CN109133161A - A kind of preparation method of strontium titanate nanoparticles - Google Patents
A kind of preparation method of strontium titanate nanoparticles Download PDFInfo
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- CN109133161A CN109133161A CN201811330169.8A CN201811330169A CN109133161A CN 109133161 A CN109133161 A CN 109133161A CN 201811330169 A CN201811330169 A CN 201811330169A CN 109133161 A CN109133161 A CN 109133161A
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- C01G23/006—Alkaline earth titanates
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/60—Particles characterised by their size
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Abstract
A kind of preparation method the present invention relates to strontium titanate nanoparticles include: 1) tetrabutyl titanate hydrolysis obtain the hydroxide of titanium；2) hydroxide of titanium is dispersed in water, potassium hydroxide is added, hydro-thermal reaction is carried out at 170-230 DEG C and obtains fibrous potassium titanate；3) it disperses fibrous potassium titanate in the mixed system of ethylene glycol and water, sequentially adds strontium nitrate and potassium hydroxide, hydro-thermal reaction obtains strontium titanate nanoparticles at 170-230 DEG C.This method can obtain strontium titanate nanoparticles of the size between 8~20nm, and dispersibility, uniformity and photocatalytic are good.
Description
Technical field
The present invention relates to inorganic material to synthesize field, and in particular to a kind of preparation method of strontium titanate nanoparticles.
Background technique
Strontium titanates is the Typical Representative of perovskite-type compounds, lattice constantBelong to cubic crystal
System.The forbidden bandwidth of strontium titanates is about 3.2eV, close with titanium dioxide.Strontium titanates nano material has excellent physics, chemistry
Property, such as superconductivity, magnetic ferroelectric, chemical stability are good etc., have extensively in the fields such as photocatalysis, temperature-sensitive, pressure-sensitive, capacitor
Application, be a kind of material being concerned at present.
The controllable preparation of strontium titanates nano material is also one of research hotspot.Currently, the preparation method master of Sr titanate powder
There are synthesis by solid state reaction, sol-gal process, hydro-thermal method etc..Compared to first two method, hydro-thermal method needs not move through high temperature
Calcining, low energy consumption, has the advantages that particle size distribution is uniform, just more and more has been favored by people.However, preparing
When strontium titanate nanoparticles, little particle is easy to reunite, and keeps the size of gained nano particle larger, the strontium titanates nanometer prepared at present
Particle often rests on tens nanometers to several hundred nanometers.
As Chinese invention patent application (106745210 A of CN) discloses a kind of Li doping SrTiO3Porous surface nanometer
The preparation method of grain, comprising: the then hydroxide precipitating that titanium is prepared with titanium sulfate and potassium hydroxide sinks the hydroxide of titanium
Shallow lake, strontium nitrate solution, potassium hydroxide solution and lithium sulfate solution are stirred to obtain presoma, carry out hydro-thermal reaction, filter, clearly
It washes, is dried to obtain.This method obtains Li doping SrTiO3Particle size between 300-350nm.
Due to nanometer size effect, smaller nano particle often has superior physicochemical properties.Therefore,
The nanocrystalline controllable preparation of small size strontium titanates is worth further and explores.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to a kind of preparation method of strontium titanate nanoparticles is provided,
Strontium titanate nanoparticles of the size between 8~20nm can be obtained, dispersibility, uniformity and photocatalytic are good.
Technical solution provided by the present invention are as follows:
A kind of preparation method of strontium titanate nanoparticles, comprising:
1) tetrabutyl titanate hydrolysis obtains the hydroxide of titanium；
2) hydroxide of titanium is dispersed in water, potassium hydroxide is added, hydro-thermal reaction is carried out at 170-230 DEG C and is obtained
Fibrous potassium titanate；
3) it disperses fibrous potassium titanate in the mixed system of ethylene glycol and water, sequentially adds strontium nitrate and hydroxide
Potassium, hydro-thermal reaction obtains strontium titanate nanoparticles at 170-230 DEG C.
The present invention synthesizes strontium titanate nanoparticles by two step hydro-thermal reactions, and size is between 8~20nm, and dispersibility
It is good with uniformity.
