CN106673057B - A kind of perovskite Li doping SrTiO3The preparation method and product of nano particle - Google Patents

A kind of perovskite Li doping SrTiO3The preparation method and product of nano particle Download PDF

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CN106673057B
CN106673057B CN201611022310.9A CN201611022310A CN106673057B CN 106673057 B CN106673057 B CN 106673057B CN 201611022310 A CN201611022310 A CN 201611022310A CN 106673057 B CN106673057 B CN 106673057B
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titanium
solution
perovskite
hydroxide
srtio
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CN106673057A (en
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徐刚
皇甫统帅
孙小磊
沈鸽
韩高荣
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Zhejiang University ZJU
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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
    • C01G23/003—Titanates
    • C01G23/006—Alkaline earth titanates
    • 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
    • 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
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • 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 relates to a kind of perovskite Li to adulterate SrTiO3The preparation method of nano particle, including：Titanium sulfate solution is prepared respectively；Ammonium hydroxide is added drop-wise in titanium sulfate solution, the hydroxide precipitation of titanium is obtained by filtration；Strontium nitrate and lithium hydroxide solution are prepared respectively；Hydroxide precipitation, strontium nitrate solution and the lithium hydroxide solution of titanium are mixed and carry out hydro-thermal reaction, then filtering is cleaned, perovskite Li doping SrTiO is obtained3Nano particle；Present invention process process is simple, easily controllable, at low cost, is easy to large-scale production.The invention further relates to perovskite Li made from above-mentioned preparation method to adulterate SrTiO3Nano particle, nano-powder size are stablized between 600~800nm, product quality, and purity is high, powder granule good dispersion.

