CN103318944A - Preparation method of zinc oxide multi-stage nanometer structure - Google Patents
Preparation method of zinc oxide multi-stage nanometer structure Download PDFInfo
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Abstract
The invention relates to a preparation method of a ZnO (zinc oxide) multi-stage nanometer structure and belongs to the technical field of material synthesis and photocatalysis. The preparation method is characterized in that a non-ionic triblock high polymer F108 is used as a template agent, zinc acetate (Zn(COOH)2.2H2O) is used as a zinc source, urea is used as an alkali source, water and glycol are used as cosolvents, and a ZnO material with the multi-stage nanometer structure is obtained by adopting a simple single-step hydrothermal synthesis method, wherein the ZnO nanometer materials with uniform morphology can be obtained by using triethanolamine (TEOA), ammonia water (NH3.H2O) and the like as the alkali sources, and the ZnO nanometer materials are different in terms of morphology and particle size. The photocatalysis test results show that the ZnO material prepared by the method has excellent photocatalytic performance, can be used for effectively solving the environmental pollution problem and has potential application prospect in the fields of energy sources, photoelectric devices and the like.
Description
Technical field
The present invention relates to a kind of preparation method of zinc oxide multi-level nano-structure, belong to material and synthesize and the photocatalysis technology field.
Background technology
ZnO is comparatively widely a kind of material of present material area research, and its pattern, specific surface area, size and degree of crystallinity etc. have very important impact for various character and the application of zinc oxide.Its energy gap at normal temperatures is 3.37 eV, is typical direct band gap semiconductor material with wide forbidden band, and its exciton binding energy reaches 60 meV simultaneously, has special performance and purposes at aspects such as sensor, photochemical catalysis and solar cells.
In recent years, scholars begin gradually to one dimension, two dimension and the development of multidimensional morphological system from zero dimension quantum material the research of nano-ZnO.Multidimensional structure ZnO material is because different, the not congruent factor of surface atom coordination of size is little, specific surface area is large, surperficial key attitude and granule interior, cause the activity site on surface to increase, formed rough atomic steps, strengthened the reaction contact surface, and then the activity and selectivity of its catalyzer is far longer than traditional catalyst.Along with the development of material preparation technology, the research of multidimensional structure ZnO material has become the focus of field of nanometer material technology.
At present, people have adopted the whole bag of tricks to prepare the ZnO nano material with different-shape and structure, mainly contain chemical gas-phase method, colloidal sol-glue method, hydrothermal method etc.Wherein, chemical gas-phase method is had relatively high expectations to reaction conditions, and is wayward, and product purity is lower, has raw material remaining.Sol-gel method is take inorganic salt or metal alkoxide as presoma, through the gradually gelation of hydrolytie polycondensation process, then does some aftertreatments and obtains required ultrafine powder.This method raw materials cost is high, sedimentary washing, filtration and dry technology that need to be higher.And hydrothermal method refers in enclosed system, take water as solvent, and under the spontaneous pressure of certain temperature and water, a kind of synthetic method that original stock reacts.It is simple to operate, and reaction conditions is gentle, and with low cost, the product structure that obtains is also more stable, is a kind of more efficient method.
Therefore, the present invention adopts a simple step hydrothermal synthesis method, take water and ethylene glycol (EG) as cosolvent, at non-ionic type three block superpolymer, polyoxyethylene-polyoxytrimethylene-polyoxyethylene (EO
132-PO
50-EO
132, under structure-directing effect F108), by the dissimilar alkali source of the selection of technique, such as urea, trolamine etc., prepare the zinc oxide material with multi-level nano-structure.The present invention adopts non-ionic type three block superpolymer (F108) as template first, and gained ZnO has obvious multi-level nano-structure, and has the advantages such as pattern is controlled, particle diameter is adjustable, well-crystallized.In addition, the photochemical catalysis experimental result shows, resulting materials has excellent photocatalysis performance, has wide prospects for commercial application.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of zinc oxide multi-level nano-structure, present method can obtain the pattern homogeneous, the ZnO material that particle diameter is adjustable, and this material has good photocatalysis performance.
