CN106311240A - Preparation method of cobalt titanate-titanium dioxide composite nanomaterial of spherical hierarchical structure - Google Patents
Preparation method of cobalt titanate-titanium dioxide composite nanomaterial of spherical hierarchical structure Download PDFInfo
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- CN106311240A CN106311240A CN201610816525.1A CN201610816525A CN106311240A CN 106311240 A CN106311240 A CN 106311240A CN 201610816525 A CN201610816525 A CN 201610816525A CN 106311240 A CN106311240 A CN 106311240A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 39
- 239000010941 cobalt Substances 0.000 title claims abstract description 37
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 37
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000001816 cooling Methods 0.000 claims abstract description 16
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 230000008520 organization Effects 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000001354 calcination Methods 0.000 claims description 26
- GYUPBLLGIHQRGT-UHFFFAOYSA-N pentane-2,4-dione;titanium Chemical compound [Ti].CC(=O)CC(C)=O GYUPBLLGIHQRGT-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 230000004044 response Effects 0.000 claims description 3
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- NICYNNGYHJJJMJ-UHFFFAOYSA-N propan-2-one;titanium Chemical compound [Ti].CC(C)=O NICYNNGYHJJJMJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 14
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 239000002105 nanoparticle Substances 0.000 abstract description 9
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 2
- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical compound [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000005245 sintering Methods 0.000 abstract 1
- 238000004729 solvothermal method Methods 0.000 abstract 1
- 238000004659 sterilization and disinfection Methods 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000007146 photocatalysis Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000011175 product filtration Methods 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000000126 substance 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 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011941 photocatalyst Substances 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
- 241000196324 Embryophyta Species 0.000 description 1
- 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
- ILPIWPKVSGQOOJ-UHFFFAOYSA-N cobalt(2+) oxygen(2-) titanium(4+) Chemical compound [O--].[O--].[Ti+4].[Co++] ILPIWPKVSGQOOJ-UHFFFAOYSA-N 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
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- -1 insulant Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007769 metal 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 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
Classifications
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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
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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
- 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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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
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Abstract
The invention belongs to the field of inorganic nonmetallic materials and particularly relates to a preparation method of a cobalt titanate-titanium dioxide composite nanomaterial of a spherical hierarchical structure. The preparation method includes dissolving titanium acetylacetonate and cobalt dichloride in a methanol solution sufficiently prior to solvothermal reaction, filtering, washing, drying, roasting and cooling to obtain the cobalt titanate-titanium dioxide composite nanomaterial of the spherical hierarchical structure. The preparation method has the advantages that the preparation method is simple, convenient and easy to implement, high in product purity, low in preparation cost and low in sintering temperature, thereby being applied to actual large-scale industrial production easily; the size of an overall large sphere of the cobalt titanate-titanium dioxide composite nanomaterial ranges from 1 micrometer to 3 micrometers, the size of nanoparticles ranges from 100 nm to 200 nm, and the cobalt titanate-titanium dioxide composite nanomaterial is excellent in uniformity and dispersity and high in visible-light catalytic activity and has a promising application prospect in the fields such as dye wastewater and indoor harmful gas degradation and photocatalytic disinfection.
Description
Technical field
The invention belongs to the preparing technical field of Inorganic Non-metallic Materials, concretely relate to a kind of spherical hierarchical organization
The preparation method of cobalt titanate-titanium dioxide composite nano material.
Background technology
Photocatalysis technology is to solve environmental pollution and energy starved new technique, is the most increasingly closed by people
Note, the wherein core being developed into this new technique of function admirable photocatalyst.In numerous semiconductor light-catalysts two
Titanium oxide (TiO2) because of its stable chemical nature, the catalysis activity advantage such as high, nontoxic, cheap be considered as most to have exploitation latent
The catalysis material of matter.But TiO2Energy gap (about 3.2 eV) wider, the utilization ratio for solar energy is relatively low, in recent years
The research come shows that the method utilizing low energy gap width material compound with titanium dioxide is improve conductor photocatalysis activity one
Plant 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, insulant, dielectric material etc..Utilize cobalt titanate and titanium dioxide to be prepared as cobalt titanate-titanium dioxide to be combined
Nano material, thus improve photocatalytic activity.At present, the method for preparation cobalt titanate-titanium dioxide composite nano material is common has
Solid-phase synthesis, sol-gel process, chemical coprecipitation etc..But all there is various defects, such as solid phase in existing preparation method
Method needs higher calcining heat and Ball-milling Time, does not utilize energy-conserving and environment-protective；Sol-gel process preparation technology need to grow very much time
Between, presoma price used is higher；The diameter of particle that chemical coprecipitation prepares is relatively big, and product purity is the highest.In order to realize
Large-scale production, it is necessary to Development and Production low cost, cobalt titanate-titanium dioxide composite Nano material that simple to operate, manufacturing cycle is short
Preparation method for material.