Description

A kind of perovskite Li doping SrTiO3The preparation method and product of nano particle
Technical field
The present invention relates to inorganic material to synthesize field, and in particular to a kind of perovskite Li doping SrTiO3The system of nano particle Preparation Method and product.
Background technology
Currently, a large amount of water environment pollution, seriously restricts the sustainable development in China, and it is strong to influence national body Health is the social concern urgently to be resolved hurrily concerning national economy.According to statistics, 70% water pollution is caused by organic pollution , the degradation removing of organic pollution is the key that administer water pollution.Conductor photocatalysis degradation is to remove organic pollution One of most effectual way has the advantages that at low cost, efficient and non-secondary pollution.Therefore, prepared by conductor photocatalysis material And the research and development of performance and application technology are by the very big attention of national governments and scientist.Wherein, SrTiO3It is typical ABO3Perovskite structure has many advantages, such as that dielectric constant is high, dielectric loss is low, thermal stability is good, is widely used in electronics, machinery And ceramic industry.Meanwhile as a kind of functional material, strontium titanates have higher photocatalytic activity, unique electromagnetic property and Redox catalysis activity, in photocatalysis such as photocatalytic hydrogen production by water decomposition, photocatalysis degradation organic contaminant and photochemical cells Field is also widely used.
Chinese invention patent (publication number CN104098125A) discloses a kind of preparation method of strontium titanates nano cubic block, should For method using titanium dioxide as titanium source, soluble strontium salt makees mineralizer as barium source, with sodium hydroxide.Titanium dioxide is surpassed first Sound is scattered in aqueous solution, then adds the soluble-salt containing strontium thereto, and continuous stirring is allowed to dissolve, and then adds alkali again, Suspension pH value is adjusted to 8~14, finally suspension is put into reaction kettle, hydro-thermal reaction is carried out and obtains strontium titanates nano cubic Block.But titanium dioxide is extremely difficult to be dissolved in water, needs ultrasound and prolonged stirring.Secondly, sodium hydroxide is selected to do mineralizer, hydrogen Sodium oxide molybdena is soluble in water to will be completely dissociated into sodium ion and hydroxide ion, can not effectively control the OH-ion in reaction system, Pattern asymmetry is caused to grow.
Invention content
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of perovskite Li doping SrTiO3Nano particle Preparation method and product, preparation process is simple, and the pattern of self assembly type structure is easy to regulate and control, size uniformity.
The present invention solves the technical solution of above-mentioned technical problem：
A kind of perovskite Li doping SrTiO3The preparation method of nano particle, includes the following steps：
1) titanium sulfate solution is prepared；
2) ammonium hydroxide is added drop-wise in titanium sulfate solution, the hydroxide precipitation of titanium is obtained by filtration；
3) strontium nitrate solution and lithium hydroxide solution are prepared respectively；
4) hydroxide of titanium precipitation, strontium nitrate solution and lithium hydroxide solution are mixed and carries out hydro-thermal reaction, filtering, so After clean, obtain perovskite Li doping SrTiO3Nano particle；
0.1~0.5mol/L of molar concentration of strontium nitrate solution in the step 3), mole of lithium hydroxide solution A concentration of 0.1~2mol/L；
Hydroxide precipitation, the mixed proportion of strontium nitrate solution and lithium hydroxide solution of titanium in the step 4) be 0.5~3g：15~20ml：10~15ml.
The present invention promotes the hydroxide of titanium to generate using titanium sulfate and strontium nitrate as reaction mass, using precipitating reagent ammonium hydroxide, Simultaneously using the growth of mineralizer lithium hydroxide regulation and control crystal, perovskite Li doping SrTiO is finally realized3The system of nano particle It is standby.Ammonium hydroxide is weak base, in being added to titanium sulfate solution, can constantly be ionized, and the hydroxide precipitation of generation is more uniform；Hydrogen-oxygen Changing lithium, solubility is not high in deionized water, with the progress of reaction, OH-It is gradually consumed, promotes the dissolving of lithium hydroxide, So OH-Ion can maintain more stable concentration, under this mild state, crystal structure cell intrinsic symmetry easy to implement Growth adulterates SrTiO to obtain perovskite Li3Nano particle.
Preferably, ammonium hydroxide is added drop-wise in titanium sulfate solution in the step 2), the hydroxide precipitation of titanium is obtained, 20~30min is stood, filters and the hydroxide for cleaning titanium with deionized water precipitates 4~5 times.
Preferably, the molar concentration of the titanium sulfate solution in the step 1) is 0.1~0.45mol/L.
Preferably, the reaction temperature of hydro-thermal reaction in the step 4) is 180~250 DEG C, the reaction time is 8~ 24h。
Further preferably, the reaction temperature is 180~200 DEG C, and the reaction time is 8~12h.