The present invention achieves the above object by the following technical solutions.Concrete operation step is as follows:
A. take by weighing 10 mmol zinc acetates (Zn (COOH) with electronic balance
22H
2O) and 0.5-2 g non-ionic type three block superpolymer, polyoxyethylene-polyoxytrimethylene-polyoxyethylene (EO
132-PO
50-EO
132, F108), it is added mixing in a certain amount of deionized water and the 20-60 ml ethylene glycol mixing solutions, stir 1 h under the normal temperature;
B. take by weighing 1-6 g urea (urea) with electronic balance, or replace to other alkali source (such as a certain amount of ammoniacal liquor (NH
3H
2O), trolamine (TEOA) etc.), add mentioned solution, normal temperature magnetic agitation 2 h;
C. above-mentioned mixing solutions is poured in the 100 ml band teflon-lined autoclave into crystallization 6-24 h under 100-180 ° of C condition;
D. after reaction is finished, product is taken out from reactor, through steps such as centrifugal, the washing of routine, oven dry, roastings, namely get the ZnO material of the multi-level nano-structure of the present invention's preparation.
In the technological process of the present invention, take zinc acetate as the zinc source, water and ethylene glycol are cosolvent, under the structure-directing effect of template F108, by the type of modulation alkali source, thereby effectively control the hydrothermal growth process of material, finally prepare and have different morphologies and the controlled ZnO material of particle diameter.
Compared with prior art, the technology of the present invention has following remarkable advantage:
The inventive method adopts F108 as template first, and technique is simple, mild condition only can realize effective control of zinc oxide different morphologies by changing alkali source, and the multiform looks ZnO material well-crystallized of gained, photocatalysis performance is excellent, can be used for prevention and the improvement of environmental pollution.
Description of drawings
Fig. 1 is the SEM photo of gained ZnO multi-level nano-structure in the embodiment of the invention 1.
Fig. 2 is gained ZnO multi-level nano-structure XRD spectra in the embodiment of the invention 1.
Fig. 3 is the photocatalysis performance figure of the embodiment of the invention 1, embodiment 2 and embodiment 3 gained ZnO nano materials.
Embodiment
All embodiment all operate by the operation steps of technique scheme.
Embodiment 1
1. take by weighing 10 mmol zinc acetates and 1g F108 with electronic balance, it is added mixing in 50 ml deionized waters and the 30 ml ethylene glycol mixing solutionss, stir 1 h under the normal temperature;
2. take by weighing 2 g urea (urea) with electronic balance and join in the mentioned solution, then normal temperature magnetic agitation 2 h;
3. above-mentioned mixing solutions is poured in the band teflon-lined autoclave of 100 ml into crystallization 12 h under 110 ° of C conditions;
4. after reaction is finished, product is taken out from reactor, through steps such as centrifugal, the washing of routine, oven dry, roastings, namely get the ZnO material of the multi-level nano-structure of the present invention's preparation.
Prepared sample is carried out physical property characterize, its partial results as shown in drawings.Resulting materials integral body is uniform ball-like structure, is mainly piled up by the multilayer zinc oxide nanometer sheet to form, and has obvious multi-level nano-structure, and its particle diameter is about 15 μ m.
Embodiment 2
Implementation process except for the following differences, other are all identical with embodiment 1.
1. take by weighing 10 mmol zinc acetates and 1.5 g F108 with electronic balance, it is added mixing in 50 ml deionized waters and the 30 ml ethylene glycol mixing solutionss, stir 1 h under the normal temperature;
2. take by weighing 10 ml trolamines (TEOA) with electronic balance and join in the mentioned solution, then normal temperature magnetic agitation 2 h;
3. above-mentioned mixing solutions is poured in the band teflon-lined autoclave of 100 ml into crystallization 12 h under 120 ° of C conditions.
Acquired results and embodiment 1 have than big difference, and difference is the similar strawberry of ZnO pattern that obtains, mainly pile up the ball-like structure that forms by many small-particles, and there are a lot of small embossments on the surface, and particle diameter is less, and its particle diameter is about 2 μ m.
Embodiment 3
Implementation process except for the following differences, other are all identical with embodiment 1.
2. take by weighing 4 ml ammoniacal liquor (NH with electronic balance
3H
2O) join in the mentioned solution, then normal temperature magnetic agitation 2 h;
3. above-mentioned mixing solutions is poured in the band teflon-lined autoclave of 100 ml into crystallization 18 h under 110 ° of C conditions.
Acquired results and embodiment 1 have notable difference, and difference is that the ZnO that obtains is hollow taraxacum shape, and its particle diameter is at 7 μ m.
