CN107082447B - A kind of preparation method of the hollow Cerium titanate microballoon of macropore - Google Patents
A kind of preparation method of the hollow Cerium titanate microballoon of macropore Download PDFInfo
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- CN107082447B CN107082447B CN201710286590.2A CN201710286590A CN107082447B CN 107082447 B CN107082447 B CN 107082447B CN 201710286590 A CN201710286590 A CN 201710286590A CN 107082447 B CN107082447 B CN 107082447B
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 35
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 58
- 239000012065 filter cake Substances 0.000 claims abstract description 36
- 239000002253 acid Substances 0.000 claims abstract description 26
- -1 isopropyl alcohol ester Chemical class 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 239000012695 Ce precursor Substances 0.000 claims abstract description 18
- 239000000047 product Substances 0.000 claims abstract description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 8
- 239000008103 glucose Substances 0.000 claims abstract description 8
- 239000003381 stabilizer Substances 0.000 claims abstract description 8
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims abstract description 3
- 238000005485 electric heating Methods 0.000 claims description 56
- 239000007788 liquid Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- 239000012153 distilled water Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 238000003760 magnetic stirring Methods 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 15
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 14
- 239000004744 fabric Substances 0.000 claims description 14
- 239000004570 mortar (masonry) Substances 0.000 claims description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 14
- 229910052573 porcelain Inorganic materials 0.000 claims description 14
- 230000001105 regulatory effect Effects 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 229910001220 stainless steel Inorganic materials 0.000 claims description 14
- 239000010935 stainless steel Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 150000002823 nitrates Chemical class 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- 239000008399 tap water Substances 0.000 claims description 7
- 235000020679 tap water Nutrition 0.000 claims description 7
- 230000005619 thermoelectricity Effects 0.000 claims description 7
- 238000011001 backwashing Methods 0.000 claims 2
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- 239000002826 coolant Substances 0.000 claims 1
- 229920001223 polyethylene glycol Polymers 0.000 claims 1
- 238000004506 ultrasonic cleaning Methods 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 abstract 2
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 abstract 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 abstract 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 238000002604 ultrasonography Methods 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 8
- 239000004927 clay Substances 0.000 description 6
- 238000009434 installation Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 4
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011796 hollow space material Substances 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical class CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
Classifications
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/12—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/653—500-1000 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/657—Pore diameter larger than 1000 nm
-
- 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
- C01P2004/34—Spheres hollow
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A kind of preparation method of the hollow Cerium titanate microballoon of macropore prepares template presoma：It is prepared with n-butanol, glucose solution, PEG 20000, dodecyl trimethyl ammonium bromide and stabilizer SY 5；Hydrothermal synthesis macropore template：Template presoma is kept the temperature into 36 h at 180 ~ 200 DEG C, sonicated, filtering, drying are made；Metatitanic acid cerium precursor：Including metatitanic acid isopropyl alcohol ester, absolute ethyl alcohol, acetone, directed agents AP 3, cerous nitrate；Hydrothermal synthesis Cerium titanate：Metatitanic acid cerium precursor is kept the temperature into 72 h at 220 ~ 240 DEG C, then through ultrasonic cleaning, filtering and drying process；Heat treatment：Filter cake is calcined into 3 ~ 6 h at 1200 ~ 1350 DEG C, is ground to obtain the final product.Preparation process condition has operability, and product particle size is uniform, shape is complete, and product photocatalytic activity is high and stablizes.
Description
Technical field
The invention belongs to environmental purification function Material Fields, and in particular to a kind of preparation side of the hollow Cerium titanate microballoon of macropore
Method.
Background technology
Large pore material（Macroporous materials）Aperture is more than 50 nm.Pore structure in large pore material can be at
Enter the channel of pore passage structure for adsorption molecule.Large pore material has that specific surface area is larger, density is low, low-refraction and heat
The features such as coefficient of expansion is relatively low so that macropore hollow material is widely used in catalyst carrier, radioresistance skin-material, chargeable
Battery etc..Macropore hollow material has unique excellent photocatalysis property, is not only due to increased specific surface area, while hollow
Structure can stablize its activated centre.In hollow shell structure particles, internal pore passage structure gap provides a large amount of suitable
It is reacted for being catalyzed in space.
