CN106311240B - A kind of preparation method of spherical shape hierarchical organization cobalt titanate-titanium dioxide composite nano material - Google Patents
A kind of preparation method of spherical shape hierarchical organization cobalt titanate-titanium dioxide composite nano material Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 42
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 239000010941 cobalt Substances 0.000 title claims abstract description 39
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 39
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 230000008520 organization Effects 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000001354 calcination Methods 0.000 claims abstract description 34
- GYUPBLLGIHQRGT-UHFFFAOYSA-N pentane-2,4-dione;titanium Chemical compound [Ti].CC(=O)CC(C)=O GYUPBLLGIHQRGT-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims abstract description 19
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 15
- 230000001699 photocatalysis Effects 0.000 claims abstract description 15
- 239000002105 nanoparticle Substances 0.000 claims abstract description 14
- 238000007146 photocatalysis Methods 0.000 claims abstract description 14
- 230000015556 catabolic process Effects 0.000 claims abstract description 12
- 238000006731 degradation reaction Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 12
- 238000002474 experimental method Methods 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 6
- 238000011156 evaluation Methods 0.000 claims description 6
- NICYNNGYHJJJMJ-UHFFFAOYSA-N propan-2-one;titanium Chemical compound [Ti].CC(C)=O NICYNNGYHJJJMJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 2
- 238000011026 diafiltration Methods 0.000 claims 5
- 238000000034 method Methods 0.000 abstract description 7
- 238000001035 drying Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000007769 metal material Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000010919 dye waste Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 238000005245 sintering Methods 0.000 abstract 1
- 238000004659 sterilization and disinfection Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 22
- 239000000463 material Substances 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000011175 product filtration Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- LFSBSHDDAGNCTM-UHFFFAOYSA-N cobalt(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Co+2] LFSBSHDDAGNCTM-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 229910019096 CoTiO3 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- ILPIWPKVSGQOOJ-UHFFFAOYSA-N cobalt(2+) oxygen(2-) titanium(4+) Chemical compound [O--].[O--].[Ti+4].[Co++] ILPIWPKVSGQOOJ-UHFFFAOYSA-N 0.000 description 2
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001048 orange dye Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention belongs to inorganic non-metallic material preparation fields, more particularly to a kind of spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material preparation method, first by titanium acetylacetone and cobaltous dichloride in methanol solution after completely dissolution, carry out solvent thermal reaction, after being filtered, washed, up to spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material after drying, calcining are cooling.Present invention process is simple and easy to do, product purity is high, preparation cost is low, and the size of the whole big ball of products obtained therefrom is 1 ~ 3 μm, and the size of nanoparticle is 100 ~ 200 nm.And homogeneity, the dispersibility of product are all fine, and the sintering temperature of production technology is low, are readily applied to industrial practical large-scale production.Spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material visible light catalysis activity with higher prepared by the present invention, in degradation of dye waste water and indoor harmful gas, the fields such as photocatalysis disinfection are with a wide range of applications.
Description
Technical field
The invention belongs to the preparation technical fields of inorganic non-metallic material, concretely relate to a kind of spherical hierarchical organization
Cobalt titanate-titanium dioxide composite nano material preparation method.
Background technique
Photocatalysis technology is the new technology for solving environmental pollution and energy shortage, in recent years increasingly by the pass of people
It infuses, wherein the core for being developed into this new technology of function admirable photochemical catalyst.Two in numerous semiconductor light-catalysts
Titanium oxide (TiO2) because the advantages that its chemical property is stable, catalytic activity is high, nontoxic, cheap is considered as most having exploitation to dive
The catalysis material of matter.But TiO2Forbidden bandwidth (about 3.2 eV) it is wider, it is lower for the utilization efficiency of solar energy, in recent years
It is coming research shows that being to improve conductor photocatalysis active one using low energy gap width material and the compound method of titanium dioxide
Kind effective way.
Cobalt titanate (CoTiO3) it is a kind of important fine inorganic chemicals material, it is widely used in light-sensitive material, wet sensitive material
Material, heat proof material, insulating materials, dielectric material etc..It is compound that with titanium dioxide cobalt titanate-titanium dioxide is prepared into using cobalt titanate
Nano material, to improve photocatalytic activity.Currently, preparing, cobalt titanate-titanium dioxide composite nano material method is common to be had
Solid-phase synthesis, sol-gel method, chemical coprecipitation etc..But existing preparation method all haves the defects that various, such as solid phase
Method needs higher calcination temperature and Ball-milling Time, does not utilize energy conservation and environmental protection；Sol-gel method preparation process need to grow very much when
Between, presoma price used is higher；Diameter of particle made from chemical coprecipitation is larger, and product purity is not high.In order to realize
Large-scale production, it is necessary to development and production cobalt titanate at low cost, easy to operate, short preparation period-titanium dioxide composite Nano material
Preparation method for material.