Tetrabutyl titanate hydrolysis includes: that butyl titanate is dissolved in ethyl alcohol in step 1) of the present invention, is slowly added to water, is obtained
The hydroxide of titanium precipitates.Wherein, the hydroxide of titanium refers to Ti (OH)4.Preferably, the butyl titanate is in ethanol
Molar concentration is 0.1-0.25mol/L.
The molar concentration of potassium hydroxide in the reaction system is 6-10mol/L in step 2) of the present invention.Wherein, it reacts
System refers to the mixture of hydro-thermal reaction in step 2), hydroxide, potassium hydroxide and water containing titanium.Preferably, the hydrogen
The molar concentration of potassium oxide in the reaction system is 7-9mol/L.
The temperature of hydro-thermal reaction is 190-210 DEG C in step 2) of the present invention, reaction time 14-18h.
The molar ratio for the potassium hydroxide being added in butyl titanate of the present invention and step 2) is 1:45-60.Preferably
1:50-55。
The volume fraction of ethylene glycol is 20-80% in step 3) mixed system of the present invention.Preferably 25-75%.
The volume of mixed system is 30-50ml in step 3) of the present invention.
The temperature of hydro-thermal reaction is 190-210 DEG C in step 3) of the present invention, reaction time 14-18h.
Molar concentration of the potassium hydroxide in mixed system is 0.25-1.0mol/L in step 3) of the present invention.Wherein,
The mixed system refers to the mixed liquor of ethylene glycol and water.
Strontium nitrate and fibrous potassium titanate are with the ratio between amount of substance of Sr and Ti for 1:0.8- in step 3) of the present invention
1.2 feed intake.
As one of preferred, the preparation method of the strontium titanate nanoparticles, comprising:
1) butyl titanate is dissolved in ethyl alcohol, is slowly added to water, obtain the hydroxide of titanium；The butyl titanate is in second
Molar concentration in alcohol is 0.1-0.11mol/L；
2) hydroxide of titanium is dispersed in water, potassium hydroxide is added, hydro-thermal reaction 15- is carried out at 195-205 DEG C
17h obtains fibrous potassium titanate；The molar concentration of the potassium hydroxide in the reaction system is 7.5-8.5mol/L；The titanium
The molar ratio for the potassium hydroxide being added in sour four butyl esters and step 2) is 1:52-54；
3) it disperses fibrous potassium titanate in the mixed system of ethylene glycol and water, sequentially adds strontium nitrate and hydroxide
Potassium, hydro-thermal reaction 15-17h, obtains strontium titanate nanoparticles at 195-205 DEG C；The volume of ethylene glycol in the mixed system
Score is 74-75%, and the volume of mixed system is 38-42ml；Molar concentration of the potassium hydroxide in mixed system be
0.4-0.6mol/L；The strontium nitrate is that 1:0.9-1.1 is thrown with the ratio between amount of substance of Sr and Ti with fibrous potassium titanate
Material.
Compared with the existing technology, the beneficial effects of the present invention are embodied in:
(1) present invention process process is simple, and reaction raw materials are easily obtained, and cost is relatively low, needs not move through high-temperature calcination, environment
It pollutes small, is easy to large-scale production.
(2) strontium titanate nanoparticles size prepared by the present invention is between 8~20nm, and dispersibility, uniformity and
Photocatalysis performance is good.
Detailed description of the invention
Fig. 1 is the SEM figure of intermediate product potassium titanate prepared by embodiment 1；
Fig. 2 is the XRD diagram of product strontium titanates prepared by embodiment 1；
Fig. 3 is the SEM figure of product strontium titanates prepared by embodiment 1；
Fig. 4 is the TEM figure of product strontium titanates prepared by embodiment 1；
Fig. 5 is the SEM figure of product strontium titanates prepared by embodiment 2；
Fig. 6 is the SEM figure of product strontium titanates prepared by comparative example 1；
Fig. 7 is the SEM figure of product strontium titanates prepared by comparative example 2；
Fig. 8 is the SEM figure of product strontium titanates prepared by comparative example 3；
Fig. 9 is the SEM figure of product strontium titanates prepared by comparative example 4；
Figure 10 is the curve graph of strontium titanates photocatalytic degradation methylene blue prepared by embodiment 1, comparative example 1 and comparative example 2.
Specific embodiment
The invention will be further described with Figure of description with reference to embodiments.
