CN105731535B - A kind of preparation method of Zinc oxide/titanium dioxide composite nano materials - Google Patents
A kind of preparation method of Zinc oxide/titanium dioxide composite nano materials Download PDFInfo
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- CN105731535B CN105731535B CN201610240700.7A CN201610240700A CN105731535B CN 105731535 B CN105731535 B CN 105731535B CN 201610240700 A CN201610240700 A CN 201610240700A CN 105731535 B CN105731535 B CN 105731535B
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- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/08—Drying; Calcining ; After treatment of titanium oxide
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
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- C01P2006/80—Compositional purity
Abstract
The invention discloses a kind of preparation method of Zinc oxide/titanium dioxide composite nano materials, comprise the following steps：Step 1, a certain amount of titania powder is taken to be dispersed in water, then toward the desired amount of soluble zinc salt and hexamethylenetetramine is added in solution, stirring obtains dispersion soln；Step 2, the dispersion soln of heating stepses 1 while stirring, makes it react 10~80min at 60~95 DEG C of temperature；Step 3, by the reacted sediment of step 2 by filtering, cleaning and drying process.The preparation method of the present invention can realize the high-volume synthesis of one-dimentional structure Zinc oxide/titanium dioxide composite nano materials, and it uses directly synthesis in aqueous under normal pressure, and not only reaction condition is gentle, and energy consumption is low, and cost is low and yield is high；Obtained product has the advantages that big specific surface area, good dispersion and crystallinity are high.
Description
Technical field
The present invention relates to a kind of preparation method of Zinc oxide/titanium dioxide composite nano materials, belong to composite nano materials
Preparation field.
Background technology
In numerous conductor oxidates, zinc oxide (ZnO) is a kind of important direct band-gap semicondictor, with wider
Band gap (3.37eV) and higher exciton bind energy (60meV), at room temperature i.e. can observe very strong excitonic luminescence.Especially
It is that zinc oxide is non-toxic, ambient stable and compatibility are good, cheap, and nano structure of zinc oxide is easily prepared.Zinc oxide
These excellent performances, make its nano material have been widely used for various fields, such as catalysis material, photovoltaic material, sensing
Device, piezoelectric, ultraviolet light detection, light emitting diode and nano laser etc..
Titanium dioxide (TiO2) identical with the band gap of zinc oxide, equally with good environment and bio-compatibility.It is many
Report also confirms that coupling and coordinative role due to titanium dioxide and zinc oxide, can improve answering for light induced electron and photohole
Close probability.Therefore Zinc oxide/titanium dioxide composite nanostructure can not only improve the performance of material, and with environment and biology
The good advantage of compatibility, has broad application prospects in photovoltaic material, catalysis material, self-cleaning material etc..
Compared to Zinc oxide nanoparticle, more preferably, electronics is in one-dimension zinc oxide for one-dimensional zinc oxide nanometer material crystallinity
With higher diffusion velocity and diffusion length, so that significantly reduce the compound of light induced electron and photohole, it is one-dimensional in addition
The more uniform rule in space between nano material, contributes to gas and liquid transporting in these spaces.So as to further
Improve its performance in solar cell, photocatalytic applications.
At present, the method for preparing the Zinc oxide/titanium dioxide with one-dimensional nano structure is concentrated mainly on nano-wire array,
Using liquid phase method in the zinc oxide nanowire Surface coating layer of titanium dioxide nano particle grown.These method and steps are numerous
Trivial, cost is high, yield poorly.And the report of direct synthesizing zinc oxide and titanium dioxide composite nano material is also seldom in the solution,
Wherein more representativeness is that patent of invention CN 103803663A disclose a kind of Zinc oxide/titanium dioxide composite nano materials
Prepare, prepared using high pressure hydro-thermal method and obtained granular mixture.Although this method yield has been compared larger with other method
Improve, but the hyperbaric environment (120~180 atmospheric pressure) used is high to equipment requirement, and the reaction time is also up to 4~10 small
When.Therefore large batch of one-dimension zinc oxide nano wire is directly synthesized under a kind of normal pressure in the solution and titanium dioxide granule is combined and received
The exploitation of rice material is necessary.