Comparative Examples(making template without F108)
1. take by weighing 10 mmol zinc acetates (Zn (COOH) with electronic balance
22H
2O), it is added mixing in 50 ml deionized waters and the 30 ml ethylene glycol mixing solutionss, stir 1 h under the normal temperature;
2. claim 2 g urea (urea) to join in the mentioned solution with electronic balance, then normal temperature magnetic agitation 2 h;
3. above-mentioned mixing solutions is poured in the band teflon-lined autoclave of 100 ml into crystallization 12 h under 110 ° of C conditions;
4. after reaction is finished, product is taken out from reactor, through steps such as centrifugal, the washing of routine, oven dry, roastings, namely get the ZnO material without template synthesis.
Experimental result shows, Comparative Examples gained ZnO is fully different from embodiment 1, is mainly unordered sheet structure.
The photocatalysis performance test of material
Accurately the ZnO sample of the above-mentioned gained of weighing 20 mg adds in the 50 ml methyl orange solutions (25 mg/L) ultra-sonic dispersion 30 min; Gained suspension lucifuge stirs 1 h makes material reach adsorption equilibrium; Take out 4 ml suspension after the balance in 7 ml centrifuge tubes, remaining suspension liquid is poured in the 50 ml silica tubes, then put into SGY-IB type light-catalyzed reaction instrument, constantly pass into air in the reaction solution catalyzer is suspended in the whole system always; Open the irradiation of 300 W mercury lamps, get 4 ml suspension in centrifuge tube every 10 min, total reaction time 1 h; Reaction finishes, each sample centrifugation of taking out, get supernatant liquor and survey its absorbancy about 465 nm with ultraviolet-visible spectrophotometer, thereby reflect that each degradation time section remains the concentration of tropeolin-D afterwards, reflect that with this present method makes the effect of ZnO photocatalyst for degrading tropeolin-D.
Referring to accompanying drawing, Fig. 1 is scanning electron microscope (SEM) picture of the embodiment of the invention 1 gained multi-level nano-structure ZnO material.Sem analysis: adopt the JSM-6700F of Jeol Ltd. type emission scan electron microscope observation material pattern.Can find out from the SEM picture, the ZnO material of the present invention's preparation is the microballoon of the relative homogeneous of pattern, and its particle diameter is about 15 μ m.In addition, this material is mainly piled up by the multilayer zinc oxide nanometer sheet and is formed, and has obvious multi-level nano-structure, and this is very beneficial for substrate molecule with contact and the diffusion of catalyzer, thereby might improve the performance such as its photochemical catalysis.
Referring to accompanying drawing, Fig. 2 is the XRD spectra of the embodiment of the invention 1 gained ZnO multi-level nano-structure.XRD analysis: carry out at Japanese RigaKu D/max-2550 type X-ray diffractometer; Adopt CuK α diffraction.As can be known, gained ZnO nano material of the present invention has typical wurtzite structure from Fig. 1, and (PDF No:36-1451) is consistent with the standard spectrogram, has no other assorted peak, proves that it is the crystalline structure of pure phase.
Referring to accompanying drawing, Fig. 3 is the photocatalysis performance figure of the embodiment of the invention 1, embodiment 2 and embodiment 3 gained ZnO nano materials.As we can see from the figure, in the photodegradation experiment of tropeolin-D, embodiment 1 has shorter degradation time and more excellent degradation rate.Degradation rate reaches more than 99% in 60 minutes, proves that it has more excellent photocatalytic activity, this may be many with it lamellas pile up the three-dimensional multistage nanostructure that forms much relations arranged, this result also matches with the SEM picture of front.