Embodiment 1
1) 6mmol butyl titanate is taken to be dissolved in 60ml dehydrated alcohol, stirring 10min makes it uniformly, is gone with dropper instillation
Ionized water obtains white precipitate, is filtered, washed to obtain the hydroxide precipitating of titanium.
2) it disperses the hydroxide precipitating of titanium in deionized water, stirring 10min makes it that 17.96g hydrogen-oxygen uniformly be added
Change potassium (0.32mol), deionized water is added to be settled to 40ml, the concentration of potassium hydroxide is 8mol/L at this time.Suspension is moved into
200 DEG C are carried out in 50ml ptfe autoclave, 16h hydro-thermal reaction cools down at room temperature, potassium titanate is obtained after washing.
Intermediate product potassium titanate carries out SEM characterization, as shown in Figure 1, pattern is threadiness.
3) it disperses potassium titanate in 30ml ethylene glycol, adding water to be settled to 40ml, (volume of ethylene glycol is divided in mixed system
For number 75%), to sequentially add mono- nitric hydrate strontium of 1.27g and 1.12g potassium hydroxide, stirring 30min makes it uniformly.At this time Sr with
The ratio between concentration of Ti is about 1:1, and the concentration of potassium hydroxide is 0.50mol/L.Suspension is moved into 50ml polytetrafluoroethyl-ne alkene reaction
200 DEG C are carried out in kettle, 16h hydro-thermal reaction.Allow reaction kettle natural cooling at room temperature later, product is used respectively deionized water,
Strontium titanate nanoparticles are just obtained after dust technology, deionized water, dehydrated alcohol washing.
XRD characterization is carried out for product, as shown in Fig. 2, diffraction maximum all in XRD spectrum is able to index to lattice constantStrontium titanates, this with PDF card 35-0734 report it is consistent, illustrate that the product is pure strontium titanates.
SEM characterization is carried out for product strontium titanates, as shown in figure 3, product is nano particle, pattern, size uniformity, dispersion
Property is good.
In order to further look at the nanocrystalline size of product strontium titanates, TEM characterization is carried out for product, as shown in figure 4, producing
The partial size of object is between 8~15nm.
Embodiment 2
It is prepared according to the method for embodiment 1, the difference is that, during strontium titanates is prepared in step 3),
Institute's spent glycol is 10ml, and equally plus water is settled to 40ml, and the volume fraction of ethylene glycol is 25% in mixed system.
2 products therefrom of embodiment is similarly strontium titanate nanoparticles, SEM characterization result as shown in figure 5, partial size 10~
20nm, uniformity and good dispersion.
Comparative example 1
It is prepared according to the method for embodiment 1, the difference is that, during strontium titanates is prepared in step 3),
Ethylene glycol is not added, equally plus water is settled to 40ml.
XRD and SEM characterization is carried out for product, although can equally obtain the pure phase of strontium titanates when not adding ethylene glycol
(not providing XRD diagram), but particle size is much larger than in hydro-thermal reaction liquid and second two is added 100-200nm (as shown in Figure 6)
Strontium titanates particle prepared by alcohol.
Comparative example 2
It is prepared according to the method for embodiment 1, the difference is that, during strontium titanates is prepared in step 3),
Water is not added, ethylene glycol is added to be settled to 40ml.
XRD and SEM characterization is carried out for product, XRD spectrum shows that products therefrom is still strontium titanates (not providing XRD diagram).
SEM photograph is as shown in Figure 7.When not adding water, product is small pieces, is unable to get strontium titanates when the use of ethylene glycol being solvent and receives
Rice grain.
Comparative example 3
1) 6mmol butyl titanate is taken to be dissolved in 60ml dehydrated alcohol, stirring 10min makes it uniformly, is gone with dropper instillation
Ionized water obtains white precipitate, is filtered, washed to obtain the hydroxide precipitating of titanium.
2) it disperses the hydroxide precipitating of titanium in 30ml ethylene glycol, adds water to be settled to 40ml, sequentially add 1.27g mono-
Nitric hydrate strontium and 1.12g potassium hydroxide, stirring 30min make it uniformly.The ratio between concentration of Sr and Ti is about 1:1, hydrogen-oxygen at this time
The concentration for changing potassium is 0.50mol/L.Suspension is moved into and carries out 200 DEG C in 50ml ptfe autoclave, 16h hydro-thermal is anti-
It answers.It allows reaction kettle natural cooling at room temperature later, product is used to deionized water, dust technology, deionized water, dehydrated alcohol respectively
Strontium titanates is just obtained after washing.