Summary of the invention
The present invention is directed to provide a kind of simple process in place of overcome the deficiencies in the prior art, purpose product high income, system
Standby at low cost, the preparation method of the high spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material of product purity.
In order to achieve the above objectives, the invention is realized in this way.
A kind of preparation method of spherical shape hierarchical organization cobalt titanate-titanium dioxide composite nano material, is by titanium acetylacetone
In methyl alcohol after completely dissolution with cobaltous dichloride, solvent thermal reaction is carried out, after being filtered, washed, after drying, calcining are cooling
Up to purpose product.
As a preferred embodiment, the molar ratio of titanium acetylacetone and cobaltous dichloride of the present invention is 2:1.The acetyl
The molar concentration of acetone titanium is 0.01~0.1 mol/L.
Further, for solvent thermal reaction temperature of the present invention at 110~220 DEG C, the reaction time is 6~48 hours.
Further, drying time of the present invention is 1~5 hour, and drying temperature is 60~150 DEG C, heating rate
It is 2~10 DEG C/min.
Further, calcination time of the present invention is 2~6 hours, and calcination temperature is 700~800 DEG C, heating speed
Rate is 2~20 DEG C/min.
The present invention utilizes solvent heat-calcining two-step method, has prepared spherical hierarchical organization cobalt titanate-titanium dioxide is compound and received
Rice material.
Compared with prior art, the present invention has following features.
(1) preparation cost of spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material is low, easy to control,
Production efficiency with higher, synthesis cobalt titanate-titanium dioxide composite nano material is spherical hierarchical organization material, the ruler of big ball
Very little is 1 ~ 3 μm.And big ball is assembled by a large amount of nanoparticle, and the size of nanoparticle is 100 ~ 200 nm.
(2) purpose product high income (99.0%~99.9%) can meet industrial application to spherical hierarchical organization metatitanic acid
The requirement of cobalt-titanium dioxide composite nano material product.
(3) purpose product spherical shape hierarchical organization cobalt titanate-titanium dioxide composite nano material, purity is high (99.95%~
99.98%), impurity content is low, and dispersibility and homogeneity are good (can be seen that by SEM figure).
(4) purpose product spherical shape hierarchical organization cobalt titanate-titanium dioxide composite nano material prepared by the present invention is used as light
Catalyst uses, and degradation rate can reach (98.5%~99.8%) within 60 minutes, catalytic activity with higher.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and specific embodiments.Protection scope of the present invention not only office
It is limited to the statement of following content.
Fig. 1 is the SEM pattern of spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material prepared by the present invention
Figure.
Fig. 2 is the SEM pattern of spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material prepared by the present invention
Figure.
Fig. 3 is the SEM pattern of spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material prepared by the present invention
Figure.
Fig. 4 is the SEM pattern of spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material prepared by the present invention
Figure.
Fig. 5 is the X-ray diffraction of spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material prepared by the present invention
Style figure.
Specific embodiment
In methyl alcohol after completely dissolution by titanium acetylacetone and cobaltous dichloride, carrying out solvent thermal reaction, (temperature exists the present invention
110~220 DEG C, the time is 6~48 hours), be filtered, washed, dry, calcine it is cooling after (drying time is purpose product to obtain the final product
1~5 hour, temperature was 60~120 DEG C, and heating rate is 2~10 DEG C/min.Calcination time is 2~6 hours, and temperature is
600~700 DEG C, heating rate is 2~20 DEG C/min).
Its preparation step is.
(1) it after by titanium acetylacetone and cobaltous dichloride according to certain molar ratio weighing, is put into methanol and sufficiently dissolves.It will
Obtained mixed solution at a certain temperature, carries out solvent thermal reaction, and solvent thermal reaction temperature is at 110~220 DEG C, solvent heat
Reaction time is 6~48 hours.
(2) solvent thermal reaction terminates, and after cooled to room temperature, is put into baking after the product that reaction obtains is filtered, washed
In case, programmed rate is 2~10 DEG C/min, 1~5 hour dry under the conditions of 60~120 DEG C.