Claims (1)
1. the preparation method of zinc oxide multi-level nano-structure is characterized in that the method has following synthesis step:
A. take by weighing 10 mmol zinc acetate Zn (COOH) with electronic balance
22H
2O and 0.5-2 g non-ionic type three block superpolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene EO
132-PO
50-EO
132, it is added mixing in a certain amount of deionized water and the 20-60 ml ethylene glycol mixing solutions, stir 1 h under the normal temperature;
B. take by weighing 1-6 g urea or ammoniacal liquor NH with electronic balance
3H
2O or trolamine TEOA add step a solution, normal temperature magnetic agitation 2 h;
C. step b mixing solutions is poured in the 100 ml band teflon-lined autoclave into crystallization 6-24 h under 100-180 ° of C condition;
D. after reaction is finished, product is taken out from reactor, through centrifugal, washing, oven dry, the roasting of routine, namely get the ZnO material of multi-level nano-structure.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103586013A (en) * | 2013-11-13 | 2014-02-19 | 河北师范大学 | Method for preparing wheat-ear-shaped nano ZnO photocatalyst |
| CN104492367A (en) * | 2014-11-26 | 2015-04-08 | 中国科学院合肥物质科学研究院 | Super high sensitivity precious metal-modified ZnO micro-nano hierarchical structure and preparation method thereof |
| CN104891553A (en) * | 2015-06-08 | 2015-09-09 | 济南大学 | Preparation method of ZnO semispherical micro-nanostructure and obtained product |
| CN104891554A (en) * | 2015-06-08 | 2015-09-09 | 济南大学 | ZnO double-flower-head structure and preparation method thereof |
| CN105460970A (en) * | 2015-12-21 | 2016-04-06 | 厦门理工学院 | Method for urea assisted hydrothermal synthesis of zinc oxide nanosheet |
| CN105645460A (en) * | 2016-03-04 | 2016-06-08 | 沈阳化工大学 | Methods for preparing and applying flower-shaped ZnO porous micro-spheres |
| CN111547761A (en) * | 2020-05-20 | 2020-08-18 | 中国科学院重庆绿色智能技术研究院 | Method for preparing zinc oxide by microwave assisted sol-gel hydrothermal method |
| CN111573713A (en) * | 2020-06-29 | 2020-08-25 | 陕西延长石油（集团）有限责任公司 | Synthesis method and application of controllable growth of crystal face of nano zinc oxide |
| CN111943253A (en) * | 2020-07-17 | 2020-11-17 | 杭州电子科技大学 | Bowl-shaped zinc oxide and preparation method thereof |
Citations (2)
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|---|---|---|---|---|
| CN101723436A (en) * | 2009-12-31 | 2010-06-09 | 厦门大学 | Self-assembly zinc oxide hollow sphere and preparation method thereof |
| CN102259907A (en) * | 2011-06-30 | 2011-11-30 | 上海大学 | Porous zinc oxide nano material and preparation method thereof |
-
2013
- 2013-06-24 CN CN201310251754XA patent/CN103318944A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723436A (en) * | 2009-12-31 | 2010-06-09 | 厦门大学 | Self-assembly zinc oxide hollow sphere and preparation method thereof |
| CN102259907A (en) * | 2011-06-30 | 2011-11-30 | 上海大学 | Porous zinc oxide nano material and preparation method thereof |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103586013A (en) * | 2013-11-13 | 2014-02-19 | 河北师范大学 | Method for preparing wheat-ear-shaped nano ZnO photocatalyst |
| CN103586013B (en) * | 2013-11-13 | 2015-04-22 | 河北师范大学 | Method for preparing wheat-ear-shaped nano ZnO photocatalyst |
| CN104492367A (en) * | 2014-11-26 | 2015-04-08 | 中国科学院合肥物质科学研究院 | Super high sensitivity precious metal-modified ZnO micro-nano hierarchical structure and preparation method thereof |
| CN104891553A (en) * | 2015-06-08 | 2015-09-09 | 济南大学 | Preparation method of ZnO semispherical micro-nanostructure and obtained product |
| CN104891554A (en) * | 2015-06-08 | 2015-09-09 | 济南大学 | ZnO double-flower-head structure and preparation method thereof |
| CN105460970A (en) * | 2015-12-21 | 2016-04-06 | 厦门理工学院 | Method for urea assisted hydrothermal synthesis of zinc oxide nanosheet |
| CN105645460A (en) * | 2016-03-04 | 2016-06-08 | 沈阳化工大学 | Methods for preparing and applying flower-shaped ZnO porous micro-spheres |
| CN111547761A (en) * | 2020-05-20 | 2020-08-18 | 中国科学院重庆绿色智能技术研究院 | Method for preparing zinc oxide by microwave assisted sol-gel hydrothermal method |
| CN111573713A (en) * | 2020-06-29 | 2020-08-25 | 陕西延长石油（集团）有限责任公司 | Synthesis method and application of controllable growth of crystal face of nano zinc oxide |
| CN111943253A (en) * | 2020-07-17 | 2020-11-17 | 杭州电子科技大学 | Bowl-shaped zinc oxide and preparation method thereof |
| CN111943253B (en) * | 2020-07-17 | 2022-07-12 | 杭州电子科技大学 | Bowl-shaped zinc oxide and preparation method thereof |
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Application publication date: 20130925 |