CN101948130B - Zinc oxide hollow microspheres and preparation method thereof - Google Patents
Zinc oxide hollow microspheres and preparation method thereof Download PDFInfo
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- CN101948130B CN101948130B CN2010105025261A CN201010502526A CN101948130B CN 101948130 B CN101948130 B CN 101948130B CN 2010105025261 A CN2010105025261 A CN 2010105025261A CN 201010502526 A CN201010502526 A CN 201010502526A CN 101948130 B CN101948130 B CN 101948130B
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Abstract
The invention discloses zinc oxide hollow microspheres and a preparation method thereof. The invention relates to an inorganic nano material, and provides the zinc oxide hollow microspheres and the preparation method thereof. The zinc oxide hollow microspheres are made of wurtzite structural zinc oxide with powder diffraction standard joint committee number 36-1451, the diameters of the microspheres are 5 to 8 microns, and the thicknesses of the sphere walls are 0.5 to 1 micron. The preparation method comprises the following steps of: dissolving zinc nitrate hexahydrate and hexamethylene tetramine into water to obtain solution A, and adding sodium citrate into the solution A to obtain solution B; putting the solution B into a closed high pressure reactor, and putting the high pressure reactor into a drying oven to perform hydrothermal reaction; and after the hydrothermal reaction, cooling the reaction product to room temperature, opening the high pressure reactor, and filtering, washing and drying the sediment to obtain the zinc oxide hollow microspheres. The preparation method has the advantages of simplicity, convenience, low temperature, high yield and low sample dislocation density; and the zinc oxide hollow microspheres have broad application value in the fields of medicament release, photocatalysis, dye-sensitized solar cells and the like.
Description
Technical field
The present invention relates to a kind of inorganic nano material, particularly a kind of zinc oxide hollow micron ball and preparation method thereof.
Background technology
Zinc oxide (ZnO) is a kind of important direct semiconductor material with wide forbidden band, and energy gap is 3.37eV under the room temperature, and exciton bind energy is up to 60meV, greater than the ionization energy 26meV under the room temperature.The nano zinc oxide material of different-shape such as nano wire, nanotube, nano belt, nano-rings etc. exist very big-difference on performance; The zinc oxide material of these nanostructures shows many excellent specific properties that are different from block zinc oxide material, is playing a significant role aspect preparation nano photoelectronic devices and the nano electron device.
In numerous patterns of zinc oxide, the hollow ball nano material is one big type of important nano structural material, and it has low density, high-ratio surface, big cavity, special polarity and optical property thereof, thereby has broad application prospects in a lot of fields.At medical science and pharmacy field; Zinc oxide hollow spheres can be used as carrier, capsule and upholder (Helmut
the and Stephen Mann of drug delivery; Higher-Order Organization by Mesoscale Self-Assembly and Transformation of Hybrid Nanostructures; Angewandte Chemie International Edition; 2003,42,2350-2365); In field of materials; Zinc oxide hollow spheres can be used as (Jiaguo Yu and Xiaoxiao Yu such as support of the catalyst, transmitter, optics, lightweight filler; Hydrothermal Synthesis and Photocatalytic Activity of Zinc Oxide Hollow Spheres, Environmental Science & Technology, 2008; 42,4902-4907); In field of dye-sensitized solar cells, its primary structure provides large specific surface to adsorb more polychromatophilia material molecule, and its secondary structure and pore structure can play the effect at scattering of light center simultaneously; Improve the utilization ratio of light, thereby finally improved photoelectric transformation efficiency (MattLaw, the Lori E.Greene of battery; Justin C.Johnson, Richard Saykally and Peidong Yang, Nanowire dye-sensitized solar cells; Nature Materials; 2005,6,455-459).At present, the preparation method of Zinc oxide hollow spheres mainly contains template (Xi Wang, Peng Hu; Yuan Fangli, and Lingjie Yu, Preparation and Characterization of ZnO Hollow Spheres and ZnO-Carbon Composite Materials Using Colloidal Carbon Spheres as Templates; Journal of Physical Chemistry C, 2007,111; 6706-6712) and method of evaporation (Pu Xian Gao and Zhong Lin Wang, Mesoporous Polyhedral Cages and Shells Formed by Textured Self-Assembly of ZnO Nanocrystals, Journal ofthe American Chemical Society; 2003,125,11299-11305); Yet no matter be template and thermal evaporation; All exist shortcoming, template needs the technology of relative complex, and thermal evaporation cost and energy consumption are higher.