Preferably, the hydroxide precipitation of titanium in the step 4), strontium nitrate solution and lithium hydroxide solution Mixed proportion is 0.7~0.9g：15~16ml：10~11ml.
Preferably, the cleaning method in the step 4) is：By the product being obtained by filtration successively with spirit of vinegar, go from Sub- water cleans five times repeatedly.It is in order to which carbon dioxide institute shape will be mixed into presoma to the cleaning of hydrothermal synthesis product with spirit of vinegar At CO3 2-、HCO3 -Removal, it is lithium ion, nitrate ion and precipitation in order to introduce reaction mass to be cleaned with deionized water When the SrTiO of ammonia radical ion and synthesis that introduces3Nano-powder is sufficiently separated, and obtains the perovskite Li doping SrTiO of pure phase3It receives Rice grain.
As a preferred embodiment, the rate of addition in the step 2) is 1~2 drop/sec；Ammonium hydroxide is added drop-wise to by controlling Rate of addition in titanium sulfate solution further controls perovskite Li and adulterates SrTiO3The pattern of nano particle.
As most preferably, 0.1~0.15mol/L of molar concentration of the titanium sulfate solution,；By ammonia under stirring Water is 1~2 drop/sec with rate of addition and is added dropwise in titanium sulfate solution, obtains the hydroxide precipitation of titanium.By strontium nitrate and hydrogen-oxygen Change lithium to be dissolved separately in deionized water, the molar concentration of strontium nitrate is 0.1~0.15mol/L, mole of lithium hydroxide solution A concentration of 0.1~0.15mol/L.The hydroxide precipitation of the 0.7~0.9g titaniums cleaned, 15~16ml strontium nitrates is water-soluble Liquid and 10~11ml lithium hydroxide solutions are added separately in reaction kettle, and 8~10 hours are kept the temperature at 180~190 DEG C and carries out heat Processing.Under conditions of above-mentioned optimal, gained perovskite Li adulterates SrTiO3The pattern of nano particle is best, and stable quality is pure Degree is high, powder granule good dispersion.
The present invention also provides a kind of perovskite Li of above-mentioned preparation method synthesis to adulterate SrTiO3Nano particle, the calcium Titanium ore Li adulterates SrTiO3The size of nano particle is 600~800nm.The size can be the straight of nano particle circumcircle Diameter or the length of side.The perovskite Li doping SrTiO being prepared3Nano particle equally has above-mentioned advantageous effect.
Beneficial effects of the present invention are embodied in：Present invention process process is simple, easily controllable, and non-environmental-pollution is at low cost, It is easy to large-scale production.Perovskite Li obtained adulterates SrTiO3Nano granule powder size is between 600~800nm.Production Amount of substance is stablized, and purity is high, powder granule good dispersion.
Description of the drawings
Fig. 1 is that the perovskite Li that embodiment 1 synthesizes adulterates SrTiO3The X-ray diffractogram of nano-powder；
Fig. 2 is that the perovskite Li that embodiment 1 synthesizes adulterates SrTiO3The scanning electron microscope diagram of nano-powder；
Fig. 3 is that the perovskite Li that embodiment 1 synthesizes adulterates SrTiO3The transmission electron microscope figure of nano-powder；
Fig. 4 is the perovskite SrTiO that comparative example 1 synthesizes3The scanning electron microscope of the ellipsoid nano-powder of porous surface Figure；
Fig. 5 is the perovskite SrTiO that comparative example 2 synthesizes3The scanning electron microscope of the cubic nanometer powder of porous surface Figure.
Specific implementation mode
The present invention is further described with Figure of description with reference to embodiments.
Embodiment 1
1) 4mmol titanium sulfates are dissolved in deionized water, adjust the molar concentration 0.1mol/L of titanium sulfate solution.
2) ammonium hydroxide being slowly added dropwise in 20ml titanium sulfate solutions under stirring, rate of addition is 1~2 drop/sec, The hydroxide precipitation for obtaining white titanium, stands 25min, filters and cleans precipitation 4 times with deionized water.
3) strontium nitrate and lithium hydroxide being dissolved separately in deionized water, the molar concentration of strontium nitrate is 0.1mol/L, The molar concentration of lithium hydroxide solution is 0.1mol/L.
4) by the hydroxide of the 0.8g titaniums cleaned precipitation, 15ml strontium nitrates aqueous solution and 10ml lithium hydroxide solutions point It is not added in 50ml reaction kettles, it is the 40% of reaction kettle liner to adjust total volume with deionized water, after stirring 2h, at 180 DEG C Lower heat preservation is heat-treated for 8 hours.Then, it is down to room temperature, takes out reaction product, filtering uses spirit of vinegar, deionized water clear successively It washes, is dried at a temperature of 60 DEG C, obtain perovskite Li doping SrTiO3Nano-powder.
Synthesized perovskite Li adulterates SrTiO3The X-ray diffractogram of nano-powder, as shown in Figure 1, product is calcium titanium Mine Li adulterates SrTiO3Nano-powder illustrates that product is the SrTiO of pure phase without other impurity peaks3.Scanning electron microscope SEM photograph as shown in Fig. 2, transmission electron microscope figure as shown in figure 3, perovskite Li obtained adulterate SrTiO3Nano-powder ruler It is very little between 600~800nm, pattern is graininess.
Embodiment 2
1) 6mmol titanium sulfates are dissolved in deionized water, adjust the molar concentration 0.3mol/L of titanium sulfate solution.