Cerium titanate is a kind of titanate material with particular advantages, by the extensive concern of all circles, it is considered to be a kind of
The environmental pollution purification type catalysis material of great development prospect.Although powder Cerium titanate has higher purification activity, urge
The recycling of agent becomes people's issues that need special attention in practical application.Nano-powder Cerium titanate photochemical catalyst is for disappearing
When except water pollutant, there are catalyst recycling, and difficult, catalyst is easy inactivation, needs to maintain catalyst by power stirring
Suspension the shortcomings of.Novel nano structure catalyst such as nanometer macropore tiny balloon etc. has low-density, the characteristic of high-ratio surface,
Catalyst can be made to be easy to detach from solution according to the difference of catalyst use condition simultaneously.Macropore hollow material is as a kind of
Novel environmental purification function material has broad application prospects.This patent discloses a kind of system of the hollow Cerium titanate microballoon of macropore
Preparation Method.
Invention content
In view of the problems of the existing technology, the present invention is intended to provide a kind of preparation side of the hollow Cerium titanate microballoon of macropore
Method.
The technical solution adopted by the present invention is：
A kind of preparation method of the hollow Cerium titanate microballoon of macropore, including following processing steps：
1, template presoma is prepared
By 30 ~ 40 mL n-butanols, 18 ~ 25 mL of glucose solution of 3 mol/L, 5.6 ~ 7.5 g PEG 20000s,
1.5 ~ 2.7 mL dodecyl trimethyl ammonium bromide and 0.5 ~ 1.2 g stabilizers SY-5 are added in 100 mL twoport round-bottomed flasks；
Flask is placed in precise temperature control electric heating packet, in flask center, interface installs spherical condensation tube, is cold with tap water
But medium, in another interface installation thermometric thermoelectricity of flask corner.By adjusting electric heating packet heating temperature to control solution temperature in flask
Degree is 60 DEG C, maintains the reflux for 50 min of time in this temperature, then cools to room temperature, spare.
2, hydrothermal synthesis macropore template
The template presoma of preparation is moved into the cup-like liner made of polytetrafluoroethylene material that volume is 100 mL,
It closes the lid, is placed in stainless steel autoclave；
Autoclave is put in constant temperature electric heating drying box, constant temperature electric heating drying box temperature is risen to 180 ~ 200 DEG C,
Keep the temperature 36 h；In the process, it is not more than to control pressure in autoclave by regulating thermostatic electrically heated drying cabinet temperature
3MPa；
After waiting until the device cools to room temperature, product is transferred in 200 mL beakers, with 45 MHz in ultrasonic cleaner
Frequency ultrasound is handled 20 minutes；
Gained solidliquid mixture is filtered by cloth funnel, after being washed with distilled water 3 times, then is washed repeatedly with absolute ethyl alcohol
It washs 3 times, obtains solid filter cake；
Filter cake is placed in constant temperature electric heating drying box, dry 6 h, then clay into power in the agate mortar at 90 DEG C,
It is spare.
3, prepared by metatitanic acid cerium precursor
5.2 ~ 6.3 mL metatitanic acid isopropyls alcohol esters, 30 ~ 35 mL absolute ethyl alcohols, 12 ~ 14 are separately added into 100 mL beakers
ML acetone and 1.2 ~ 1.3 g directed agents AP-3, stir 20 min, as A liquid on magnetic stirring apparatus；
30 mL absolute ethyl alcohols, 3.6 g Surfactant OPs -3,500 mg macropores templates, 50 are added in 200 mL beakers
~ 60 mL distilled water and 1.5 ~ 2.1 g cerous nitrates, stir 20 min, as B liquid on magnetic stirring apparatus；
A drops are added in B liquid during magnetic agitation and continue to stir 30 min, by mixed liquor in ultrasonic cleaning
It is ultrasonically treated 1 h with 45 MHz frequencies in device, it is spare.
4, hydrothermal synthesis Cerium titanate
Metatitanic acid cerium precursor is moved into the cup-like liner made of polytetrafluoroethylene material that volume is 200 mL, is covered
Lid is placed in stainless steel autoclave；
Autoclave is put in constant temperature electric heating drying box, constant temperature electric heating drying box temperature is risen to 220 ~ 240 DEG C,
Keep the temperature 72 h.In the process, it is not more than to control pressure in autoclave by regulating thermostatic electrically heated drying cabinet temperature
3MPa；
After waiting until the device cools to room temperature, product is transferred in 200 mL beakers, with 45 MHz in ultrasonic cleaner
Frequency ultrasound is handled 20 minutes；
Gained solidliquid mixture is filtered by cloth funnel, after being washed with distilled water 3 times, then is washed repeatedly with absolute ethyl alcohol
It washs 3 times, obtains solid filter cake；
Filter cake is placed in constant temperature electric heating drying box, dry 6 h, spare at 120 DEG C.