(3) it is above-mentioned it is dried after, obtained product is directly calcined in Muffle furnace, the liter of temperature programming in Muffle furnace
Warm speed range is in 2~20 DEG C/min.Calcination time is 2~6 hours, and calcination temperature is 700~800 DEG C.After natural cooling
Obtain spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material.
(4) using prepared spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material as photochemical catalyst
(0.1g/L), the methyl orange solution for 10 mg/L that degrade.Light source used is 300W xenon lamp in photocatalysis experiment.Before irradiation, contain
The methyl orange solution of catalysis material stirs 30 minutes in the dark, carries out illumination after reaching adsorption equilibrium.It is measured with spectrophotometric
Determine the variation of methyl orange dye concentration.
Referring to shown in Fig. 1~4, for spherical hierarchical organization cobalt titanate-titanium dioxide composite Nano material prepared by the present invention
Expect scanning electron microscope (SEM) figure carried out, products obtained therefrom spherical shape hierarchical organization cobalt titanate-titanium dioxide composite nano material, material
Good dispersion, big ball is having a size of 1 ~ 3 μm；The size of nanoparticle is 100 ~ 200 nm.Fig. 5 is ball prepared by the present invention
Shape hierarchical organization cobalt titanate-titanium dioxide composite nano material X-ray diffraction pattern figure, wherein cobalt titanate (CoTiO3)
PDF card number is 15-0866；Titanium dioxide (TiO2) PDF card number be 21-1276.
Embodiment 1.
The ratio for being 2:1 according to molar ratio by titanium acetylacetone and cobaltous dichloride, be put into after precise methanol (12C,
99.95%) stirring and dissolving in, the molar concentration of titanium acetylacetone are 0.01 mol/L.Obtained mixed solution is subjected to solvent heat
Reaction, for solvent thermal reaction temperature at 220 DEG C, the solvent thermal reaction time is 12 hours.After solvent thermal reaction, natural cooling
To room temperature, will be put into baking oven after product filtration washing that reaction obtains, 10 DEG C/min of programmed rate, in 120 DEG C of items
It is 2 hours dry under part.Then it is placed in Muffle furnace and calcines, calcination time is 5 hours, and calcination temperature is 700 DEG C, heating rate
It is 10 DEG C/min.Spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material is obtained after natural cooling.The ruler of big ball
Very little is 3 μm, and the size of nanoparticle is 100 nm, and the yield of product is 99.0%.Product purity 99.95%, impurity carbon content
Less than 0.05%.In the experiment of photocatalysis evaluation catalytic activity, 60 minutes degradation rates are 98.5%.
Embodiment 2.
The ratio for being 2:1 according to molar ratio by titanium acetylacetone and cobaltous dichloride, be put into after precise methanol (12C,
99.95%) stirring and dissolving in, the molar concentration of titanium acetylacetone are 0.02 mol/L.Obtained mixed solution is subjected to solvent heat
Reaction, for solvent thermal reaction temperature at 110 DEG C, the solvent thermal reaction time is 48 hours.After solvent thermal reaction, natural cooling
To room temperature, will be put into baking oven after product filtration washing that reaction obtains, 10 DEG C/min of programmed rate, in 60 DEG C of items
It is 5 hours dry under part.Then it is placed in Muffle furnace and calcines, calcination time is 6 hours, and calcination temperature is 800 DEG C, heating rate
It is 20 DEG C/min.Spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material is obtained after natural cooling.The ruler of big ball
Very little is 3 μm, and the size of nanoparticle is 200 nm, and the yield of product is 99.6%.Product purity 99.96%, impurity carbon content
Less than 0.04%.In the experiment of photocatalysis evaluation catalytic activity, 60 minutes degradation rates are 99.2%.
Embodiment 3.
The ratio for being 2:1 according to molar ratio by titanium acetylacetone and cobaltous dichloride, be put into after precise methanol (12C,
99.95%) stirring and dissolving in, the molar concentration of titanium acetylacetone are 0.03 mol/L.Obtained mixed solution is subjected to solvent heat
Reaction, for solvent thermal reaction temperature at 220 DEG C, the solvent thermal reaction time is 10 hours.After solvent thermal reaction, natural cooling
To room temperature, will be put into baking oven after product filtration washing that reaction obtains, 10 DEG C/min of programmed rate, in 100 DEG C of items
It is 2 hours dry under part.Then it is placed in Muffle furnace and calcines, calcination time is 6 hours, and calcination temperature is 700 DEG C, heating rate
It is 10 DEG C/min.Spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material is obtained after natural cooling.The ruler of big ball
Very little is 2 μm, and the size of nanoparticle is 150 nm, and the yield of product is 99.8%.Product purity 99.97%, impurity carbon content
Less than 0.03%.In the experiment of photocatalysis evaluation catalytic activity, 60 minutes degradation rates are 99.5%.