2) ammonium hydroxide being slowly added dropwise in 20ml titanium sulfate solutions under stirring, rate of addition is 1~2 drop/sec, The hydroxide precipitation for obtaining white titanium, stands 25min, filters and cleans precipitation 5 times with deionized water.
3) strontium nitrate and lithium hydroxide being dissolved separately in deionized water, the molar concentration of strontium nitrate is 0.3mol/L, The molar concentration of lithium hydroxide solution is 1mol/L.
4) by the hydroxide of the 0.8g titaniums cleaned precipitation, 15ml strontium nitrates aqueous solution and 10ml lithium hydroxide solutions point It is not added in 50ml reaction kettles, it is the 40% of reaction kettle liner to adjust total volume with deionized water, after stirring 2h, at 220 DEG C Lower heat preservation is heat-treated for 16 hours.Then, it is down to room temperature, takes out reaction product, spirit of vinegar, deionized water are used in filtering successively It cleans, is dried at a temperature of 60 DEG C, obtain perovskite Li doping SrTiO3Nano-powder.
Embodiment 3
1) 8mmol titanium sulfates are dissolved in deionized water, adjust the molar concentration 0.45mol/L of titanium sulfate solution.
2) ammonium hydroxide being slowly added dropwise in 20ml titanium sulfate solutions under stirring, rate of addition is 1~2 drop/sec, The hydroxide precipitation for obtaining white titanium, stands 25min, filters and cleans precipitation 5 times with deionized water.
3) strontium nitrate and lithium hydroxide being dissolved separately in deionized water, the molar concentration of strontium nitrate is 0.5mol/L, The molar concentration of lithium hydroxide solution is 2mol/L.
4) by the hydroxide of the 0.8g titaniums cleaned precipitation, 15ml strontium nitrates aqueous solution and 10ml lithium hydroxide solutions point It is not added in 50ml reaction kettles, it is the 40% of reaction kettle liner to adjust total volume with deionized water, after stirring 2h, at 250 DEG C Lower heat preservation is heat-treated for 24 hours.Then, it is down to room temperature, takes out reaction product, spirit of vinegar, deionized water are used in filtering successively It cleans, is dried at a temperature of 60 DEG C, obtain perovskite Li doping SrTiO3Nano-powder.
Comparative example 1
1) 6mmol titanium sulfates are dissolved in deionized water, adjust the molar concentration 0.3mol/L of titanium sulfate solution.
2) ammonium hydroxide being slowly added dropwise in 20ml titanium sulfate solutions under stirring, rate of addition is 1~2 drop/sec, The hydroxide precipitation for obtaining white titanium, stands 25min, filters and cleans precipitation 4 times with deionized water.
3) strontium nitrate and potassium hydroxide being dissolved separately in deionized water, the molar concentration of strontium nitrate is 0.3mol/L, The molar concentration of lithium hydroxide solution is 1mol/L.
4) by the hydroxide of the 0.8g titaniums cleaned precipitation, 15ml strontium nitrates aqueous solution and 10ml potassium hydroxide solutions point It is not added in 50ml reaction kettles, it is the 40% of reaction kettle liner to adjust total volume with deionized water, after stirring 2h, at 220 DEG C Lower heat preservation is heat-treated for 16 hours.Then, it is down to room temperature, takes out reaction product, spirit of vinegar, deionized water are used in filtering successively It cleans, is dried at a temperature of 60 DEG C, obtain perovskite SrTiO3The ellipsoid nano-powder of porous surface.
Scanning electron microscope SEM photograph is as shown in figure 4, obtained strontium titanates is the ellipsoidal particle of porous surface.K ratios Li metallicity is stronger, more vivaciously, so K+Ion ratio Li+Ion have it is stronger ionic, can be with temperature in product formation stages Degree is increased and is entered in lattice, when temperature starts to reduce, K+Ion is with respect to Li+Ion is more empty easily to be escaped from lattice, is formed The structure of porous surface.
Comparative example 2
1) 6mmol titanium sulfates and 0.2mol potassium hydroxide are dissolved separately in deionized water, adjust titanium sulfate solution The molar concentration of molar concentration 0.3mol/L, potassium hydroxide solution are 8mol/L.
2) potassium hydroxide solution is slowly added dropwise in 20ml titanium sulfate solutions under stirring, rate of addition is 1~2 Drop/sec, the hydroxide precipitation of white titanium is obtained, 25min is stood, filters and cleans precipitation 4 times with deionized water.
3) strontium nitrate, potassium hydroxide and lithium nitrate are dissolved separately in deionized water, the molar concentration of strontium nitrate is The molar concentration of 0.3mol/L, potassium hydroxide solution are 1mol/L, and the molar concentration of lithium nitrate solution is 0.8mol/L.
4) by the hydroxide of the 0.8g titaniums cleaned precipitation, 15ml strontium nitrates aqueous solution, 10ml potassium hydroxide solutions and 10ml lithium nitrate solutions are added separately in 50ml reaction kettles, and it is the 40% of reaction kettle liner to adjust total volume with deionized water, After stirring 2h, at 220 DEG C keeping the temperature 16 hours is heat-treated.Then, it is down to room temperature, takes out reaction product, filtering is used successively Spirit of vinegar, deionized water are cleaned, and are dried at a temperature of 60 DEG C, obtained SrTiO3There is deeper hole on surface, as shown in figure 5, nothing Method obtains perovskite Li doping SrTiO3Nano particle.

