CN105883910B - A kind of perovskite SrTiO3The preparation method and product of porous nano particle - Google Patents
A kind of perovskite SrTiO3The preparation method and product of porous nano particle Download PDFInfo
- Publication number
- CN105883910B CN105883910B CN201610319404.6A CN201610319404A CN105883910B CN 105883910 B CN105883910 B CN 105883910B CN 201610319404 A CN201610319404 A CN 201610319404A CN 105883910 B CN105883910 B CN 105883910B
- Authority
- CN
- China
- Prior art keywords
- solution
- titanium
- potassium hydroxide
- nitrate solution
- nano particle
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 77
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims abstract description 48
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000001556 precipitation Methods 0.000 claims abstract description 28
- 229910002370 SrTiO3 Inorganic materials 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 21
- 239000010936 titanium Substances 0.000 claims abstract description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 20
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims abstract description 18
- 229910000348 titanium sulfate Inorganic materials 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 238000005119 centrifugation Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000008367 deionised water Substances 0.000 description 19
- 229910021641 deionized water Inorganic materials 0.000 description 19
- 229910002367 SrTiO Inorganic materials 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229910052712 strontium Inorganic materials 0.000 description 6
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 5
- 229960000907 methylthioninium chloride Drugs 0.000 description 5
- 230000001186 cumulative effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011858 nanopowder Substances 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 4
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical class [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 3
- 239000000052 vinegar Substances 0.000 description 3
- 235000021419 vinegar Nutrition 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- -1 as shown in figure 1 Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 159000000008 strontium salts Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- 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
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to a kind of perovskite SrTiO3The preparation method of porous nano particle, comprises the following steps：1) using titanium sulfate and potassium hydroxide as raw material, the hydroxide precipitation of titanium is prepared；2) strontium nitrate solution, potassium hydroxide solution and lithium nitrate solution are prepared respectively；3) the hydroxide precipitation of titanium, strontium nitrate solution, potassium hydroxide solution and lithium nitrate solution are mixed, in the case where reaction temperature is 150~220 DEG C, carries out 3~32h of hydro-thermal reaction, then centrifugation cleans, obtain perovskite SrTiO3Porous nano particle.The preparation process is simple, and the pattern of porous structural is easy to regulation and control, size uniformity and surface has pore passage structure.
Description
Technical field
Field is synthesized the present invention relates to inorganic material, and in particular to a kind of perovskite SrTiO3The preparation of porous nano particle
Method and product.
Background technology
In recent years research finds that the performance of nano material is not only influenced by their size, is also influenceed by its pattern, therefore grind
Study carefully personnel and substantial amounts of research has been done to various patterns.The preparation of nanostructured causes people and greatly paid close attention to, not only zero dimension
Nano particle, monodimension nano stick, nanofiber and three-dimensional branch crystal, also there is many nano-particles self assemble Mesoporous Spheres, nanotube
Or nanometer sheet self-assembled nano structures etc..
Strontium titanates SrTiO3As a kind of typical Ca-Ti ore type ternary oxide, not only with dielectric constant height, dielectric
The advantages of low, heat endurance is good is lost, is widely used in electronics, machinery and ceramic industry, and its energy gap is 3.2Ev,
Also by as a kind of excellent photochemical catalyst, applied to the photocatalytic degradation of organic pollution and the photocatalytic cleavage of water to prepare
Clean energy resource hydrogen.
In recent years, on the SrTiO with different-shape feature3Preparation and performance study cause the very big emerging of people
Interest.Solid reaction process, the precipitation method, sol-gel process and hydrothermal synthesis method are SrTiO3Conventional preparation method.Wherein first three
Method is both needed to the calcining by higher temperature, and synthesized powder reuniting is serious, and pattern of the particle without rule.Middle promulgated by the State Council
Bright patent (publication number CN102320651A) discloses a kind of preparation method of strontium titanate nano powder, weigh tetra-n-butyl titanate and
Strontium nitrate is simultaneously added into reaction vessel, is added sodium hydroxide solution and is stirred with glass bar；It is fitted into microwave reaction instrument and heats up
Speed is heated；Solution is poured out into addition hydrochloric acid after room temperature is down to, then precipitation is filtered with deionized water cyclic washing, will be resulting
Precipitation be placed in baking oven in 70 DEG C drying, obtain strontium titanate nano powder.The preparation method prepares pure phase using microwave method
Strontium titanate nano powder, but do not control SrTiO3Granule-morphology.