Embodiment 4.
The ratio for being 2:1 according to molar ratio by titanium acetylacetone and cobaltous dichloride, be put into after precise methanol (12C,
99.95%) stirring and dissolving in, the molar concentration of titanium acetylacetone are 0.05 mol/L.Obtained mixed solution is subjected to solvent heat
Reaction, for solvent thermal reaction temperature at 220 DEG C, the solvent thermal reaction time is 12 hours.After solvent thermal reaction, natural cooling
To room temperature, will be put into baking oven after product filtration washing that reaction obtains, 10 DEG C/min of programmed rate, in 110 DEG C of items
It is 3 hours dry under part.Then it is placed in Muffle furnace and calcines, calcination time is 2 hours, and calcination temperature is 800 DEG C, heating rate
It is 20 DEG C/min.Spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material is obtained after natural cooling.The ruler of big ball
Very little is 1.5 μm, and the size of nanoparticle is 100 nm, and the yield of product is 99.6%.Product purity 99.98%, carbon impurity contains
Amount is less than 0.02%.In the experiment of photocatalysis evaluation catalytic activity, 60 minutes degradation rates are 99.8%.
Embodiment 5.
The ratio for being 2:1 according to molar ratio by titanium acetylacetone and cobaltous dichloride, be put into after precise methanol (12C,
99.95%) stirring and dissolving in, the molar concentration of titanium acetylacetone are 0.1 mol/L.Obtained mixed solution is subjected to solvent heat
Reaction, for solvent thermal reaction temperature at 220 DEG C, the solvent thermal reaction time is 12 hours.After solvent thermal reaction, natural cooling
To room temperature, will be put into baking oven after product filtration washing that reaction obtains, 10 DEG C/min of programmed rate, in 120 DEG C of items
It is 5 hours dry under part.Then it is placed in Muffle furnace and calcines, calcination time is 6 hours, and calcination temperature is 800 DEG C, heating rate
It is 15 DEG C/min.Spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material is obtained after natural cooling.The ruler of big ball
Very little is 3 μm, and the size of nanoparticle is 150 nm, and the yield of product is 99.2%.Product purity 99.95%, impurity carbon content
Less than 0.05%.In the experiment of photocatalysis evaluation catalytic activity, 60 minutes degradation rates are 98.5%.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (5)
1. a kind of preparation method of spherical shape hierarchical organization cobalt titanate-titanium dioxide composite nano material, it is characterised in that: by acetyl
The ratio that acetone titanium and cobaltous dichloride are 2:1 according to molar ratio is put into stirring and dissolving in methanol, titanium acetylacetone after precise
Molar concentration be 0.01 mol/L；By obtained mixed solution carry out solvent thermal reaction, solvent thermal reaction temperature at 220 DEG C,
The solvent thermal reaction time is 12 hours；After solvent thermal reaction, the product that reaction obtains is crossed diafiltration by cooled to room temperature
It is put into baking oven after washing, 10 DEG C/min of programmed rate, it is 2 hours dry under the conditions of 120 DEG C；Then it is placed on Muffle furnace
Middle calcining, calcination time are 5 hours, and calcination temperature is 700 DEG C, and heating rate is 10 DEG C/min；It is obtained after natural cooling
Spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material；The size of big ball is 3 μm, and the size of nanoparticle is
100nm, the yield of product are 99.0%；Product purity 99.95%, impurity carbon content is less than 0.05%；It evaluates and is catalyzed in photocatalysis
In active experiment, 60 minutes degradation rates are 98.5%.
2. a kind of preparation method of spherical shape hierarchical organization cobalt titanate-titanium dioxide composite nano material, it is characterised in that: by acetyl
The ratio that acetone titanium and cobaltous dichloride are 2:1 according to molar ratio is put into stirring and dissolving in methanol, titanium acetylacetone after precise
Molar concentration be 0.02 mol/L；By obtained mixed solution carry out solvent thermal reaction, solvent thermal reaction temperature at 110 DEG C,
The solvent thermal reaction time is 48 hours；After solvent thermal reaction, the product that reaction obtains is crossed diafiltration by cooled to room temperature
It is put into baking oven after washing, 10 DEG C/min of programmed rate, it is 5 hours dry under the conditions of 60 DEG C；Then it is placed on Muffle furnace
Middle calcining, calcination time are 6 hours, and calcination temperature is 800 DEG C, and heating rate is 20 DEG C/min；It is obtained after natural cooling
Spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material；The size of big ball is 3 μm, and the size of nanoparticle is
200nm, the yield of product are 99.6%；Product purity 99.96%, impurity carbon content is less than 0.04%；It evaluates and is catalyzed in photocatalysis
In active experiment, 60 minutes degradation rates are 99.2%.