Summary of the invention
The object of the present invention is to provide a kind of zinc oxide hollow micron ball.
The preparation method of the zinc oxide hollow micron ball that another object of the present invention is to provide that a kind of technology is easy, cost and energy consumption is lower.
Said zinc oxide hollow micron ball is (the Joint Committee on Powder Diffraction Standards of JCPDS; JCPDS) be numbered the wurtzite structure zinc oxide of 36-1451; The diameter of said zinc oxide hollow micron ball is 5～8 μ m; The ball wall thickness of zinc oxide hollow micron ball is 0.5～1 μ m, and the spherical shell surface of zinc oxide hollow micron ball has porous network structure.
The preparation method of said zinc oxide hollow micron ball may further comprise the steps:
1) zinc nitrate hexahydrate and hexamethylenetetramine is soluble in water, get solution A, again Trisodium Citrate is added in the solution A, get solution B;
2) solution B is carried out the hydro-thermal reaction postcooling to room temperature, with sedimentation and filtration, washing, drying promptly gets zinc oxide hollow micron ball.
In step 1), said water is preferably deionized water, and the molar concentration rate of said zinc nitrate hexahydrate and hexamethylenetetramine can be 1: (0.5～2) is preferably 1: 1; Zn in the said solution B
2+Volumetric molar concentration can be 0.1～0.3mol/L, and the Trisodium Citrate volumetric molar concentration can be 0.02～0.06mol/L.
In step 2) in, said hydro-thermal reaction can be put into airtight autoclave with solution B, again autoclave is put into loft drier and carries out hydro-thermal reaction; Said loft drier can be the electric heating constant temperature air dry oven; The temperature of said hydro-thermal reaction can be 120～160 ℃, and the time of hydro-thermal reaction can be 2～12h; Said washing can be used deionized water wash earlier, uses absolute ethanol washing again; Said drying can be at 50～60 ℃ of down dry 3～5h.
Advantage such as that the preparation method of zinc oxide hollow micron ball according to the invention has is easy, low temperature, output capacity height and sample dislocation desity are little.Consumption through reconciliation statement surface-active agent Trisodium Citrate in hydro-thermal reaction; Can prepare more fine zinc oxide hollow micron ball; Meet (the Joint Committee on Powder Diffraction Standards of JCPDS; JCPDS) be numbered the wurtzite structure zinc oxide of 36-1451; The diameter of said zinc oxide hollow micron ball is 5～8 μ m, and the ball wall thickness of zinc oxide hollow micron ball is 0.5～1 μ m, and the spherical shell surface of zinc oxide hollow micron ball has porous network structure.Said zinc oxide hollow micron ball has wide application value in fields such as drug release, photochemical catalysis and dye sensitization solar batterys.
Description of drawings
Fig. 1 is X-ray diffraction (XRD) spectrogram of the zinc oxide hollow micron ball of the present invention's preparation.In Fig. 1, X-coordinate is diffraction angle (degree), and ordinate zou is a diffraction peak intensity; The from left to right corresponding respectively JCPDS of diffraction peak is numbered (100) of the wurtzite structure zinc oxide of 36-1451, (002), (101); (102), (110), (103); (200), the diffraction peak of (112) and (201) crystal face explains that the product of preparation is pure wurtzite structure zinc oxide.
Fig. 2 is low power ESEM (SEM) photo of the zinc oxide hollow micron ball of the present invention's preparation.The diameter range of zinc oxide hollow micron ball is 5～8 μ m.In Fig. 2, scale is 10 μ m.
Fig. 3 is the high power stereoscan photograph of the zinc oxide hollow micron ball of the present invention's preparation.The diameter of said zinc oxide hollow micron ball is about 6 μ m, and the thickness of ball wall is about 0.8 μ m, and the spherical shell surface has porous network structure.In Fig. 3, scale is 2 μ m.