5, it is heat-treated
Filter cake is put into porcelain crucible and is placed in program-controlled cabinet-type electric furnace, with 10 DEG C/min heating rates by furnace temperature
1200 ~ 1350 DEG C are risen to, in 3 ~ 6 h of this temperature calcination.It is taken out after electric furnace is cooled to room temperature, grinds and be made in porcelain mortar
The hollow Cerium titanate microballoon of macropore.
Compared with the prior art, the advantages of the present invention are as follows：
1, the present invention provides a kind of method preparing the hollow Cerium titanate microballoon of new macroporous, the key technology of this method is
To the reasonably optimizing of preparation process and composition of raw materials；
2, the present invention has reasonably selected macropore template and the solvent in metatitanic acid cerium precursor solution and key component, to system
The selection of standby parameters of technique process also fully takes into account the stability of material prepared and active needs；
3, preparation process condition provided by the invention has operability, and product particle size is uniform, shape is complete, product
Photocatalytic activity is high and stablizes.
Specific implementation mode
Embodiment 1
A kind of preparation method of the hollow Cerium titanate microballoon of macropore, including following processing steps：
Step 1：Prepare template presoma
By 32 mL n-butanols, 18 mL of glucose solution of 3 mol/L, 5.6 g PEG 20000s, 1.6 mL 12
Alkyl trimethyl ammonium bromide and 0.7 g stabilizers SY-5 are added in 100 mL twoport round-bottomed flasks；
Flask is placed in precise temperature control electric heating packet, in flask center, interface installs spherical condensation tube, is cold with tap water
But medium, in another interface installation thermometric thermoelectricity of flask corner；By adjusting electric heating packet heating temperature to control solution temperature in flask
Degree is 60 DEG C, maintains the reflux for 50 min of time in this temperature, then cools to room temperature, spare.
Step 2：Hydrothermal synthesis macropore template
The template presoma of preparation is moved into the cup-like liner made of polytetrafluoroethylene material that volume is 100 mL,
It closes the lid, is placed in stainless steel autoclave；
Autoclave is put in constant temperature electric heating drying box, constant temperature electric heating drying box temperature is risen to 180 ~ 200 DEG C,
Keep the temperature 36 h.In the process, it is not more than to control pressure in autoclave by regulating thermostatic electrically heated drying cabinet temperature
3MPa；
After waiting until the device cools to room temperature, product is transferred in 200 mL beakers, with 45 MHz in ultrasonic cleaner
Frequency ultrasound is handled 20 minutes；
Gained solidliquid mixture is filtered by cloth funnel, after being washed with distilled water 3 times, then is washed repeatedly with absolute ethyl alcohol
It washs 3 times, obtains solid filter cake；
Filter cake is placed in constant temperature electric heating drying box, dry 6 h, then clay into power in the agate mortar at 90 DEG C,
It is spare.
Step 3：It is prepared by metatitanic acid cerium precursor
Be separately added into 100 mL beakers 5.3 mL metatitanic acid isopropyls alcohol esters, 30 mL absolute ethyl alcohols, 12 mL acetone and
1.2 g directed agents AP-3, stir 20 min, as A liquid on magnetic stirring apparatus；
30 mL absolute ethyl alcohols, 3.6 g Surfactant OPs -3,500 mg macropores templates, 50 are added in 200 mL beakers
ML distilled water and 1.5 g cerous nitrates, stir 20 min, as B liquid on magnetic stirring apparatus；
A drops are added in B liquid during magnetic agitation and continue to stir 30 min, by mixed liquor in ultrasonic cleaning
It is ultrasonically treated 1 h with 45 MHz frequencies in device, it is spare.
Step 4：Hydrothermal synthesis Cerium titanate
Metatitanic acid cerium precursor is moved into the cup-like liner made of polytetrafluoroethylene material that volume is 200 mL, is covered
Lid is placed in stainless steel autoclave；
Autoclave is put in constant temperature electric heating drying box, constant temperature electric heating drying box temperature is risen to 220 ~ 240 DEG C,
Keep the temperature 72 h.In the process, it is not more than to control pressure in autoclave by regulating thermostatic electrically heated drying cabinet temperature
3MPa；
After waiting until the device cools to room temperature, product is transferred in 200 mL beakers, with 45 MHz in ultrasonic cleaner
Frequency ultrasound is handled 20 minutes；
Gained solidliquid mixture is filtered by cloth funnel, after being washed with distilled water 3 times, then is washed repeatedly with absolute ethyl alcohol
It washs 3 times, obtains solid filter cake；
Filter cake is placed in constant temperature electric heating drying box, dry 6 h, spare at 120 DEG C.