Chinese invention patent (publication number CN104098125A) discloses a kind of preparation method of strontium titanates nano cubic block, should
Method is using titanium dioxide as titanium source, and soluble strontium salt does acid-base modifier as barium source with sodium hydroxide.First by titanium dioxide
Titanium ultrasonic disperse is among the aqueous solution, then adds the soluble-salt containing strontium thereto, and constantly stirring is allowed to dissolve, and then adds again
Suspension is finally put into reactor by alkali, regulation suspension pH value to 8~14, carries out hydro-thermal reaction.Reaction product is by washing
Wash, separate, being dried to obtain the strontium titanates nano cubic block of regular appearance and size uniformity.The application patent system is for strontium titanates surface
It is porous, it is more beneficial for adsorbing organic pollution, photocatalysis effect is more excellent.
The content of the invention
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 SrTiO3Porous nano particle
Preparation method and product, preparation process are simple, and the pattern of porous structural is easy to regulation and control, size uniformity and surface has duct knot
Structure.
The present invention solves the technical scheme of above-mentioned technical problem：
A kind of perovskite SrTiO3The preparation method of porous nano particle, comprises the following steps：
1) using titanium sulfate and potassium hydroxide as raw material, the hydroxide precipitation of titanium is prepared；
2) strontium nitrate solution, potassium hydroxide solution and lithium nitrate solution are prepared respectively；Mole of described strontium nitrate solution
0.2~0.6mol/L of concentration, the molar concentration of potassium hydroxide solution is 1~3mol/L, lithium nitrate solution molar concentration 0.6~
1mol/L；
3) the hydroxide precipitation of titanium, strontium nitrate solution, potassium hydroxide solution and lithium nitrate solution are mixed, in reaction temperature
Spend at 150~220 DEG C, to carry out 3~32h of hydro-thermal reaction, then centrifugation cleans, obtain perovskite SrTiO3Porous nano
Grain；The hydroxide precipitation of described titanium, strontium nitrate solution, the mixed proportion of potassium hydroxide solution and lithium nitrate solution are：0.6
~2g：5~10ml：10~15ml：5~10ml.
Above-mentioned technical proposal promotes the hydrogen-oxygen of titanium using precipitating reagent potassium hydroxide using titanium sulfate and strontium nitrate as reaction mass
The generation of compound, while adulterating lithium nitrate to regulate and control the growth of crystal, finally realizes perovskite SrTiO3Porous nano particle
Preparation.Potassium hydroxide is highly basic, OH-Ion concentration is higher, and crystal growth easily deviates the intrinsic symmetry of its structure cell, simultaneously
The edges and corners surface of crystal grain can be higher, and in order to drop low-surface-energy, corner angle can dissolve precipitation and form new particle, so gained particle
Corner is rounding off.Lithium ion can promote plane of crystal OH-Dehydration, upset the constituent of liquid level, reduction absorption
Resistance, OH-Crystals are readily diffused into, OH during natural cooling-Ion is escaped, and forms the structure of porous surface.With table
The perovskite SrTiO of the porous structure in face3With more excellent photocatalysis performance.
Preferably, described step 1) in prepare titanium hydroxide precipitation method be：Molar concentration is prepared respectively
The potassium hydroxide solution of titanium sulfate solution and 6~10mol/L for 0.15~0.5mol/L；Potassium hydroxide solution is added drop-wise to sulphur
In sour titanium solution, the hydroxide precipitation of titanium is filtrated to get.
Be used as further preferred, described step 1) in potassium hydroxide solution is added drop-wise in titanium sulfate solution, obtain titanium
Hydroxide precipitation, stand 15~20min, the hydroxide that titanium is cleaned with deionized water precipitates and centrifuge 4~5 times.
It is used as 2~4 drops/sec further preferred, described of rate of addition.By controlling rate of addition, further control
SrTiO3The pattern of loose structure.
Preferably, described step 3) in reaction temperature be 160~180 DEG C, the reaction time be 3~6h.
Preferably, described step 3) in titanium hydroxide precipitation, strontium nitrate solution, potassium hydroxide solution and nitre
The mixed proportion of sour lithium solution is：0.6~0.8g：5~8ml：10~13ml：5~8ml.