Claims (2)

1. a kind of perovskite Li adulterates SrTiO3The preparation method of nano particle, which is characterized in that include the following steps：
1) titanium sulfate solution, 0.1~0.15mol/L of molar concentration of the titanium sulfate solution are prepared；
2) it is 1~2 drop/sec with rate of addition by ammonium hydroxide under stirring to be added dropwise in titanium sulfate solution, titanium is obtained by filtration Hydroxide precipitates；
3) strontium nitrate solution and lithium hydroxide solution are prepared respectively, the molar concentration of strontium nitrate solution is 0.1~0.15mol/L, The molar concentration of lithium hydroxide solution is 0.1~0.15mol/L；
4) hydroxide of titanium precipitation, strontium nitrate solution and lithium hydroxide solution are mixed and carries out hydro-thermal reaction, filtering, then clearly It washes, obtains perovskite Li doping SrTiO3Nano particle；The reaction temperature of the hydro-thermal reaction is 180~190 DEG C, the reaction time For 8~10h；
Hydroxide precipitation, the mixed proportion of strontium nitrate solution and lithium hydroxide solution of titanium in the step 4) are 0.7 ~0.9g：15~16mL：10~11mL.
2. perovskite Li according to claim 1 adulterates SrTiO3The preparation method of nano particle, which is characterized in that described Step 4) in cleaning method be：The product being obtained by filtration is cleaned five times with spirit of vinegar, deionized water repeatedly successively.
CN201611022310.9A 2016-11-16 2016-11-16 A kind of perovskite Li doping SrTiO3The preparation method and product of nano particle Expired - Fee Related CN106673057B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105727922A (en) * 2016-03-24 2016-07-06 浙江大学 Li-doped SrTiO3 octadecahedron nano-particles and preparation method thereof
CN105883910A (en) * 2016-05-13 2016-08-24 浙江大学 Preparation method and product for perovskite SrTiO3 porous nano particles

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105727922A (en) * 2016-03-24 2016-07-06 浙江大学 Li-doped SrTiO3 octadecahedron nano-particles and preparation method thereof
CN105883910A (en) * 2016-05-13 2016-08-24 浙江大学 Preparation method and product for perovskite SrTiO3 porous nano particles

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"SrTiO3纳米晶多面体可控生长及其生物学行为研究";董灵庆;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20140815(第8期);B020-25,正文第19页第2.2节、第25页倒数第1段至第32页第3段 *

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