Step 5：Heat treatment
Filter cake is put into porcelain crucible and is placed in program-controlled cabinet-type electric furnace, with 10 DEG C/min heating rates by furnace temperature
1200 DEG C are risen to, in 5 h of this temperature calcination.It is taken out after electric furnace is cooled to room temperature, it is hollow that obtained macropore is ground in porcelain mortar
Cerium titanate microballoon.
Involved in the present embodiment to the rotating speed of magnetic stirring apparatus be 200 r/min.
Embodiment 2
A kind of preparation method of the hollow Cerium titanate microballoon of macropore, including following processing steps：
Step 1：Prepare template presoma
By 35 mL n-butanols, 21 mL of glucose solution of 3 mol/L, 6 g PEG 20000s, 1.9 mL dodecanes
Base trimethylammonium bromide and 0.7 g stabilizers SY-5 are added in 100 mL twoport round-bottomed flasks；
Flask is placed in precise temperature control electric heating packet, in flask center, interface installs spherical condensation tube, is cold with tap water
But medium, in another interface installation thermometric thermoelectricity of flask corner.By adjusting electric heating packet heating temperature to control solution temperature in flask
Degree is 60 DEG C, maintains the reflux for 50 min of time in this temperature, then cools to room temperature, spare.
Step 2：Hydrothermal synthesis macropore template
The template presoma of preparation is moved into the cup-like liner made of polytetrafluoroethylene material that volume is 100 mL,
It closes the lid, is placed in stainless steel autoclave；
Autoclave is put in constant temperature electric heating drying box, constant temperature electric heating drying box temperature is risen to 180 ~ 200 DEG C,
Keep the temperature 36 h.In the process, it is not more than to control pressure in autoclave by regulating thermostatic electrically heated drying cabinet temperature
3MPa；
After waiting until the device cools to room temperature, product is transferred in 200 mL beakers, with 45 MHz in ultrasonic cleaner
Frequency ultrasound is handled 20 minutes；
Gained solidliquid mixture is filtered by cloth funnel, after being washed with distilled water 3 times, then is washed repeatedly with absolute ethyl alcohol
It washs 3 times, obtains solid filter cake；
Filter cake is placed in constant temperature electric heating drying box, dry 6 h, then clay into power in the agate mortar at 90 DEG C,
It is spare.
Step 3：It is prepared by metatitanic acid cerium precursor
Be separately added into 100 mL beakers 5.8 mL metatitanic acid isopropyls alcohol esters, 32 mL absolute ethyl alcohols, 12 mL acetone and
1.2 g directed agents AP-3, stir 20 min, as A liquid on magnetic stirring apparatus；
30 mL absolute ethyl alcohols, 3.6 g Surfactant OPs -3,500 mg macropores templates, 55 are added in 200 mL beakers
ML distilled water and 1.8 g cerous nitrates, stir 20 min, as B liquid on magnetic stirring apparatus；
A drops are added in B liquid during magnetic agitation and continue to stir 30 min, by mixed liquor in ultrasonic cleaning
It is ultrasonically treated 1 h with 45 MHz frequencies in device, it is spare.
Step 4：Hydrothermal synthesis Cerium titanate
Metatitanic acid cerium precursor is moved into the cup-like liner made of polytetrafluoroethylene material that volume is 200 mL, is covered
Lid is placed in stainless steel autoclave；
Autoclave is put in constant temperature electric heating drying box, constant temperature electric heating drying box temperature is risen to 220 ~ 240 DEG C,
Keep the temperature 72 h.In the process, it is not more than to control pressure in autoclave by regulating thermostatic electrically heated drying cabinet temperature
3MPa；
After waiting until the device cools to room temperature, product is transferred in 200 mL beakers, with 45 MHz in ultrasonic cleaner
Frequency ultrasound is handled 20 minutes；
Gained solidliquid mixture is filtered by cloth funnel, after being washed with distilled water 3 times, then is washed repeatedly with absolute ethyl alcohol
It washs 3 times, obtains solid filter cake；
Filter cake is placed in constant temperature electric heating drying box, dry 6 h, spare at 120 DEG C.
Step 5：Heat treatment
Filter cake is put into porcelain crucible and is placed in program-controlled cabinet-type electric furnace, with 10 DEG C/min heating rates by furnace temperature
1260 DEG C are risen to, in 5 h of this temperature calcination.It is taken out after electric furnace is cooled to room temperature, it is hollow that obtained macropore is ground in porcelain mortar
Cerium titanate microballoon.