Preferably, described step 3) in cleaning method be：By the product being filtrated to get successively with spirit of vinegar, go from
Sub- water cleaning.Plus spirit of vinegar stirs that the SrCO that carbon dioxide is formed will be mixed into presoma3Remove, use deionized water
Cleaning is the nitrate ion, potassium ion and the perovskite SrTiO of synthesis in order to which reaction mass is introduced3Porous nano particle fills
Separation, obtains the perovskite SrTiO of pure phase3Porous nano particle.
Preferably, described step 1) in prepare titanium hydroxide precipitation method be：Molar concentration is prepared respectively
The potassium hydroxide solution of titanium sulfate solution and 5.5~6.5mol/L for 0.13~0.17mol/L；Potassium hydroxide solution is being stirred
Mix under state 2~3 drops/sec to be added drop-wise in titanium sulfate solution, be filtrated to get the hydroxide precipitation of titanium；Described step 2) in nitre
0.18~0.22mol/L of molar concentration of sour strontium solution, the molar concentration of potassium hydroxide solution is 0.9~1.1mol/L, nitric acid
0.5~0.7mol/L of lithium solution molar concentration；Described step 3) in by the hydroxide of 0.6~0.7g titaniums precipitation, 5~6ml
The strontium nitrate aqueous solution, 10~11ml potassium hydroxide solutions and 5~6ml lithium nitrate solutions are mixed to join in reactor, 160
Insulation is heat-treated for 3~5 hours at~170 DEG C.Under the conditions described above, gained perovskite SrTiO3Porous nanometer structure
Pattern preferably, steady quality, purity is high, powder granule good dispersion.
The present invention also provides a kind of perovskite SrTiO of above-mentioned preparation method synthesis3Porous nano particle.Described calcium titanium
Ore deposit SrTiO3The size of porous nano particle is 300~600nm.Described size be the circumscribed diameter of a circle of porous nano particle or
The length of side of person's porous nano particle.The perovskite SrTiO prepared3Porous nano particle equally has above-mentioned beneficial effect.
Compared with the existing technology, beneficial effects of the present invention are embodied in：
(1) present invention process process is simple, it is easy to control, and non-environmental-pollution, cost is low, it is easy to large-scale production.
(2) perovskite SrTiO made from3The nano-powder size of porous nano particle is between 300~600nm and surface
With loose structure.Product quality is stable, and purity is high, powder granule good dispersion.
Brief description of the drawings
Fig. 1 is the perovskite SrTiO that embodiment 1 is synthesized3The X-ray diffractogram of porous nano particle；
Fig. 2 is the perovskite SrTiO that embodiment 1 is synthesized3The scanning electron microscope diagram of porous nano particle；
Fig. 3 is the perovskite SrTiO that comparative example 1 is synthesized3The scanning electron microscope diagram of porous nano particle；
Fig. 4 is the perovskite SrTiO that embodiment 1 is synthesized3The degraded figure of porous nano pellet degradation methylene blue；
Fig. 5 schemes for methylene blue from degraded.
Embodiment
With reference to embodiments the present invention is further illustrated with accompanying drawing.
Embodiment 1
1) 4mmol titanium sulfates and 0.15mol potassium hydroxide are dissolved separately in deionized water, regulation titanium sulfate solution
Molar concentration 0.15mol/L, the molar concentration of potassium hydroxide solution is 6mol/L.
2) potassium hydroxide solution is slowly added dropwise in titanium sulfate solution under stirring, rate of addition is 2 drops/sec,
The hydroxide precipitation of white titanium is obtained, 20min is stood, centrifuges 4~5 times.
3) strontium nitrate, potassium hydroxide and lithium nitrate are dissolved separately in deionized water, the molar concentration of strontium nitrate is
0.2mol/L, the molar concentration of potassium hydroxide solution is 1mol/L, and the molar concentration of lithium nitrate solution is 0.6mol/L.
4) by the hydroxide precipitation of the 0.6g titaniums cleaned, the 5ml strontium nitrates aqueous solution, 10ml potassium hydroxide solutions and
5ml lithium nitrate solutions are added separately in 50ml reactors, and it is the 40% of reactor inner bag to adjust cumulative volume with deionized water, is stirred
Mix after 2h, be incubated and be heat-treated at 160 DEG C for 4 hours.Then, room temperature is down to, reaction product, filtering, successively with dilute is taken out
Acetic acid, deionized water are cleaned, and are dried at a temperature of 60 DEG C, are obtained perovskite SrTiO3Porous nano particle.