Embodiment
Embodiment 1
1) zinc nitrate hexahydrate and hexamethylenetetramine are dissolved in the deionized water; Under the state of stirring at room, add Trisodium Citrate; Be mixed with homogeneous transparent solution after the stirring and dissolving; Wherein the volumetric molar concentration of zinc nitrate hexahydrate and hexamethylenetetramine is 1: 2, and the volume of deionized water is 20mL, fully is configured to Zn after the stirring and dissolving
2+Volumetric molar concentration is that 0.1mol/L, sodium citrate concentration are the mixing solutions of 0.02mol/L;
2) mixing solutions is put into airtight autoclave, again autoclave is inserted in the electric heating constant temperature air dry oven, under 120 ℃, carry out hydro-thermal reaction 2h;
3) naturally cool to room temperature after reaction finishes, open autoclave, white precipitate is filtered,, use absolute ethanol washing again 2 times, obtaining zinc oxide hollow micron ball after descending dry 3h at 50 ℃ with deionized water wash 2 times.
Zinc oxide hollow micron ball is used the x-ray diffractometer analysis, find that product is the wurtzite structure zinc oxide (referring to Fig. 1) that JCPDS is numbered 36-1451; Zinc oxide hollow micron ball is observed with the low power sem, and the diameter range of gained zinc oxide micrometer ball is 5～8 μ m (referring to Fig. 2); Zinc oxide hollow micron ball is observed discovery with the high power sem: the diameter of hollow ball is about 6 μ m, and the thickness of ball wall is about 0.8 μ m, and surperficial spherical shell has porous network structure (referring to Fig. 3).
Embodiment 2
1) zinc nitrate hexahydrate and hexamethylenetetramine are dissolved in the deionized water; Under the state of stirring at room, add Trisodium Citrate; Be mixed with homogeneous transparent solution after the stirring and dissolving; Wherein the volumetric molar concentration of zinc nitrate hexahydrate and hexamethylenetetramine is 1: 1, and the volume of deionized water is 24mL, fully is configured to Zn after the stirring and dissolving
2+Volumetric molar concentration is that 0.2mol/L, sodium citrate concentration are the mixing solutions of 0.04mol/L;
2) mixing solutions is put into airtight autoclave, again autoclave is inserted in the electric heating constant temperature air dry oven, under 140 ℃, carry out hydro-thermal thermal response 7h;
3) naturally cool to room temperature after reaction finishes, open autoclave, white precipitate is filtered,, use absolute ethanol washing again 2 times, obtaining zinc oxide hollow micron ball after descending dry 4h at 55 ℃ with deionized water wash 2 times.
Embodiment 3
1) zinc nitrate hexahydrate and hexamethylenetetramine are dissolved in the deionized water; Under the state of stirring at room, add Trisodium Citrate; Be mixed with homogeneous transparent solution after the stirring and dissolving; Wherein the volumetric molar concentration of zinc nitrate hexahydrate and hexamethylenetetramine is 2: 1, and the volume of deionized water is 28mL, fully is configured to Zn after the stirring and dissolving
2+Volumetric molar concentration is that 0.3mol/L, sodium citrate concentration are the mixing solutions of 0.06mol/L;
2) mixing solutions is put into airtight autoclave, again autoclave is inserted in the electric heating constant temperature air dry oven, under 160 ℃, carry out hydro-thermal thermal response 12h;
3) naturally cool to room temperature after reaction finishes, open autoclave, white precipitate is filtered,, use absolute ethanol washing again 2 times, obtaining zinc oxide hollow micron ball after descending dry 5h at 60 ℃ with deionized water wash 2 times.
Claims (5)
1. the preparation method of zinc oxide hollow micron ball is characterized in that may further comprise the steps:
1) zinc nitrate hexahydrate and hexamethylenetetramine is soluble in water, get solution A, again Trisodium Citrate is added in the solution A, get solution B; The molar concentration rate of said zinc nitrate hexahydrate and hexamethylenetetramine is 1: 0.5～2; Zn in the said solution B
2+Volumetric molar concentration is 0.1～0.3mol/L, and the Trisodium Citrate volumetric molar concentration is 0.02～0.06mol/L;
2) solution B is carried out the hydro-thermal reaction postcooling to room temperature, with sedimentation and filtration, washing, drying promptly gets zinc oxide hollow micron ball; The temperature of said hydro-thermal reaction is 120～160 ℃, and the time of hydro-thermal reaction is 2～12h;
Said zinc oxide hollow micron ball is the wurtzite structure zinc oxide that JCPDS is numbered 36-1451; The diameter of said zinc oxide hollow micron ball is 5～8 μ m; The ball wall thickness of zinc oxide hollow micron ball is 0.5～1 μ m, and the spherical shell surface of zinc oxide hollow micron ball has porous network structure.