Summary of the invention
It is contemplated that provide a kind of technique simple in place of overcoming the deficiencies in the prior art, purpose product yield is high, system
Standby low cost, the preparation method of spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material that product purity is high.
For reaching above-mentioned purpose, the present invention is realized in.
The preparation method of a kind of spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material, is by titanium acetylacetone
After fully dissolving in methanol with cobalt dichloride, carry out solvent thermal reaction, after filtering, washing, after drying, calcining cooling
Obtain purpose product.
As a kind of preferred version, the mol ratio of titanium acetylacetone of the present invention and cobalt dichloride is 2:1.Described acetyl
The molar concentration of acetone titanium is 0.01～0.1 mol/L.
Further, solvent thermal reaction temperature of the present invention is at 110～220 DEG C, and the response time is 6～48 hours.
Further, drying time of the present invention is 1～5 hour, and baking temperature is 60～150 DEG C, heating rate
It it is 2～10 DEG C/min.
Further, calcination time of the present invention is 2～6 hours, and calcining heat is 700～800 DEG C, and heat up speed
Rate is 2～20 DEG C/min.
The present invention utilizes solvent thermal-calcining two-step method, has prepared that spherical hierarchical organization cobalt titanate-titanium dioxide is compound to be 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,
Having higher production efficiency, synthesis cobalt titanate-titanium dioxide composite nano material is spherical hierarchical organization material, the chi of big ball
Very little is 1 ~ 3 μm.And big ball is to be assembled by substantial amounts of nanoparticle, and the size of nanoparticle is 100 ~ 200 nm.
(2) purpose product yield is high (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 hierarchical organization cobalt titanate-titanium dioxide composite nano material, its purity high (99.95%～
99.98%), impurity content is low, dispersibility and homogeneity good (being can be seen that by SEM figure).
(4) purpose product spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material that prepared by the present invention is used as light
Catalyst uses, and within 60 minutes, degradation rate can reach (98.5%～99.8%), has higher catalysis activity.
Accompanying drawing explanation
The invention will be further described with detailed description of the invention below in conjunction with the accompanying drawings.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 the spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material prepared by the present invention
Figure.
Fig. 2 is the SEM pattern of the spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material prepared by the present invention
Figure.
Fig. 3 is the SEM pattern of the spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material prepared by the present invention
Figure.
Fig. 4 is the SEM pattern of the spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material prepared by the present invention
Figure.
Fig. 5 is the X-ray diffraction of the spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material prepared by the present invention
Style figure.
Detailed description of the invention
After titanium acetylacetone and cobalt dichloride are fully dissolved in methanol by the present invention, (temperature exists to carry out solvent thermal reaction
110～220 DEG C, the time is 6～48 hours), filter, wash, be dried, calcine cooling after i.e. obtain purpose product (drying time be
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 process is.
(1) by titanium acetylacetone and cobalt dichloride according to certain molar ratio weighing after, put in methanol and fully dissolve.Will
The mixed solution obtained at a certain temperature, carries out solvent thermal reaction, solvent thermal reaction temperature at 110～220 DEG C, solvent thermal
Response time is 6～48 hours.
(2) solvent thermal reaction terminates, and after naturally cooling to room temperature, the product that reaction obtained filters, put into baking after washing
In case, programmed rate is 2～10 DEG C/min, under the conditions of 60～120 DEG C, is dried 1～5 hour.
(3) above-mentioned dried after, by obtained product directly in Muffle furnace calcine, Muffle furnace Program heat up liter
Temperature speed range is at 2～20 DEG C/min.Calcination time is 2～6 hours, and calcining heat is 700～800 DEG C.After natural cooling
I.e. prepare spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material.
(4) the spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material prepared by utilization is as photocatalyst
(0.1g/L), degrade the methyl orange solution of 10 mg/L.In photocatalysis experiment, light source used is 300W xenon lamp.Before irradiation, contain
The methyl orange solution of catalysis material stirs 30 minutes in the dark, carries out illumination after reaching adsorption equilibrium.Measure with spectrophotometric
Determine methyl orange dye concentration change.