SEM characterization is carried out for product, as shown in Figure 8, it can be seen that in the form of sheets, thickness is in 10-20nm for product.It can not obtain
To strontium titanates nano particle the main reason for be to use the hydroxide of titanium to precipitate as titanium source.
Comparative example 4
It is prepared according to the method for comparative example 3, the difference is that, during strontium titanates is prepared in step 2),
Institute's spent glycol volume is 10ml, and equally plus water is settled to 40ml.
The SEM of product schemes as shown in figure 9, when ethylene glycol content used is less, and prepared strontium titanates is nano particle, grain
Diameter is between 30-60nm.Strontium titanate nanoparticles are larger-size main reason is that the hydroxide using titanium makees titanium source.
Performance test
It is real that photocatalytic degradation methylene blue has been carried out to the strontium titanates of embodiment 1, comparative example 1 and comparative example 2 preparation respectively
It tests.Strontium titanates used is 100mg in experiment, and methylene blue solution concentration is 10-5M first carries out hour before illumination
Dark reaction, degradation rate are as shown in Figure 10.
The particle that size prepared by embodiment 1 is faster than 100 rans in the strontium titanates degradation rate of 10 rans is (right
It is prepared by ratio 1) and nanoplatelets (preparation of comparative example 2).This may be since smaller size of strontium titanate nanoparticles have
Bigger specific surface area contacts more abundant with liquid.In smaller size of nano particle, by the electronics of valence to conduction band
It is more easy to migrate that reduction reaction occurs to surface, reduce compound with hole in motion process, improves photo-catalysis capability.
Claims (9)
1. a kind of preparation method of strontium titanate nanoparticles characterized by comprising
1) tetrabutyl titanate hydrolysis obtains the hydroxide of titanium；
2) hydroxide of titanium is dispersed in water, potassium hydroxide is added, hydro-thermal reaction is carried out at 170-230 DEG C and obtains fiber
Shape potassium titanate；
3) it disperses fibrous potassium titanate in the mixed system of ethylene glycol and water, sequentially adds strontium nitrate and potassium hydroxide,
Hydro-thermal reaction obtains strontium titanate nanoparticles at 170-230 DEG C.
2. the preparation method of strontium titanate nanoparticles according to claim 1, which is characterized in that hydrogen-oxygen in the step 2)
Changing the molar concentration of potassium in the reaction system is 6-10mol/L.
3. the preparation method of strontium titanate nanoparticles according to claim 1, which is characterized in that hydro-thermal in the step 2)
The temperature of reaction is 190-210 DEG C, reaction time 14-18h.
4. the preparation method of strontium titanate nanoparticles according to claim 1, which is characterized in that the butyl titanate with
The molar ratio for the potassium hydroxide being added in step 2) is 1:45-60.
5. the preparation method of strontium titanate nanoparticles according to claim 1, which is characterized in that the step 3) mixture
The volume fraction of ethylene glycol is 20-80% in system.
6. the preparation method of strontium titanate nanoparticles according to claim 5, which is characterized in that mixing in the step 3)
The volume of system is 30-50ml.
7. the preparation method of strontium titanate nanoparticles according to claim 1, which is characterized in that hydro-thermal in the step 3)
The temperature of reaction is 190-210 DEG C, reaction time 14-18h.
8. the preparation method of strontium titanate nanoparticles according to claim 1, which is characterized in that hydrogen-oxygen in the step 3)
Changing molar concentration of the potassium in mixed system is 0.25-1.0mol/L.
9. the preparation method of strontium titanate nanoparticles according to claim 1, which is characterized in that nitric acid in the step 3)
Strontium is that 1:0.8-1.2 feeds intake with the ratio between amount of substance of Sr and Ti with fibrous potassium titanate.
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| CN110203967A (en) * | 2019-07-05 | 2019-09-06 | 西安电子科技大学 | The preparation method of sheet strontium titanates nano crystal body |
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| CN106186051A (en) * | 2016-06-22 | 2016-12-07 | 许昌学院 | A kind of preparation method of hollow structure strontium titanate nanoparticles |
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| CN110203967A (en) * | 2019-07-05 | 2019-09-06 | 西安电子科技大学 | The preparation method of sheet strontium titanates nano crystal body |
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