CN103641153B - Method of preparing zinc oxide photocatalytic nanomaterial by template free method - Google Patents

Method of preparing zinc oxide photocatalytic nanomaterial by template free method Download PDF

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CN103641153B
CN103641153B CN201310680336.2A CN201310680336A CN103641153B CN 103641153 B CN103641153 B CN 103641153B CN 201310680336 A CN201310680336 A CN 201310680336A CN 103641153 B CN103641153 B CN 103641153B
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zinc oxide
solution
nanomaterial
zinc
butylamine
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CN103641153A (en
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张海娇
焦正
周洪顺
冯蓓
胡赛
王栋海
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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Abstract

The invention relates to a method for preparing a zinc oxide photocatalytic nanomaterial by a template-free method. According to the low-cost template-free method, raw materials include water, ethanol, zinc nitrate and n-butylamine, wherein zinc nitrate is a zinc source, water and ethanol serve as solvents, and n-butylamine is an alkali source, and a simple hydro-thermal synthesis method is carried out to finally obtain the zinc oxide nanomaterial with a unique spherical structure with coarse surface by adopting. Shown in XRD (X-Ray Diffraction) spectrogram, the prepared zinc oxide material has a typical wurtzite structure and is good in crystallization. The photocatalytic test results show that the prepared zinc oxide material has excellent photocatalytic performance, can effectively solve the problems of environmental pollution and the like, and further has a potential application prospect in the fields of energy sources, biomedicines and the like.

Description

Without the method for template synthesis zinc oxide photocatalytic nanomaterial
Technical field
The present invention relates to a kind of preparation method of zinc oxide photocatalytic nanomaterial, particularly a kind of method without template synthesis zinc oxide photocatalytic nanomaterial.
Background technology
Zinc oxide is a kind of typical metal oxide semiconductor material, compared with common zinc oxide product, nano zine oxide have active high, specific area is large, a series of special performances such as material fineness, purity and material shape are adjustable, having application in a lot of field, is current application high functional inorganic materials comparatively widely.Due to the granular of nano granular of zinc oxide size, specific area can enlarge markedly, surface molecular arrangement, electronic structure and crystal structure all can change, thus make it have physics, chemistry, the surface and interface character of a series of excellence, be widely used in magnetic, optical, electrical, catalysis etc.
Wherein, nano zine oxide is also more active in the application of photocatalysis field.Harmful organic substances in water, as organic chloride, agricultural chemicals, pigment etc., fully remove more difficult, and zinc oxide can make organic substance decomposing as photochemical catalyst with current water technology, avoids it to the pollution of environment.Research shows, the reaction speed of nano zine oxide is 100 ~ 1000 times of common zinc oxide, and compared with ordinary particle, nano zine oxide causes the scattering of light hardly.The nano zine oxide with suitable dimension size can also reclaim well, thus can recycle, and reduces financial cost.
At present, the method for synthesis of nano-zinc oxide has a lot, mainly contains chemical precipitation method, sol-gal process, emulsion process etc.Wherein, hydrothermal synthesis method has the outstanding advantages such as equipment is simple, easy and simple to handle, products collection efficiency is high, well-crystallized because of it, shows good diversity, thus more and more applied in synthesis of nano-zinc oxide material.However, a lot of problem needing to solve still is there is in water heat transfer process, for preparing nano zinc oxide by hydro thermal method, the factors such as the selection of template and raw material, the concentration of reactant, reaction temperature, reaction time not only affect the size of product, pattern and performance, but also relate to pollution and financial cost problem.So by adjustment reaction condition and parameter, the controlledly synthesis realizing nano zinc oxide material will become the research topic that has challenge.
Summary of the invention
The object of the present invention is to provide the method without template synthesis zinc oxide photocatalytic nanomaterial, it is homogeneous that this method can obtain size, good dispersion, has the nano zinc oxide material of unique strawberry shape pattern and desirable photocatalysis effect.
For achieving the above object, the present invention by the following technical solutions, now describes technical scheme of the present invention in detail.Concrete operation step is as follows:
Without a method for template synthesis zinc oxide photocatalytic nanomaterial, it is characterized in that the step of the method is as follows:
A. zinc nitrate is dissolved in deionized water and is mixed with the solution A that concentration is 0.15 ~ 0.30 mol/L;
B. n-butylamine and ethanol are pressed (0.15 ~ 0.30): the volume ratio of 1 mixes, and is mixed with solution B;
C. solution B obtained above dropwise joined in solution A, obtain mixed solution C, wherein the volume ratio of solution A and solution B is: (0.4 ~ 1.5): 1, continues stirring 1 h at ambient temperature;
D. under 120 ~ 180 DEG C of conditions, 1 ~ 24 h is reacted in the C solution tape loaded teflon-lined autoclave upper step obtained; Products therefrom through routine centrifugal, washing, dry after, obtain the zinc oxide photocatalytic nanomaterial of preparation.
The present invention adopts a simple step hydrothermal synthesis method, and under the condition of not adding any template, take zinc nitrate as zinc source, the mixed solution of water and ethanol is reaction dissolvent, prepares the nano zinc oxide material of strawberry shape under the guiding of Small molecular alkali n-butylamine.The product of gained of the present invention, pattern is homogeneous, and its particle diameter is at about 1 μm, and favorable dispersibility; The more important thing is, this method technique is simple, with low cost and environmentally friendly.In addition, photocatalysis experimental result shows that this product has good photocatalysis effect, thus has wide industrial applications prospect.
In technical process of the present invention, be first dissolved completely in deionized water by zinc nitrate, n-butylamine is dissolved in ethanol, and both mix, under the alkaline environment of Small molecular alkali n-butylamine, and Zn 2+first nucleation in synthetic system, then generates the presoma [Zn (OH) of zinc oxide gradually through an Ostwald ripening process 4] 2-, in follow-up water-heat process, presoma continued growth, is finally converted into pattern homogeneous, and single dispersing is good, shaggy particulate oxidation zinc product.
Compared with prior art, the technology of the present invention has following remarkable advantage:
The inventive method technique is simple, low cost, without template, and high yield, environmentally friendly; And without the need to the roasting process through high temperature, can directly generate size homogeneous, the strawberry shape nano zinc oxide material of favorable dispersibility, this product has good photocatalysis effect, can be used for the prevention and management etc. of environmental pollution.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of gained nano zinc oxide material in the embodiment of the present invention 1.
Fig. 2 is the SEM picture of gained nano zinc oxide material in the embodiment of the present invention 1.
Fig. 3 is the photocatalysis effect figure of gained nano zinc oxide material in the embodiment of the present invention 1.
Detailed description of the invention
All embodiments all operate by the operating procedure of technique scheme.
Embodiment 1
A. take 0.01 mol zinc nitrate and 1.5 mol deionized waters respectively with electronic balance, put it into mixing and stirring in beaker, until zinc nitrate dissolves completely, obtain solution A;
B. measure n-butylamine and the 60 ml ethanol of 10 ml with graduated cylinder respectively, put it into mixing and stirring in beaker, obtain solution B;
C. B solution is dropwise joined in solution A, continue stirring 1 h at ambient temperature, obtain mixed solution C;
D. by C solution tape loaded teflon-lined autoclave, under 120 ~ 180 DEG C of conditions, 6 h are reacted;
E., after having reacted, product is taken out from reactor, with deionized water and ethanol cyclic washing, centrifugal after, product is dried at 80 DEG C, obtains finely dispersed strawberry shape nano zinc oxide material prepared by the present invention.
Obtained sample is carried out physical property sign, and its partial results as shown in drawings.Gained zinc oxide material is shaggy chondritic (being similar to strawberry), and its particle diameter is at about 1 μm.
Embodiment 2
Preparation process and the step of the present embodiment are substantially the same manner as Example 1, unlike in a and b step
A. take 0.01 mol zinc nitrate and 3.0 mol deionized waters respectively with electronic balance, put it into mixing and stirring in beaker, until zinc nitrate dissolves completely;
B. n-butylamine and the 30 ml ethanol of 10 ml are measured respectively with graduated cylinder, by its mixing and stirring.
Acquired results and embodiment 1 slightly difference, the surperficial relative smooth of the Zinc oxide nanoparticle obtained, particle diameter is also large than the Zinc oxide nanoparticle in embodiment 1.
Embodiment 3
Preparation process and the step of the present embodiment are substantially the same manner as Example 1, unlike in Step d
D. by above-mentioned mixed solution tape loaded teflon-lined autoclave, under 160 DEG C of conditions, 1 h is reacted.
Acquired results and embodiment 1 have bigger difference, obtained zinc oxide particle surfaces smoother, and size is not very even, reunites more serious.
the photocatalysis performance test of material
The nano zinc oxide material of precise 0.02 g adds in 50 ml rhodamine (RhB) solution (10 mg/L), ultrasonic disperse; Gained suspension lucifuge stirs 0.5 h makes material reach adsorption equilibrium; Take out 4 ml suspension after balance in 5 ml centrifuge tubes, remaining suspension liquid is poured in 50 ml quartz ampoules, then put into SGY-IB type light-catalyzed reaction instrument, in reactant liquor, constantly pass into air catalyst is fully suspended in whole system always; Open 300 W Hg lamp irradiation, get 4 ml suspension in centrifuge tube every 10 min, total reaction time 1 h; Reaction terminates, each sample centrifugation of taking out, get supernatant ultraviolet-visible spectrophotometer and survey its absorbance at about 552 nm, thus reflect that each degradation time section remains the concentration of rhodamine afterwards, reflect that this method obtains the effect of photocatalyst of zinc oxide degraded rhodamine with this.
See accompanying drawing, Fig. 1 is the XRD spectra of the embodiment of the present invention 1 gained nano zinc oxide material.XRD analysis: carry out on Japanese RigaKu D/max-2550 type X-ray diffractometer; Adopt CuK α diffraction.Known from Fig. 1, gained nano zinc oxide material of the present invention has typical wurtzite structure, consistent with standard spectrogram (JCPDS:36-1451), has no other assorted peak, proves the crystal structure of its pure phase.
See accompanying drawing, Fig. 2 is ESEM (SEM) picture of the embodiment of the present invention 1 gained nano zinc oxide material.Sem analysis: adopt NEC company JSM-6700F type emission scan electron microscope observation material morphology.As can be seen from SEM picture, the nano zinc oxide material that the present invention obtains, rough surface, be the globular nanostructures piled up by many little nano particles, its particle diameter is at about 1 μm.
See accompanying drawing, Fig. 3 is the photocatalysis performance figure of the embodiment of the present invention 1 gained nano zinc oxide material.As we can see from the figure, in the light degradation experiment of rhodamine, gained catalyst is almost degradable by rhodamine in 40 min, prove that it has excellent photocatalytic activity, this may be relevant with the nanostructured of its uniqueness, as uniform pattern, less particle diameter, good monodispersity and coarse surface etc.

Claims (1)

1., without a method for template synthesis zinc oxide photocatalytic nanomaterial, it is characterized in that the step of the method is as follows:
A. zinc nitrate is dissolved in deionized water and is mixed with the solution A that concentration is 0.15 ~ 0.30 mol/L;
B. n-butylamine and ethanol are pressed (0.15 ~ 0.30): the volume ratio of 1 mixes, and is mixed with solution B;
C. solution B obtained above dropwise joined in solution A, obtain mixed solution C, wherein the volume ratio of solution A and solution B is: (0.4 ~ 1.5): 1, continues stirring 1 h at ambient temperature;
D. under 120 ~ 180 DEG C of conditions, 1 ~ 24 h is reacted in the C solution tape loaded teflon-lined autoclave upper step obtained; Products therefrom through routine centrifugal, washing, dry after, obtain the zinc oxide photocatalytic nanomaterial of preparation.
CN201310680336.2A 2013-12-13 2013-12-13 Method of preparing zinc oxide photocatalytic nanomaterial by template free method Expired - Fee Related CN103641153B (en)

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CN112915991A (en) * 2021-01-19 2021-06-08 西南交通大学 Preparation method of lamellar aggregated flower-shaped zinc oxide photocatalyst
CN113735158A (en) * 2021-09-09 2021-12-03 陕西科技大学 Method for preparing high-dispersity spherical nano zinc oxide by microwave hydrothermal method
CN116272947A (en) * 2023-03-21 2023-06-23 中国民航大学 Method for synthesizing nano zinc oxide photocatalyst and indoor organic pollutant purifying device

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CN102167391A (en) * 2011-04-29 2011-08-31 西北大学 Method for preparing zinc oxide nanometer needle array
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US8252256B2 (en) * 2012-01-01 2012-08-28 King Abdulaziz City for Science and Technology (KACST) Synthesis of zinc-oxide nanoparticles and their use for photo catalytic degradation of cyanide

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CN102951672A (en) * 2012-09-27 2013-03-06 清华大学 Preparation method of ZnO nanocrystals

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