See shown in Fig. 1～4, the spherical hierarchical organization cobalt titanate-titanium dioxide composite Nano material prepared by the present invention
Scanning electron microscope (SEM) figure that material is carried out, products obtained therefrom spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material, material
Good dispersion, big ball a size of 1 ~ 3 μm；The size of nanoparticle is 100 ~ 200 nm.Fig. 5 is the ball prepared by the present invention
The X-ray diffraction pattern figure of shape hierarchical organization cobalt titanate-titanium dioxide composite nano material, wherein cobalt titanate (CoTiO3)
PDF card number is 15-0866；Titanium dioxide (TiO2) PDF card number be 21-1276.
Embodiment 1.
Be the ratio of 2:1 by titanium acetylacetone and cobalt dichloride according to mol ratio, put into after precise methanol (12C,
99.95%) stirring and dissolving in, the molar concentration of titanium acetylacetone is 0.01 mol/L.The mixed solution obtained is carried out solvent thermal
Reaction, solvent thermal reaction temperature is at 220 DEG C, and the solvent thermal reaction time is 12 hours.After solvent thermal reaction terminates, natural cooling
To room temperature, putting in baking oven after product filtration washing reaction obtained, programmed rate 10 DEG C/min, at 120 DEG C of bars
It is dried 2 hours under part.Then being placed in Muffle furnace calcining, calcination time is 5 hours, and calcining heat is 700 DEG C, heating rate
It it is 10 DEG C/min.Spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material is i.e. obtained after natural cooling.The chi of big ball
Very little is 3 μm, and the size of nanoparticle is 100 nm, and the yield of its product is 99.0%.Product purity 99.95%, carbon impurity content
Less than 0.05%.In the experiment of photocatalysis evaluation catalysis activity, the degradation rate of 60 minutes is 98.5%.
Embodiment 2.
Be the ratio of 2:1 by titanium acetylacetone and cobalt dichloride according to mol ratio, put into after precise methanol (12C,
99.95%) stirring and dissolving in, the molar concentration of titanium acetylacetone is 0.02 mol/L.The mixed solution obtained is carried out solvent thermal
Reaction, solvent thermal reaction temperature is at 110 DEG C, and the solvent thermal reaction time is 48 hours.After solvent thermal reaction terminates, natural cooling
To room temperature, putting in baking oven after product filtration washing reaction obtained, programmed rate 10 DEG C/min, at 60 DEG C of bars
It is dried 5 hours under part.Then being placed in Muffle furnace calcining, calcination time is 6 hours, and calcining heat is 800 DEG C, heating rate
It it is 20 DEG C/min.Spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material is i.e. obtained after natural cooling.The chi of big ball
Very little is 3 μm, and the size of nanoparticle is 200 nm, and the yield of its product is 99.6%.Product purity 99.96%, carbon impurity content
Less than 0.04%.In the experiment of photocatalysis evaluation catalysis activity, the degradation rate of 60 minutes is 99.2%.
Embodiment 3.
Be the ratio of 2:1 by titanium acetylacetone and cobalt dichloride according to mol ratio, put into after precise methanol (12C,
99.95%) stirring and dissolving in, the molar concentration of titanium acetylacetone is 0.03 mol/L.The mixed solution obtained is carried out solvent thermal
Reaction, solvent thermal reaction temperature is at 220 DEG C, and the solvent thermal reaction time is 10 hours.After solvent thermal reaction terminates, natural cooling
To room temperature, putting in baking oven after product filtration washing reaction obtained, programmed rate 10 DEG C/min, at 100 DEG C of bars
It is dried 2 hours under part.Then being placed in Muffle furnace calcining, calcination time is 6 hours, and calcining heat is 700 DEG C, heating rate
It it is 10 DEG C/min.Spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material is i.e. obtained after natural cooling.The chi of big ball
Very little is 2 μm, and the size of nanoparticle is 150 nm, and the yield of its product is 99.8%.Product purity 99.97%, carbon impurity content
Less than 0.03%.In the experiment of photocatalysis evaluation catalysis activity, the degradation rate of 60 minutes is 99.5%.
Embodiment 4.
Be the ratio of 2:1 by titanium acetylacetone and cobalt dichloride according to mol ratio, put into after precise methanol (12C,
99.95%) stirring and dissolving in, the molar concentration of titanium acetylacetone is 0.05 mol/L.The mixed solution obtained is carried out solvent thermal
Reaction, solvent thermal reaction temperature is at 220 DEG C, and the solvent thermal reaction time is 12 hours.After solvent thermal reaction terminates, natural cooling
To room temperature, putting in baking oven after product filtration washing reaction obtained, programmed rate 10 DEG C/min, at 110 DEG C of bars
It is dried 3 hours under part.Then being placed in Muffle furnace calcining, calcination time is 2 hours, and calcining heat is 800 DEG C, heating rate
It it is 20 DEG C/min.Spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material is i.e. obtained after natural cooling.The chi of big ball
Very little is 1.5 μm, and the size of nanoparticle is 100 nm, and the yield of its product is 99.6%.Product purity 99.98%, carbon impurity contains
Amount is less than 0.02%.In the experiment of photocatalysis evaluation catalysis activity, the degradation rate of 60 minutes is 99.8%.