The content of the invention
Goal of the invention：The technical problems to be solved by the invention are to provide Zinc oxide/titanium dioxide composite nano materials
Preparation method, this method can at ambient pressure, and directly high-volume synthesis has zinc oxide/bis- of one-dimensional nano structure in the solution
Titanium oxide composite nano materials, and yield is high, prepares cost low.
In order to solve the above technical problems, the technical solution adopted in the present invention is：
A kind of preparation method of Zinc oxide/titanium dioxide composite nano materials, comprises the following steps：
Step 1, a certain amount of titania powder is taken to be dispersed in water, then toward adding the desired amount of soluble Zn in solution
Salt and hexamethylenetetramine, stirring obtain dispersion soln；
Step 2, the dispersion soln of heating stepses 1 while stirring, makes it react 10~80min at 60~95 DEG C of temperature；
Step 3, by the reacted sediment of step 2 is by filtering, cleaning and drying process is that can obtain zinc oxide/dioxy
Change titanium composite nano materials.
Wherein, in step 1, the particle diameter of the titania powder is 5~50nm, if the particle diameter of titanium dioxide is received more than 50
Rice, can reduce the dispersed effect of product.
Wherein, in step 1, the soluble zinc salt is one kind in zinc nitrate, zinc acetate, zinc sulfate or zinc chloride or appoints
Several combination of meaning.
Wherein, in step 1, the hexamethylenetetramine can also be substituted with monoethanolamine or urea, if highly basic is selected in ammonia source,
During such as ammoniacal liquor or sodium hydroxide, product is the mixing of nano particle, it is impossible to obtain the product of one-dimensional nano structure.
Wherein, in step 1, in the dispersion soln, the concentration of zinc ion is 0.01~0.5mol/L, and equivalent nitrogen is dense
Spend for 2~8 times of zinc ion concentration.
Wherein, in the Zinc oxide/titanium dioxide composite nano materials, the mass percentage content of titanium dioxide for 3~
20%.
The principle of preparation method of the present invention：The growth course of one-dimensional nano structure generally comprises two ranks of nucleation and growth
Section, forms seed crystal (nucleation) by reaction product supersaturation first, and the speed of growth is far above these subsequent seed crystals in one direction
Other directions form one-dimensional nano structure (anisotropic growth).Nucleation needs higher degree of supersaturation and fiercer reaction ring
Border, but all directions speed of growth difference is smaller, generally yields substantial amounts of nano particle；And the growth of one-dimensional nano structure needs
Relatively mild reaction environment, gentle reaction environment is conducive to obtaining one-dimensional nano structure, but because nucleation is difficult, 1-dimention nano
Number of structures is less, and yield is relatively low.Reaction environment required by the two above-mentioned stages mutually conflicts and with larger difference.
In the present invention, the raw material and soluble zinc salt that can slowly release amino during using heating in water carry out reaction generation oxidation
Zinc, reaction condition is more gentle, is conducive to generating one-dimension zinc oxide nanostructured；Simultaneously add titania nanoparticles and
Zinc oxide affinity is higher, can as zinc oxide growth nuclearing centre, required for solving one-dimension zinc oxide nanostructured
On The Nucleation, the quantity of generation nanometer rods can be significantly improved, obtain a large amount of many by nucleating point or starting point of titanium dioxide
Branch one-dimensional nano structure, thus reduce the sizes of nanometer rods within 100 nanometers, so as to be conducive to increasing the ratio surface of product
Product.
Beneficial effect：The preparation method of the present invention can realize that the Zinc oxide/titanium dioxide of one-dimensional nano structure is compound and receive
The high-volume synthesis of rice material, it uses directly synthesis in aqueous under normal pressure, and not only reaction condition is gentle, energy consumption
Low, cost is low and obtained product purity is high, at the same also have the advantages that surface area greatly, good dispersion and crystallinity it is high.
Brief description of the drawings
Fig. 1 is the XRD for the Zinc oxide/titanium dioxide composite nano materials that preparation method of the present invention is obtained；
Fig. 2 is the SEM figures for the Zinc oxide/titanium dioxide composite nano materials that preparation method of the present invention is obtained；
Fig. 3 is the TEM figures for the Zinc oxide/titanium dioxide composite nano materials that preparation method of the present invention is obtained.
