, water and n-propyl alcohol are made mixed liquor A, PVP, water and n-propyl alcohol quality volume volume ratio W/V/V are 1.6-2:25:75 (unit: g/ml/ml), by Ti (SO
4)
2solution is slowly poured in mixed liquor A, and after stirring, 70 DEG C of heating in water bath 3h-6h obtain mixed liquid B, after mixed liquid B is cooled to room temperature, centrifugal, washing, be 60 DEG C of ageing 12h in 1-1.8mol/LKOH solution in volumetric molar concentration, centrifugal, washing, dry after obtain presoma TiO
2powder C;
(2) precursor powder C and solvent D is mixed, precursor powder C and solvent D mass volume ratio W/V is 0.4:20 (unit: g/ml), insert water heating kettle and heat 2h at 180 DEG C, centrifugal, washing, dry after obtain the micro-nano hierarchy TiO of lichee shape
2crystal powder.
2. the micro-nano hierarchy TiO of a kind of lichee shape as claimed in claim 1
2the preparation method of crystal, is characterized in that: in described step (1), Ti (SO
4)
2solution volumetric molar concentration is 0.8mol/L, Ti (SO
4)
2solution and described mixed liquor A volume ratio V/V (unit: ml/ml) are 1:2.
3. the micro-nano hierarchy TiO of a kind of lichee shape as claimed in claim 1
2the preparation method of crystal, is characterized in that: in described step (2), and solvent D is ethylene glycol, the 0.01g/mL cetyl trimethylammonium bromide aqueous solution or volume ratio are one in the DMF/ aqueous solution of 1:1.
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| 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 |
| CN107445201B (en) * | 2017-09-11 | 2019-01-08 | 广东工业大学 | A kind of preparation method of rear-earth-doped anatase titanium dioxide micro-nano-sphere |
| CN109794290B (en) * | 2019-01-31 | 2021-08-27 | 天津城建大学 | Spiral titanyl oxalate photocatalyst and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102795664A (en) * | 2012-08-10 | 2012-11-28 | 东华大学 | Preparation method of mesoporous titanium dioxide microballoons with controllable particle size |
| CN103739013A (en) * | 2014-01-07 | 2014-04-23 | 天津大学 | Porous spherical titanium dioxide with controllable diameter and preparation and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102795664A (en) * | 2012-08-10 | 2012-11-28 | 东华大学 | Preparation method of mesoporous titanium dioxide microballoons with controllable particle size |
| CN103739013A (en) * | 2014-01-07 | 2014-04-23 | 天津大学 | Porous spherical titanium dioxide with controllable diameter and preparation and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 粒径可控球形TiO2的制备;扈玫珑等;《物理化学学报》;20081231(第12期);2287-2292 * |
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