Embodiment 5.
Be the ratio of 2:1 by titanium acetylacetone and cobalt dichloride according to mol ratio, put into after precise methanol (12C,
99.95%) stirring and dissolving in, the molar concentration of titanium acetylacetone is 0.1 mol/L.The mixed solution obtained is carried out solvent thermal
Reaction, solvent thermal reaction temperature is at 220 DEG C, and the solvent thermal reaction time is 12 hours.After solvent thermal reaction terminates, natural cooling
To room temperature, putting in baking oven after product filtration washing reaction obtained, programmed rate 10 DEG C/min, at 120 DEG C of bars
It is dried 5 hours under part.Then being placed in Muffle furnace calcining, calcination time is 6 hours, and calcining heat is 800 DEG C, heating rate
It it is 15 DEG C/min.Spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material is i.e. obtained after natural cooling.The chi of big ball
Very little is 3 μm, and the size of nanoparticle is 150 nm, and the yield of its product is 99.2%.Product purity 99.95%, carbon impurity content
Less than 0.05%.In the experiment of photocatalysis evaluation catalysis activity, the degradation rate of 60 minutes is 98.5%.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, that is made any repaiies
Change, equivalent, improvement etc., should be included within the scope of the present invention.
Claims (5)
1. the preparation method of spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material, it is characterised in that: by acetyl
After acetone titanium and cobalt dichloride fully dissolve in methanol, carry out solvent thermal reaction, after filtering, washing, drying, calcining
Purpose product is i.e. obtained after cooling.
The preparation side of a kind of spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material the most according to claim 1
Method, it is characterised in that: the mol ratio of described titanium acetylacetone and cobalt dichloride is 2:1；The molar concentration of described titanium acetylacetone
It is 0.01～0.1 mol/L.
3. according to arbitrary described one spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material of claim 1～2
Preparation method, it is characterised in that: described solvent thermal reaction temperature is at 110～220 DEG C, and the response time is 6～48 hours.
The preparation side of a kind of spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material the most according to claim 3
Method, it is characterised in that: described drying time is 1～5 hour, and baking temperature is 60～120 DEG C, heating rate is 2～10 DEG C/
Minute.
The preparation side of a kind of spherical hierarchical organization cobalt titanate-titanium dioxide composite nano material the most according to claim 4
Method, it is characterised in that: described calcination time is 2～6 hours, and calcining heat is 700～800 DEG C, and heating rate is 2～20
DEG C/min.
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Cited By (3)
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| CN107293724A (en) * | 2017-07-17 | 2017-10-24 | 中南大学 | A kind of cobalt titanate/titanium dioxide/cobalt@carbon composites and preparation method thereof and it is used as the application of sodium ion negative material |
| CN110790348A (en) * | 2019-11-21 | 2020-02-14 | 齐齐哈尔大学 | Preparation method and application of cobalt titanate-titanium dioxide composite catalyst electrode |
| CN114100613A (en) * | 2021-11-23 | 2022-03-01 | 哈尔滨工业大学（深圳） | Use of cobalt titanate materials and catalyst compositions |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107293724A (en) * | 2017-07-17 | 2017-10-24 | 中南大学 | A kind of cobalt titanate/titanium dioxide/cobalt@carbon composites and preparation method thereof and it is used as the application of sodium ion negative material |
| CN107293724B (en) * | 2017-07-17 | 2019-11-12 | 中南大学 | A kind of cobalt titanate/titanium dioxide/cobalt@carbon composite and preparation method thereof and application as sodium ion negative electrode material |
| CN110790348A (en) * | 2019-11-21 | 2020-02-14 | 齐齐哈尔大学 | Preparation method and application of cobalt titanate-titanium dioxide composite catalyst electrode |
| CN114100613A (en) * | 2021-11-23 | 2022-03-01 | 哈尔滨工业大学（深圳） | Use of cobalt titanate materials and catalyst compositions |
| CN114100613B (en) * | 2021-11-23 | 2024-03-26 | 哈尔滨工业大学（深圳） | Use of cobalt titanate material and catalyst composition |
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