Synthesized perovskite SrTiO3The X-ray diffractogram of porous nano particle, as shown in figure 1, product is perovskite
SrTiO3Porous particle, does not have other impurities peak, illustrates the SrTiO that product is pure phase3。
SEM SEM photograph is as shown in Fig. 2 obtained perovskite SrTiO3Porous nano particle size between
300~600nm, pattern is the porous cube of rounding off, and surface has loose structure.
Embodiment 2
1) 6mmol titanium sulfates and 0.2mol potassium hydroxide are dissolved separately in deionized water, regulation titanium sulfate solution
Molar concentration 0.3mol/L, the molar concentration of potassium hydroxide solution is 8mol/L.
2) potassium hydroxide solution is slowly added dropwise in titanium sulfate solution under stirring, rate of addition is 4 drops/sec,
The hydroxide precipitation of white titanium is obtained, 20min is stood, centrifuges 4~5 times.
3) strontium nitrate, potassium hydroxide and lithium nitrate are dissolved separately in deionized water, the molar concentration of strontium nitrate is
0.4mol/L, the molar concentration of potassium hydroxide solution is 2mol/L, and the molar concentration of lithium nitrate solution is 0.8mol/L.
4) by the hydroxide precipitation of the 0.8g titaniums cleaned, the 8ml strontium nitrates aqueous solution, 13ml potassium hydroxide solutions and
8ml lithium nitrate solutions are added separately in 50ml reactors, and it is the 40% of reactor inner bag to adjust cumulative volume with deionized water, is stirred
Mix after 2h, be incubated and be heat-treated at 200 DEG C for 12 hours.Then, room temperature is down to, reaction product is taken out, sequentially adds dilute vinegar
Acid and deionized water are dried at a temperature of centrifuging 4~5 times, 60 DEG C, obtain perovskite SrTiO3Porous nano particle.
Comparative example 1：
1) 6mmol titanium sulfates and 0.2mol potassium hydroxide are dissolved separately in deionized water, regulation titanium sulfate solution
Molar concentration 0.3mol/L, the molar concentration of potassium hydroxide solution is 8mol/L.
2) potassium hydroxide solution is slowly added dropwise in titanium sulfate solution under stirring, rate of addition is 4 drops/sec,
The hydroxide precipitation of white titanium is obtained, 20min is stood, centrifuges 4~5 times.
3) strontium nitrate, potassium hydroxide are dissolved separately in deionized water, the molar concentration of strontium nitrate is 0.4mol/L,
The molar concentration of potassium hydroxide solution is 2mol/L.
4) the hydroxide precipitation of the 0.8g titaniums cleaned, the 8ml strontium nitrates aqueous solution, 13ml potassium hydroxide solutions are distinguished
It is added in 50ml reactors, it is the 40% of reactor inner bag to adjust cumulative volume with deionized water, after stirring 2h, at 200 DEG C
Insulation is heat-treated for 12 hours.Then, room temperature is down to, reaction product is taken out, spirit of vinegar and deionized water centrifugation 4 is sequentially added
Dried at a temperature of~5 times, 60 DEG C.
SEM SEM photograph is as shown in figure 3, be the smooth elliposoidal SrTiO in surface3Particle, it is impossible to obtain
Perovskite SrTiO3Porous nano particle.
Comparative example 2：
1) 4mmol titanium sulfates and 0.15mol potassium hydroxide are dissolved separately in deionized water, regulation titanium sulfate solution
Molar concentration 0.15mol/L, the molar concentration of potassium hydroxide solution is 6mol/L.
2) potassium hydroxide solution is slowly added dropwise in titanium sulfate solution under stirring, rate of addition is 2 drops/sec,
The hydroxide precipitation of white titanium is obtained, 20min is stood, centrifuges 4~5 times.
3) strontium nitrate, tetramethyl aqua ammonia and lithium nitrate are dissolved separately in deionized water, strontium nitrate it is mole dense
Spend for 0.2mol/L, the molar concentration of tetramethyl Dilute Ammonia Solution is 1mol/L, and the molar concentration of lithium nitrate solution is
0.6mol/L。
4) by the hydroxide precipitation of the 0.6g titaniums cleaned, the 5ml strontium nitrates aqueous solution, 10ml tetramethyls aqua ammonia and
5ml lithium nitrate solutions are added separately in 50ml reactors, and it is the 40% of reactor inner bag to adjust cumulative volume with deionized water, is stirred
Mix after 2h, be incubated and be heat-treated at 160 DEG C for 4 hours.Then, room temperature is down to, reaction product, filtering, successively with dilute is taken out
Acetic acid, deionized water are cleaned, and are dried at a temperature of 60 DEG C.It is demonstrated experimentally that perovskite SrTiO can not be obtained3Porous nano particle.