Involved in the present embodiment to the rotating speed of magnetic stirring apparatus be 200 r/min.
Embodiment 3
A kind of preparation method of the hollow Cerium titanate microballoon of macropore, including following processing steps：
Step 1：Prepare template presoma
By 38 mL n-butanols, 25 mL of glucose solution of 3 mol/L, 7.3 g PEG 20000s, 2.5 mL 12
Alkyl trimethyl ammonium bromide and 1.1 g stabilizers SY-5 are added in 100 mL twoport round-bottomed flasks；
Flask is placed in precise temperature control electric heating packet, in flask center, interface installs spherical condensation tube, is cold with tap water
But medium, in another interface installation thermometric thermoelectricity of flask corner.By adjusting electric heating packet heating temperature to control solution temperature in flask
Degree is 60 DEG C, maintains the reflux for 50 min of time in this temperature, then cools to room temperature, spare.
Step 2：Hydrothermal synthesis macropore template
The template presoma of preparation is moved into the cup-like liner made of polytetrafluoroethylene material that volume is 100 mL,
It closes the lid, is placed in stainless steel autoclave；
Autoclave is put in constant temperature electric heating drying box, constant temperature electric heating drying box temperature is risen to 180 ~ 200 DEG C,
Keep the temperature 36 h.In the process, it is not more than to control pressure in autoclave by regulating thermostatic electrically heated drying cabinet temperature
3MPa；
After waiting until the device cools to room temperature, product is transferred in 200 mL beakers, with 45 MHz in ultrasonic cleaner
Frequency ultrasound is handled 20 minutes；
Gained solidliquid mixture is filtered by cloth funnel, after being washed with distilled water 3 times, then is washed repeatedly with absolute ethyl alcohol
It washs 3 times, obtains solid filter cake；
Filter cake is placed in constant temperature electric heating drying box, dry 6 h, then clay into power in the agate mortar at 90 DEG C,
It is spare.
Step 3：It is prepared by metatitanic acid cerium precursor
6 mL metatitanic acid isopropyls alcohol esters, 35 mL absolute ethyl alcohols, 13 mL acetone and 1.2 are separately added into 100 mL beakers
G directed agents AP-3, stir 20 min on magnetic stirring apparatus, as A liquid；
30 mL absolute ethyl alcohols, 3.6 g Surfactant OPs -3,500 mg macropores templates, 60 are added in 200 mL beakers
ML distilled water and 2.1 g cerous nitrates, stir 20 min, as B liquid on magnetic stirring apparatus；
A drops are added in B liquid during magnetic agitation and continue to stir 30 min, by mixed liquor in ultrasonic cleaning
It is ultrasonically treated 1 h with 45 MHz frequencies in device, it is spare.
Step 4：Hydrothermal synthesis Cerium titanate
Metatitanic acid cerium precursor is moved into the cup-like liner made of polytetrafluoroethylene material that volume is 200 mL, is covered
Lid is placed in stainless steel autoclave；
Autoclave is put in constant temperature electric heating drying box, constant temperature electric heating drying box temperature is risen to 220 ~ 240 DEG C,
Keep the temperature 72 h.In the process, it is not more than to control pressure in autoclave by regulating thermostatic electrically heated drying cabinet temperature
3MPa；
After waiting until the device cools to room temperature, product is transferred in 200 mL beakers, with 45 MHz in ultrasonic cleaner
Frequency ultrasound is handled 20 minutes；
Gained solidliquid mixture is filtered by cloth funnel, after being washed with distilled water 3 times, then is washed repeatedly with absolute ethyl alcohol
It washs 3 times, obtains solid filter cake；
Filter cake is placed in constant temperature electric heating drying box, dry 6 h, spare at 120 DEG C.
Step 5：Heat treatment
Filter cake is put into porcelain crucible and is placed in program-controlled cabinet-type electric furnace, with 10 DEG C/min heating rates by furnace temperature
1300 DEG C are risen to, in 5 h of this temperature calcination.It is taken out after electric furnace is cooled to room temperature, it is hollow that obtained macropore is ground in porcelain mortar
Cerium titanate microballoon.
Involved in the present embodiment to the rotating speed of magnetic stirring apparatus be 200 r/min.