2. the preparation method of zinc oxide hollow micron ball as claimed in claim 1 is characterized in that in step 1), and said water is deionized water.
3. the preparation method of zinc oxide hollow micron ball as claimed in claim 1 is characterized in that in step 2) in, said hydro-thermal reaction is that solution B is put into airtight autoclave, again autoclave is put into loft drier and carries out hydro-thermal reaction.
4. the preparation method of zinc oxide hollow micron ball as claimed in claim 3 is characterized in that said loft drier is the electric heating constant temperature air dry oven.
5. the preparation method of zinc oxide hollow micron ball as claimed in claim 1 is characterized in that in step 2) in, said washing is to use deionized water wash earlier, uses absolute ethanol washing again; Said drying is at 50～60 ℃ of down dry 3～5h.
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| CN102259906A (en) * | 2011-06-02 | 2011-11-30 | 西北工业大学 | Method for preparing hollow zinc oxide microspheres |
| CN102390862A (en) * | 2011-08-15 | 2012-03-28 | 天津理工大学 | Liquid-phase precipitation preparation method of zinc oxide porous hollow balls |
| CN103048363B (en) * | 2011-10-12 | 2015-01-14 | 中国科学院合肥物质科学研究院 | Metallic oxide material with mesoporous-macroporous composite structure as well as preparation method and application thereof |
| CN102515246B (en) * | 2011-12-02 | 2013-12-04 | 南京林业大学 | Preparation method of porous nano zinc oxide (ZnO) |
| CN102583508B (en) * | 2012-03-05 | 2014-10-22 | 厦门大学 | ZnO microsphere and preparation method thereof |
| CN103182307B (en) * | 2013-03-05 | 2014-11-12 | 华南理工大学 | Cu-doped ZnO/graphene composite photocatalyst and preparation method thereof |
| CN104118902B (en) * | 2014-07-25 | 2015-11-11 | 济南大学 | A kind of ZnO microsphere and preparation method thereof |
| CN104971708B (en) * | 2015-07-03 | 2017-09-26 | 陕西科技大学 | Ce doping spherical ZnO photocatalysts applied to dye wastewater treatment and preparation method thereof |
| CN104928753A (en) * | 2015-07-10 | 2015-09-23 | 厦门大学 | Method for manufacturing zinc oxide nanometer net structure |
| CN105084413A (en) * | 2015-08-11 | 2015-11-25 | 扬州大学 | Method for preparing three-shell ZnO flowerlike micro-spheres with high solar-energy conversion efficiency |
| CN107256972A (en) * | 2017-05-27 | 2017-10-17 | 武汉理工大学 | A kind of method based on the sour nickel nano film of the porous cobalt of hollow carbon sphere template growth |
| CN107572578A (en) * | 2017-09-07 | 2018-01-12 | 东南大学 | A kind of method that no template prepares zinc oxide spherical shell |
| CN110773169B (en) * | 2019-11-04 | 2021-11-19 | 中国科学院山西煤炭化学研究所 | Shell-like CoTiO3Nano semiconductor photocatalyst and preparation method and application thereof |
| CN112158877A (en) * | 2020-10-19 | 2021-01-01 | 南京工程学院 | Controllable preparation method of core structure of core-shell zinc oxide |
| CN113003560A (en) * | 2021-03-30 | 2021-06-22 | 北京工业大学 | Method for hydro-thermal synthesis of 'sea urchin-like' nitrogen-doped hollow carbon microspheres by in-situ self-growth template |
| CN113135586B (en) * | 2021-04-21 | 2022-08-23 | 内蒙古大学 | Zinc oxide microsphere, electrode and preparation method thereof |
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| CN101723436B (en) * | 2009-12-31 | 2011-05-11 | 厦门大学 | Self-assembly zinc oxide hollow sphere and preparation method thereof |
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