Degradation of methylene blue performance test：
10-5The perovskite SrTiO prepared by 0.1g embodiments 1 is added in mol/L 100mL methylene blue solution3
Irradiated under ultraviolet light after porous particle, dark stirring 40min, a sample, gained uv-visible absorption spectra are taken every 20min
As shown in Figure 4.
It is control group separately to make one group of experiment that ultraviolet degradation methylene blue is carried out without any catalyst, and gained is purple
Outside-visible absorption spectra is as shown in Figure 5.By contrast, the perovskite SrTiO prepared by this method3Porous nano particle
With preferable photocatalysis performance.
Claims (1)
1. a kind of perovskite SrTiO3The preparation method of porous nano particle, it is characterised in that comprise the following steps：
1) using titanium sulfate and potassium hydroxide as raw material, the hydroxide precipitation of titanium is prepared；The described hydroxide for preparing titanium sinks
The method in shallow lake is：It is 0.13~0.17mol/L titanium sulfate solution and 5.5~6.5mol/L hydrogen-oxygen to prepare molar concentration respectively
Change potassium solution；Potassium hydroxide solution is added drop-wise in titanium sulfate solution for 2~3 drops/sec under stirring, the hydrogen of titanium is filtrated to get
Oxide precipitation；
2) strontium nitrate solution, potassium hydroxide solution and lithium nitrate solution are prepared respectively；The molar concentration of described strontium nitrate solution
0.2~0.22mol/L, the molar concentration of potassium hydroxide solution is 1~1.1mol/L, lithium nitrate solution molar concentration 0.6~
0.7mol/L；
3) the hydroxide precipitation of titanium, strontium nitrate solution, potassium hydroxide solution and lithium nitrate solution are mixed, is in reaction temperature
At 160~170 DEG C, 3~5h of hydro-thermal reaction is carried out, then centrifugation cleans, obtain perovskite SrTiO3Porous nano particle；Institute
The hydroxide precipitation of the titanium stated, strontium nitrate solution, the mixed proportion of potassium hydroxide solution and lithium nitrate solution are：0.6~
0.7g：5~6ml：10~11ml：5~6ml.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610319404.6A CN105883910B (en) | 2016-05-13 | 2016-05-13 | A kind of perovskite SrTiO3The preparation method and product of porous nano particle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610319404.6A CN105883910B (en) | 2016-05-13 | 2016-05-13 | A kind of perovskite SrTiO3The preparation method and product of porous nano particle |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105883910A CN105883910A (en) | 2016-08-24 |
| CN105883910B true CN105883910B (en) | 2017-10-13 |
Family
ID=56716388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610319404.6A Expired - Fee Related CN105883910B (en) | 2016-05-13 | 2016-05-13 | A kind of perovskite SrTiO3The preparation method and product of porous nano particle |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105883910B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106673057B (en) * | 2016-11-16 | 2018-07-24 | 浙江大学 | A kind of perovskite Li doping SrTiO3The preparation method and product of nano particle |
| CN106745210B (en) * | 2017-01-06 | 2018-06-29 | 浙江大学 | A kind of Li adulterates SrTiO3The preparation method and product of porous surface nano particle |
| CN106745211B (en) * | 2017-01-06 | 2018-06-29 | 浙江大学 | A kind of Li adulterates SrTiO3The preparation method and product of square nano particle |
| CN110952143B (en) * | 2019-12-03 | 2021-09-03 | 华东理工大学 | Synthesis method of mesoporous single-crystal strontium titanate |
| CN116459819A (en) * | 2022-01-12 | 2023-07-21 | 中国科学院化学研究所 | Titanium-based perovskite material with different microstructures, preparation method thereof and application of titanium-based perovskite material in photocatalytic antibiotic degradation |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5219811A (en) * | 1989-08-31 | 1993-06-15 | Central Glass Company, Limited | Powder composition for sintering into modified barium titanate semiconductive ceramic |
| CN101092244A (en) * | 2007-06-19 | 2007-12-26 | 浙江大学 | Method for preparing porous balls of strontium titanate |