Embodiment 4
A kind of preparation method of the hollow Cerium titanate microballoon of macropore, including following processing steps：
Step 1：Prepare template presoma
By 30 mL n-butanols, 19 mL of glucose solution of 3 mol/L, 5.6 g PEG 20000s, 1.5 mL 12
Alkyl trimethyl ammonium bromide and 0.5 g stabilizers SY-5 are added in 100 mL twoport round-bottomed flasks；
Flask is placed in precise temperature control electric heating packet, in flask center, interface installs spherical condensation tube, is cold with tap water
But medium, in another interface installation thermometric thermoelectricity of flask corner；By adjusting electric heating packet heating temperature to control solution temperature in flask
Degree is 60 DEG C, maintains the reflux for 50 min of time in this temperature, then cools to room temperature, spare.
Step 2：Hydrothermal synthesis macropore template
The template presoma of preparation is moved into the cup-like liner made of polytetrafluoroethylene material that volume is 100 mL,
It closes the lid, is placed in stainless steel autoclave；
Autoclave is put in constant temperature electric heating drying box, constant temperature electric heating drying box temperature is risen to 180 ~ 200 DEG C,
Keep the temperature 36 h.In the process, it is not more than to control pressure in autoclave by regulating thermostatic electrically heated drying cabinet temperature
3MPa；
After waiting until the device cools to room temperature, product is transferred in 200 mL beakers, with 45 MHz in ultrasonic cleaner
Frequency ultrasound is handled 20 minutes；
Gained solidliquid mixture is filtered by cloth funnel, after being washed with distilled water 3 times, then is washed repeatedly with absolute ethyl alcohol
It washs 3 times, obtains solid filter cake；
Filter cake is placed in constant temperature electric heating drying box, dry 6 h, then clay into power in the agate mortar at 90 DEG C,
It is spare.
Step 3：It is prepared by metatitanic acid cerium precursor
Be separately added into 100 mL beakers 5.2 mL metatitanic acid isopropyls alcohol esters, 30 mL absolute ethyl alcohols, 12 mL acetone and
1.25 g directed agents AP-3, stir 20 min, as A liquid on magnetic stirring apparatus；
30 mL absolute ethyl alcohols, 3.6 g Surfactant OPs -3,500 mg macropores templates, 50 are added in 200 mL beakers
ML distilled water and 1.5 g cerous nitrates, stir 20 min, as B liquid on magnetic stirring apparatus；
A drops are added in B liquid during magnetic agitation and continue to stir 30 min, by mixed liquor in ultrasonic cleaning
It is ultrasonically treated 1 h with 45 MHz frequencies in device, it is spare.
Step 4：Hydrothermal synthesis Cerium titanate
Metatitanic acid cerium precursor is moved into the cup-like liner made of polytetrafluoroethylene material that volume is 200 mL, is covered
Lid is placed in stainless steel autoclave；
Autoclave is put in constant temperature electric heating drying box, constant temperature electric heating drying box temperature is risen to 220 ~ 240 DEG C,
Keep the temperature 72 h.In the process, it is not more than to control pressure in autoclave by regulating thermostatic electrically heated drying cabinet temperature
3MPa；
After waiting until the device cools to room temperature, product is transferred in 200 mL beakers, with 45 MHz in ultrasonic cleaner
Frequency ultrasound is handled 20 minutes；
Gained solidliquid mixture is filtered by cloth funnel, after being washed with distilled water 3 times, then is washed repeatedly with absolute ethyl alcohol
It washs 3 times, obtains solid filter cake；
Filter cake is placed in constant temperature electric heating drying box, dry 6 h, spare at 120 DEG C.
Step 5：Heat treatment
Filter cake is put into porcelain crucible and is placed in program-controlled cabinet-type electric furnace, with 10 DEG C/min heating rates by furnace temperature
1200 DEG C are risen to, in 6 h of this temperature calcination.It is taken out after electric furnace is cooled to room temperature, it is hollow that obtained macropore is ground in porcelain mortar
Cerium titanate microballoon.
Involved in the present embodiment to the rotating speed of magnetic stirring apparatus be 200 r/min.
Embodiment 5
A kind of preparation method of the hollow Cerium titanate microballoon of macropore, including following processing steps：
Step 1：Prepare template presoma
By 40 mL n-butanols, 18 mL of glucose solution of 3 mol/L, 7.5 g PEG 20000s, 2.7mL dodecanes
Base trimethylammonium bromide and 1.2 g stabilizers SY-5 are added in 100 mL twoport round-bottomed flasks；
Flask is placed in precise temperature control electric heating packet, in flask center, interface installs spherical condensation tube, is cold with tap water
But medium, in another interface installation thermometric thermoelectricity of flask corner；By adjusting electric heating packet heating temperature to control solution temperature in flask
Degree is 60 DEG C, maintains the reflux for 50 min of time in this temperature, then cools to room temperature, spare.
Step 2：Hydrothermal synthesis macropore template
The template presoma of preparation is moved into the cup-like liner made of polytetrafluoroethylene material that volume is 100 mL,
It closes the lid, is placed in stainless steel autoclave；
Autoclave is put in constant temperature electric heating drying box, constant temperature electric heating drying box temperature is risen to 180 ~ 200 DEG C,
Keep the temperature 36 h.In the process, it is not more than to control pressure in autoclave by regulating thermostatic electrically heated drying cabinet temperature
3MPa；
After waiting until the device cools to room temperature, product is transferred in 200 mL beakers, with 45 MHz in ultrasonic cleaner
Frequency ultrasound is handled 20 minutes；
Gained solidliquid mixture is filtered by cloth funnel, after being washed with distilled water 3 times, then is washed repeatedly with absolute ethyl alcohol
It washs 3 times, obtains solid filter cake；
Filter cake is placed in constant temperature electric heating drying box, dry 6 h, then clay into power in the agate mortar at 90 DEG C,
It is spare.
Step 3：It is prepared by metatitanic acid cerium precursor
Be separately added into 100 mL beakers 6.3 mL metatitanic acid isopropyls alcohol esters, 35 mL absolute ethyl alcohols, 14 mL acetone and
1.3g directed agents AP-3, stir 20 min on magnetic stirring apparatus, as A liquid；
30 mL absolute ethyl alcohols, 3.6 g Surfactant OPs -3,500 mg macropores templates, 60 are added in 200 mL beakers
ML distilled water and 2.1 g cerous nitrates, stir 20 min, as B liquid on magnetic stirring apparatus；
A drops are added in B liquid during magnetic agitation and continue to stir 30 min, by mixed liquor in ultrasonic cleaning
It is ultrasonically treated 1 h with 45 MHz frequencies in device, it is spare.
Step 4：Hydrothermal synthesis Cerium titanate
Metatitanic acid cerium precursor is moved into the cup-like liner made of polytetrafluoroethylene material that volume is 200 mL, is covered
Lid is placed in stainless steel autoclave；
Autoclave is put in constant temperature electric heating drying box, constant temperature electric heating drying box temperature is risen to 220 ~ 240 DEG C,
Keep the temperature 72 h.In the process, it is not more than to control pressure in autoclave by regulating thermostatic electrically heated drying cabinet temperature
3MPa；
After waiting until the device cools to room temperature, product is transferred in 200 mL beakers, with 45 MHz in ultrasonic cleaner
Frequency ultrasound is handled 20 minutes；
Gained solidliquid mixture is filtered by cloth funnel, after being washed with distilled water 3 times, then is washed repeatedly with absolute ethyl alcohol
It washs 3 times, obtains solid filter cake；
Filter cake is placed in constant temperature electric heating drying box, dry 6 h, spare at 120 DEG C.
Step 5：Heat treatment
Filter cake is put into porcelain crucible and is placed in program-controlled cabinet-type electric furnace, with 10 DEG C/min heating rates by furnace temperature
1350 DEG C are risen to, in 3 h of this temperature calcination.It is taken out after electric furnace is cooled to room temperature, it is hollow that obtained macropore is ground in porcelain mortar
Cerium titanate microballoon.
Involved in the present embodiment to the rotating speed of magnetic stirring apparatus be 200 r/min.