Embodiment
Technical scheme is described further below in conjunction with accompanying drawing, but the scope of protection of present invention is simultaneously
It is not limited to this.
Embodiment 1
The preparation method of Zinc oxide/titanium dioxide composite nano materials of the present invention, comprises the following steps：
Step 1, it is that 0.274g/L weighs P25 type titania powders by concentration, is scattered in deionized water, utilizes magnetic force
Or electric stirring is well mixed；Again by zinc ion concentration be 25mmol/L toward zinc nitrate hexahydrate solution in solution and by concentration
For 25mmol/L toward add in solution hexamethylenetetramine (the addition mol ratio of soluble zinc salt and hexamethylenetetramine is between 1:
Between 0.5~2), it is well mixed to obtain dispersion soln；
Step 2, the dispersion soln of heating stepses 1 while stirring, makes it react 20min at 95 DEG C of temperature, completes growth
Process；
Step 3, the reacted sediment of step 2 be can obtain into end-product after filtering, cleaning, drying process.
In Zinc oxide/titanium dioxide composite nano materials made from embodiment 1, the mass percent of titanium dioxide is
14%.Fig. 1 is the X-ray diffractogram of Zinc oxide/titanium dioxide composite nano materials made from embodiment 1, can from Fig. 1
Go out, be labeled as the crystal face of the strong diffraction maximum correspondence zinc oxide of " * ", other crystal faces for being labeled as the peak correspondence titanium dioxide of " # " spread out
Penetrate.Fig. 2 is the scanning electron micrograph of Zinc oxide/titanium dioxide composite nano materials made from embodiment 1, can be with from Fig. 2
Find out, zinc oxide nano rod forms flower-shaped multiple-branching construction, the center of flower-like structure is titanium dioxide from a nuclearing centre
Titanium nano particle, the diameter of nanometer rods is about 100 nanometers, and length is about 1 micron.Fig. 3 is zinc oxide/bis- made from embodiment 1
The transmission electron microscope figure of titanium oxide composite nano materials, from figure 3, it can be seen that the product point that preparation method of the present invention is obtained
Scattered property is good, and surface area is big.Obtained product purity is more than 99% (i.e. using titanium dioxide as the one-dimensional nano structure of core or many points
The accounting of branch one-dimensional nano structure).
Embodiment 2
The preparation method of Zinc oxide/titanium dioxide composite nano materials of the present invention, comprises the following steps：
Step 1, it is that 0.274g/L weighs P25 type titania powders by concentration, is scattered in deionized water, utilizes magnetic force
Or electric stirring is well mixed；It is again that 25mmol/L is 25mmol/L toward zinc acetate in solution and by concentration by zinc ion concentration
Hexamethylenetetramine is added into solution, it is well mixed to obtain dispersion soln；
Step 2, the dispersion soln of heating stepses 1 while stirring, makes it react 40min at 80 DEG C of temperature, completes growth
Process；
Step 3, it is that can obtain end-product by filtering, cleaning, drying process by the reacted sediment of step 2.
In Zinc oxide/titanium dioxide composite nano materials made from embodiment 2, the mass percent of titanium dioxide is
20%.As a result product is shown in addition to nanowire diameter is about 80 nanometers, and the pattern and structure and the product of embodiment 1 of product are basic
It is identical.
Preparation method of the present invention is in the addition of titanium dioxide, because zinc oxide nano rod is preferential using titanium dioxide as core
Growth, if therefore titanium dioxide addition not enough, the quantity of flower-like structure is few in product, and product size can become big, nanometer
Rod is thicker；If the addition increase of titanium dioxide, flower-like structure quantity will become many, nanometer rods can attenuate, and length shortens.
The present invention prepares the Zinc oxide/titanium dioxide composite Nano material of one-dimensional nano structure using liquid phase hydrothermal synthesis method
Material, this method has the advantages that synthesis temperature is low, energy consumption is low, cost is low, environment compatibility is good and can produce in enormous quantities；Production
There is coupling and coordinative role in thing between titanium dioxide and zinc oxide, so as to improve its performance in terms of photocatalysis；This hair
It is empty between one-dimensional nano structure or multiple-limb one-dimensional nano structure of the product that bright method is obtained using titanium dioxide as core, nanostructured
Gap is uniform sequential, is conducive to gas and liquid to be transmitted in these spaces；Therefore the composite Nano that preparation method of the present invention is obtained
Material has a good application prospect in photocatalytic pollutant degradation in terms of improving atmosphere and water pollution.