3. a kind of preparation method of spherical shape hierarchical organization cobalt titanate-titanium dioxide composite nano material, it is characterised in that: by acetyl
The ratio that acetone titanium and cobaltous dichloride are 2:1 according to molar ratio is put into stirring and dissolving in methanol, titanium acetylacetone after precise
Molar concentration be 0.03 mol/L；By obtained mixed solution carry out solvent thermal reaction, solvent thermal reaction temperature at 220 DEG C,
The solvent thermal reaction time is 10 hours；After solvent thermal reaction, the product that reaction obtains is crossed diafiltration by cooled to room temperature
It is put into baking oven after washing, 10 DEG C/min of programmed rate, it is 2 hours dry under the conditions of 100 DEG C；Then it is placed on Muffle furnace
Middle calcining, calcination time are 6 hours, and calcination temperature is 700 DEG C, and heating rate is 10 DEG C/min；It is obtained after natural cooling
Spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material；The size of big ball is 2 μm, and the size of nanoparticle is
150nm, the yield of product are 99.8%；Product purity 99.97%, impurity carbon content is less than 0.03%；It evaluates and is catalyzed in photocatalysis
In active experiment, 60 minutes degradation rates are 99.5%.
4. a kind of preparation method of spherical shape hierarchical organization cobalt titanate-titanium dioxide composite nano material, it is characterised in that: by acetyl
The ratio that acetone titanium and cobaltous dichloride are 2:1 according to molar ratio is put into stirring and dissolving in methanol, titanium acetylacetone after precise
Molar concentration be 0.05 mol/L；By obtained mixed solution carry out solvent thermal reaction, solvent thermal reaction temperature at 220 DEG C,
The solvent thermal reaction time is 12 hours；After solvent thermal reaction, the product that reaction obtains is crossed diafiltration by cooled to room temperature
It is put into baking oven after washing, 10 DEG C/min of programmed rate, it is 3 hours dry under the conditions of 110 DEG C；Then it is placed on Muffle furnace
Middle calcining, calcination time are 2 hours, and calcination temperature is 800 DEG C, and heating rate is 20 DEG C/min；It is obtained after natural cooling
Spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material；The size of big ball is 1.5 μm, and the size of nanoparticle is
100 nm, the yield of product are 99.6%；Product purity 99.98%, impurity carbon content is less than 0.02%；It is urged in photocatalysis evaluation
Change in active experiment, 60 minutes degradation rates are 99.8%.
5. a kind of preparation method of spherical shape hierarchical organization cobalt titanate-titanium dioxide composite nano material, it is characterised in that: by acetyl
The ratio that acetone titanium and cobaltous dichloride are 2:1 according to molar ratio is put into stirring and dissolving in methanol, titanium acetylacetone after precise
Molar concentration be 0.1 mol/L；By obtained mixed solution carry out solvent thermal reaction, solvent thermal reaction temperature at 220 DEG C,
The solvent thermal reaction time is 12 hours；After solvent thermal reaction, the product that reaction obtains is crossed diafiltration by cooled to room temperature
It is put into baking oven after washing, 10 DEG C/min of programmed rate, it is 5 hours dry under the conditions of 120 DEG C；Then it is placed on Muffle furnace
Middle calcining, calcination time are 6 hours, and calcination temperature is 800 DEG C, and heating rate is 15 DEG C/min；It is obtained after natural cooling
Spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material；The size of big ball is 3 μm, and the size of nanoparticle is
150nm, the yield of product are 99.2%；Product purity 99.95%, impurity carbon content is less than 0.05%；It evaluates and is catalyzed in photocatalysis
In active experiment, 60 minutes degradation rates are 98.5%.
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| CN105047904A (en) * | 2015-06-17 | 2015-11-11 | 中国矿业大学 | Preparation method and application of titanium-cobalt spinel |
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| CN102086047A (en) * | 2011-01-12 | 2011-06-08 | 宣城晶瑞新材料有限公司 | Titanium dioxide powder with ultrahigh water dispersion and high photocatalytic activity and preparation method thereof |
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