Claims (4)
1. a kind of preparation method of the hollow Cerium titanate microballoon of macropore, which is characterized in that including following processing steps：
Step 1：Prepare template presoma；
Step 1.1：By 30 ~ 40 mL n-butanols, 18 ~ 25 mL of glucose solution of 3 mol/L, 5.6 ~ 7.5 g polyethylene glycol
20000,1.5 ~ 2.7 mL dodecyl trimethyl ammonium bromide and 0.5 ~ 1.2 g stabilizers SY-5 are added 100 mL twoport round bottoms and burn
In bottle；
Step 1.2：Flask is placed in precise temperature control electric heating packet, in flask center, interface installs spherical condensation tube, with tap water
For cooling medium, thermometric thermoelectricity corner is installed in another interface of flask；It is molten in flask to control by adjusting electric heating packet heating temperature
Liquid temperature is 60 DEG C, maintains the reflux for 50 min of time in this temperature, then cools to room temperature, and prepares template presoma, spare；
Step 2：Hydrothermal synthesis macropore template；
Step 2.1：The template presoma of preparation is moved into the cup-shaped made of polytetrafluoroethylene material that volume is 100 mL
It in lining, closes the lid, is placed in stainless steel autoclave；
Step 2.2：Autoclave is put in constant temperature electric heating drying box, constant temperature electric heating drying box temperature is risen to 180 ~ 200
DEG C, keep the temperature 36 h；
Step 2.3：After autoclave is cooled to room temperature, product is transferred in 200 mL beakers, in ultrasonic cleaner
It is middle to be ultrasonically treated 20 minutes；
Step 2.4：Gained solidliquid mixture is filtered by cloth funnel, after being washed with distilled water 3 times, then it is anti-with absolute ethyl alcohol
After backwashing is washed 3 times, and solid filter cake is obtained；
Step 2.5：Filter cake is placed in constant temperature electric heating drying box, dry 6 h, then wear into the agate mortar at 90 DEG C
Powder obtains macropore template, spare；
Step 3：It is prepared by metatitanic acid cerium precursor；
Step 3.1：Be separately added into 100 mL beakers 5.2 ~ 6.3 mL metatitanic acid isopropyls alcohol esters, 30 ~ 35 mL absolute ethyl alcohols,
12 ~ 14 mL acetone and 1.2 ~ 1.3 g directed agents AP-3, stir 20 min, as A liquid on magnetic stirring apparatus；
Step 3.2：30 mL absolute ethyl alcohols, 3.6 g Surfactant OPs -3, the big casements of 500 mg are added in 200 mL beakers
Plate, 50 ~ 60 mL distilled water and 1.5 ~ 2.1 g cerous nitrates, stir 20 min, as B liquid on magnetic stirring apparatus；
Step 3.3：A drops are added in B liquid during magnetic agitation and continue to stir 30 min, by mixed liquor in ultrasonic wave
It is ultrasonically treated 1 h in washer, obtains metatitanic acid cerium precursor, it is spare；
Step 4：Hydrothermal synthesis Cerium titanate；
Step 4.1：Metatitanic acid cerium precursor is moved into the cup-like liner made of polytetrafluoroethylene material that volume is 200 mL,
It closes the lid, is placed in stainless steel autoclave；
Step 4.2：Autoclave is put in constant temperature electric heating drying box, the temperature of constant temperature electric heating drying box is risen to 220 ~
240 DEG C, keep the temperature 72 h；In the process, pressure is controlled in autoclave not by regulating thermostatic electrically heated drying cabinet temperature
More than 3MPa；
Step 4.3：After autoclave is cooled to room temperature, product is transferred in 200 mL beakers, in ultrasonic cleaner
It is middle to be ultrasonically treated 20 minutes；
Step 4.4：Gained solidliquid mixture is filtered by cloth funnel, after being washed with distilled water 3 times, then it is anti-with absolute ethyl alcohol
After backwashing is washed 3 times, and solid filter cake is obtained；
Step 4.5：Filter cake is placed in constant temperature electric heating drying box, dry 6 h, spare at 120 DEG C；
Step 5：Heat treatment；
Filter cake is put into porcelain crucible and is placed in program-controlled cabinet-type electric furnace, is risen to furnace temperature with 10 DEG C/min heating rates
1200 ~ 1350 DEG C, in 3 ~ 6 h of this temperature calcination；It is taken out after electric furnace is cooled to room temperature, is ground in porcelain mortar and macropore is made
Hollow Cerium titanate microballoon.
2. a kind of preparation method of the hollow Cerium titanate microballoon of macropore according to claim 1, which is characterized in that the magnetic force
The rotating speed of blender is 200 r/min.
3. a kind of preparation method of the hollow Cerium titanate microballoon of macropore according to claim 1, which is characterized in that the step
In 2.2 insulating process, 3MPa is not more than to control pressure in autoclave by regulating thermostatic electrically heated drying cabinet temperature.
4. a kind of preparation method of the hollow Cerium titanate microballoon of macropore according to claim 1, which is characterized in that
The ultrasonic cleaner is ultrasonically treated with 45 MHz frequencies.
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| CN108246361B (en) * | 2018-01-08 | 2020-10-30 | 沈阳理工大学 | Method for preparing molecular sieve type titanium cerium oxide photocatalytic material |
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| CN1476929A (en) * | 2003-07-08 | 2004-02-25 | 浙江大学 | Denitration catalyst using CeTi2Ob as carrier and its preparation method |
| CN102502798A (en) * | 2011-11-09 | 2012-06-20 | 南京航空航天大学 | Preparation method for monodisperse barium titanate nanopowder |
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