| CN102167396A (en) * | 2011-03-18 | 2011-08-31 | 浙江大学 | Method for preparing strontium titanate mesoporous sphere |
| CN105399138A (en) * | 2015-12-15 | 2016-03-16 | 浙江大学 | Perovskite SrTiO3 tetragonal nanoparticle preparation method and product |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2558357B2 (en) * | 1989-02-22 | 1996-11-27 | セントラル硝子株式会社 | Barium titanate-based powder for semiconductor porcelain and its manufacturing method |
-
2016
- 2016-05-13 CN CN201610319404.6A patent/CN105883910B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5219811A (en) * | 1989-08-31 | 1993-06-15 | Central Glass Company, Limited | Powder composition for sintering into modified barium titanate semiconductive ceramic |
| CN101092244A (en) * | 2007-06-19 | 2007-12-26 | 浙江大学 | Method for preparing porous balls of strontium titanate |
| CN102167396A (en) * | 2011-03-18 | 2011-08-31 | 浙江大学 | Method for preparing strontium titanate mesoporous sphere |
| CN105399138A (en) * | 2015-12-15 | 2016-03-16 | 浙江大学 | Perovskite SrTiO3 tetragonal nanoparticle preparation method and product |
Non-Patent Citations (1)
| 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);摘要第2段、正文第19页第2.2节、第26页第1段及图3.1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105883910A (en) | 2016-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105883910B (en) | A kind of perovskite SrTiO3The preparation method and product of porous nano particle | |
| CN108147462A (en) | A kind of tungsten trioxide nano-rod and its preparation with photocatalysis performance | |
| CN106542560B (en) | A kind of preparation method of rare earth oxysulfate | |
| CN110201655B (en) | One-step method for preparing hollow TiO2Method and application of nano-microspheres | |
| CN107098381A (en) | The preparation method of the zinc titanate catalysis material of special appearance | |
| CN108636395A (en) | A kind of composite photo-catalyst of weakly visible photoresponse and its preparation and application | |
| CN103263906A (en) | Nanocrystal tin oxide photocatalyst and preparation method thereof | |
| CN105727922B (en) | A kind of Li adulterates SrTiO3The preparation method and product of ten octahedron nanometer particles | |
| CN114130410A (en) | Bismuth iron titanium oxyhalide photocatalytic material and preparation method and application thereof | |
| CN106830069B (en) | A kind of flower-shaped mesoporous TiO 2 hierarchy and preparation method thereof | |
| CN105399138A (en) | Perovskite SrTiO3 tetragonal nanoparticle preparation method and product | |
| CN107803170A (en) | A kind of preparation method of titanium dioxide/nickel oxide bivalve hollow ball | |
| CN104909405B (en) | Spindle nano titanium oxide based on cellulose base template and preparation method thereof | |
| CN109261180A (en) | Utilize the Ti of dimethyl sulfoxide intercalation and layering3C2Fabricated in situ TiO2@Ti3C2Method and product | |
| CN105836796A (en) | Preparation method of bell-type core-shell structured nano-TiO2(at)void(at)SiO2 powder | |
| CN105688874B (en) | A kind of TiO with classification cavernous structure2Nano-powder and preparation method thereof | |
| CN107115856A (en) | A kind of preparation method of sheet bismuth titanates chlorine oxygen bismuth composite | |
| Wang et al. | Template-free fabrication of rattle-type TiO 2 hollow microspheres with superior photocatalytic performance | |
| CN107913712A (en) | A kind of titanium dioxide/modification infusorial earth composite material, film and its preparation method and application | |
| CN105214694B (en) | A kind of method that soft template method prepares BiOCl hollow shells | |
| CN106745210B (en) | A kind of Li adulterates SrTiO3The preparation method and product of porous surface nano particle | |
| CN109794290A (en) | A kind of screw type titanium oxyoxalate salt photochemical catalyst and preparation method thereof | |
| CN103074661A (en) | Method for controlling hydrophily and hydrophobicity of array surface of titanium dioxide nanotube | |
| CN103588244B (en) | Without the method for the sandwich hollow titanium dioxide nano material of template synthesis | |
| CN109553128A (en) | Rutile titanium dioxide is nanocrystalline, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171013 Termination date: 20190513 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |