CN102658111B - Method for preparation of ZnO/diatomite nanoscale composite material by layer-by-layer self-assembly - Google Patents
Method for preparation of ZnO/diatomite nanoscale composite material by layer-by-layer self-assembly Download PDFInfo
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- CN102658111B CN102658111B CN2012100939523A CN201210093952A CN102658111B CN 102658111 B CN102658111 B CN 102658111B CN 2012100939523 A CN2012100939523 A CN 2012100939523A CN 201210093952 A CN201210093952 A CN 201210093952A CN 102658111 B CN102658111 B CN 102658111B
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Abstract
The invention relates to a method for preparation of a ZnO/diatomite nanoscale composite material by layer-by-layer self-assembly. The method comprises the following steps of 1, slowly and dropwisely adding an alcoholic solution of one or more alkalis into an alcoholic solution of zinc acetate, after dropwise addition is finished, sequentially stirring, and carrying out ultrasonic dispersion to obtain ZnO sol, 2, immersing diatomite in the ZnO sol, stirring, filtering, washing by deionized water, immersing the treated diatomite in a negatively charged polyelectrolyte solution, stirring, filtering, washing by deionized water, repeating the above processes n times to obtain a self-assembled ZnO/diatomite material having n+1 layers, wherein n is great than or equal to 0 and less than or equal to 10, and 3, drying the self-assembled ZnO/diatomite material obtained by the step 2 in an oven, and carrying out calcination at a temperature of 300 to 500 DEG C. The method provided by the invention has simple processes, adopts simple production equipment and realizes industrial production easily. The ZnO/diatomite nanoscale composite material loaded with ZnO nanoscale particles and obtained by the method has a strong adsorption capability and a good photocatalytic activity, can be recovered easily and has wide application prospects.
Description
Technical field
The invention belongs to the preparation field of nano composite material, particularly a kind of self-assembly method layer by layer prepares the method for zinc oxide/diatomite nano composite.
Background technology
The advantages such as it is one of key subjects of present facing mankind that water pollutes, and the method for sewage disposal has a variety of, and absorption method is large because of its adsorbance, and adsorption efficiency is high, and raw material sources are extensive become sewage water treatment method commonly used.In principle, any solid material that contains microcellular structure all can be applicable to adsorbent, this natural material with ordered micro-cellular structure of diatomite, specific area is large, heavy metal ion and a lot of organic matter there is absorption property, and rich in mineral resources, cost is low, for it is providing wide prospect aspect sewage disposal.
Diatomite is a kind of biogenic silicalite, and its main component is SiO
2, can know under high-power microscope see they have many difformities such as rotary strainer shape, column, band shape, straight chain shape (D.Losic, J.G.Mitchell, N.H.Voelcker.Advanced Materials, 2009,21:2947-2958).The diatomite surface is covered by a large amount of silicon hydroxyls and has hydrogen bond to exist.Srigate M.F proposes porous SiO
2There are isolated, adhesion, twin three types silicon hydroxyl (M.F.Srigate, F.Coradium, G.Frachini.Interaction of exchanged Zn in surface
2+Montmorillonite.Clays and Clay Minerals, 1994,42:288-296).The silicon hydroxyl in the aqueous solution from solving H
+, the pH value goes out certain surperficial elecrtonegativity greater than 2 o'clock its particle performance, and it can make other positively charged elimination of colloid stability by charge neutrality in water, but very little to other electronegative particle effect.Simultaneously, after the diatomite saturated adsorption, no longer can continue to adsorb the organic pollution in waste water, must can continue to use through regeneration.And by introduce functional inorganic nanoparticles on the diatomite surface, that can regulate surperficial electrokinetic potential electrically also can give diatomite some new functions.
Reported light radiation TiO in photocell from Fujishima in 1972 and Honda
2Since the redox reaction of water can occurring and producing hydrogen, photocatalysis technology has obtained research widely.In recent years, the ZnO photocatalysis technology is nontoxic owing to having, reaction condition is gentle, selectively good, photocatalysis performance is excellent and have the good advantages such as biocompatibility, coming into one's own processing aspect the difficult degradation pollutant.
Zinc oxide is the broad stopband direct band-gap semicondictor with wurtzite crystal structure, can band gap be 3.37eV under room temperature, exciton bind energy, up to 60meV, demonstrates near ultraviolet scattering, photocatalytic and piezoelectric property, has again good heat and chemical stability simultaneously.It is little that nano zine oxide has a particle size, specific area is large, has quantum size effect, small-size effect, skin effect etc., have the incomparable special nature of general Zinc oxide powder and new purposes at aspects such as light, electricity, magnetic, sensitivities, especially unique advantage is being arranged aspect human survival and healthy closely-related organic substance decomposing and antibacterial and deodouring, thereby can be used as high efficiency photocatalyst and carry out organic pollution in degradation water.The people such as Ashraf Shafaei use respectively ZnO, TiO
2Processing contains the waste water of terephthalic acid (TPA), found that, the photocatalytic degradation ability that both all has high efficiency photocatalysis ability and ZnO is better than TiO
2(Ashraf Shafaei, Manouchehr Nikazar, Mokhtar Arami.Desalination, 2010,4 (252), 8-16).
Because the ZnO of nano-scale has very high photocatalytic activity and antibiotic property, but, because diameter of particle is little, reclaim difficulty, process waste water cost with its high, be difficult to obtain practical application.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of self-assembly method layer by layer and prepares the method for zinc oxide/diatomite nano composite, the method is simple, required production equipment is simple, the zinc oxide that obtains/diatomite nano composite have high adsorption capacity, photocatalytic activity good, be easy to the characteristics such as recovery.
A kind of self-assembly method layer by layer of the present invention prepares the method for zinc oxide/diatomite nano composite, comprising:
(1) preparation of zinc oxide colloidal sol
Zinc acetate is dissolved in the lower alcohol of C1-C4, stirs until obtain transparent zinc acetate alcoholic solution under 70 ~ 80 ° of C; At room temperature, inorganic strong alkali is dissolved in the lower alcohol of C1-C4, stirs it is dissolved fully, obtain alkali alcosol; Above-mentioned alkali alcosol slowly is added drop-wise in the zinc acetate alcoholic solution, and the mol ratio of zinc acetate and inorganic strong alkali is 1:10 ~ 1:1, is added dropwise to complete rear continuation and stirs 30 ~ 60min, and ultrasonic dispersion 30 ~ 60min obtains ZnO colloidal sol;
(2) self assembling process layer by layer
Diatomite is immersed in above-mentioned ZnO colloidal sol, stirring, filtration, deionized water washing, then immerse in electronegative polyelectrolyte solution, stir, filter, the deionized water washing, obtain the ZnO/ diatomite material (this process has been self assembly bilayer, being called for short the self assembly number of plies is 1 layer) of one deck self assembly; (the ZnO/ diatomite material that is about to above-mentioned one deck self assembly immerses in above-mentioned ZnO colloidal sol to repeat said process, stirring, filtration, deionized water washing, then immerse in electronegative polyelectrolyte solution, stir, filter, the deionized water washing) n time, obtain the ZnO/ diatomite material of n+1 layer self assembly, wherein 0≤n≤10;
(3) powder drying, calcining
The product that step (2) obtains is dried under 40 ~ 60 ° of C, drying time is 5 ~ 12h, then calcines 3 ~ 6h under 300 ~ 500 ° of C, obtains ZnO/ diatomite nano composite.
Zn in the described zinc acetate alcoholic solution of step (1)
2+Concentration range be 0.01～0.15M.
The lower alcohol of the described C1-C4 of step (1) is methyl alcohol, ethanol, isopropyl alcohol or n-butanol.
The described inorganic strong alkali of step (1) is one or more in NaOH, potassium hydroxide or lithium hydroxide.