Obviously, above-described embodiment is only intended to clearly illustrate example of the present invention, and is not to the present invention
The restriction of embodiment.For those of ordinary skill in the field, it can also be made on the basis of the above description
Its various forms of changes or variation.There is no necessity and possibility to exhaust all the enbodiments.And these belong to this hair
Among the obvious changes or variations that bright spirit is extended out is still in protection scope of the present invention.
Claims (6)
1. a kind of preparation method of Zinc oxide/titanium dioxide composite nano materials, it is characterised in that comprise the following steps：
Step 1, take a certain amount of titania powder to be dispersed in water, then toward add in solution the desired amount of soluble zinc salt and
Hexamethylenetetramine, stirring obtains dispersion soln；
Step 2, the dispersion soln of heating stepses 1 while stirring, makes it react 10~80min at 60~95 DEG C of temperature；
Step 3, by the reacted sediment of step 2 is by filtering, cleaning and drying process is that can obtain Zinc oxide/titanium dioxide
Composite nano materials.
2. the preparation method of Zinc oxide/titanium dioxide composite nano materials according to claim 1, it is characterised in that：Step
In rapid 1, the particle diameter of the titania powder is 5~50nm.
3. the synthetic method of Zinc oxide/titanium dioxide composite nano materials according to claim 1, it is characterised in that：Step
In rapid 1, the soluble zinc salt is one kind in zinc nitrate, zinc acetate, zinc sulfate or zinc chloride or any several combination.
4. the synthetic method of Zinc oxide/titanium dioxide composite nano materials according to claim 1, it is characterised in that：Step
In rapid 1, the hexamethylenetetramine can be substituted with monoethanolamine or urea.
5. the synthetic method of Zinc oxide/titanium dioxide composite nano materials according to claim 1, it is characterised in that：Step
In rapid 1, in the dispersion soln, the concentration of zinc ion is 0.01~0.5mol/L, and equivalent nitrogen concentration is zinc ion concentration
2~8 times.
6. the synthetic method of Zinc oxide/titanium dioxide composite nano materials according to claim 1, it is characterised in that：Institute
State in Zinc oxide/titanium dioxide composite nano materials, the mass percentage content of titanium dioxide is 3~20%.
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| CN106001552A (en) * | 2016-07-07 | 2016-10-12 | 中国科学院合肥物质科学研究院 | Preparation method of silver @ metallic oxide composite nanometer line |
| CN108548098B (en) * | 2018-04-18 | 2020-09-15 | 广东职业技术学院 | Ultraviolet LED lamp bead capable of degrading organic volatile matter of methyl-oleoresin, and preparation method and application thereof |
| CN108906020A (en) * | 2018-07-23 | 2018-11-30 | 张家港市汇鼎新材料科技有限公司 | A kind of preparation method of titanium dioxide-zinc oxide composite catalyzing material |
| CN109012756A (en) * | 2018-09-17 | 2018-12-18 | 南京景铄新材料科技有限公司 | A kind of catalysis material and preparation method thereof with high stability |
| CN113083276B (en) * | 2021-03-11 | 2023-02-28 | 浙江理工大学 | Titanium dioxide/zinc oxide heterojunction material with dendritic structure and preparation method thereof |
| CN113662866B (en) * | 2021-08-21 | 2023-06-09 | 集韵化妆品(上海)有限公司 | Preparation method of moisturizing sun-screening liquid |
| CN114590834B (en) * | 2022-03-30 | 2023-07-14 | 广州天赐高新材料股份有限公司 | Nanometer titanium dioxide-zinc oxide hybrid material and synthetic method thereof |
| CN115281284A (en) * | 2022-09-26 | 2022-11-04 | 北京中科泰训科技有限公司 | Antibacterial peptide composite nano-particles, preparation method and application of antibacterial peptide composite nano-particles as feed additive |
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