In the described alkali alcosol of step (1), the concentration range of alkali is 0.2～1.5M.
In the ZnO colloidal sol that step (1) obtains, zinc oxide grain is of a size of 8～25nm, is crystalline state, and the electrokinetic potential on surface is electropositive.
The mixing time of the stirring described in step (2) is 1 ~ 5min, and the deionized water washing is washing 3 ~ 5 times.
Electronegative polyelectrolyte described in step (2) is kayexalate, polyvinyl sulfuric acid salt, asuro or polyacrylic acid, preferentially uses polyacrylic acid.
In electronegative polyelectrolyte solution described in step (2), the concentration of polyelectrolyte is 0.002 ~ 0.2mmol/L.
Chemical reaction involved in step (1) is:
Zn
2++2OH
-=ZnO+H
2O
The lower alcohols such as the ethanol in solvent can partly be adsorbed on the zinc oxide nucleus that at first forms, and avoid it to become crystal seed and continue very soon to grow up, and can lower alcohol be the key that obtain stable sol as medium.
ZnO being fixed on the inert carrier of free settling, is the effective ways that solve catalyst separation, reclaim difficulty.The loose structure of diatomite uniqueness and absorption property provide suitable carrier for photochemical catalyst, and simultaneously its particle size is many carrys out the loaded with nano photochemical catalyst more than ten microns with it, can solve photochemical catalyst and reclaim the problem of difficulty after with sewage disposal.In addition, the nano zine oxide that antibiotic property is good loads on inexpensive porous carrier under the prerequisite that does not affect antibacterial effect, can also save the consumption of nano zine oxide.
The zinc oxide colloidal sol that the present invention gets a certain amount of sol-gel process preparation, immerse certain hour in zinc oxide colloidal sol with diatomite, filtration washing, then immerse certain hour in electronegative polyelectrolyte, filtration washing.This process, as one deck self assembly, repeats such process and can obtain the ZnO/ diatomite nano composite of different loads amount.Final products are dried, calcined to obtain to product.
Principal character of the present invention be take zinc acetate as zinc salt, NaOH is initiation material, ethanol is solvent, prepares zinc oxide colloidal sol, and by self-assembly method layer by layer, has prepared zinc oxide/diatomite nano composite., by changing the self assembly number of plies, can obtain the zinc oxide of different zinc oxide load capacity/diatomite nano composite.
This composite has realized that zinc oxide is lip-deep dispersed at diatomite particle, kept the distinctive loose structure of diatomite, have good photocatalysis performance and anti-microbial property, can be used as the photochemical catalyst of easy recovery and the anti-biotic material that can save zinc oxide dosage.
Beneficial effect:
(1) synthesis technique of the present invention is simple, and required production equipment is simple, is easy to realize suitability for industrialized production;
(2) load that obtains of the present invention the diatomite of ZnO nano particle have high adsorption capacity, photocatalytic activity good, be easy to the characteristics such as recovery, can be used for Kaolinite Preparation of Catalyst and carrier, adsorbent, waste water treating agent, antiseptic etc., have good application prospect in the purified treatment of the waste water that contains organic pollution and the waste liquid that contains bacterial virus.
Description of drawings
Fig. 1: the X-ray diffractogram of zinc oxide colloidal sol;
Fig. 2: the ZnO/ diatomite sample of one deck self assembly and diatomite X-ray diffractogram;
Fig. 3: the emission scan Electronic Speculum figure of the ZnO/ diatomite sample of one deck self assembly;
Fig. 4: the ZnO/ diatomite sample of five layers of self assembly and diatomite X-ray diffractogram;
Fig. 5: the field emission scanning electron microscope figure of the ZnO/ diatomite sample of five layers of self assembly.
The specific embodiment
, below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only are not used in and limit the scope of the invention for explanation the present invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
Under room temperature, measure the 150ml absolute ethyl alcohol in there-necked flask, add 2.82g Zn (CH
3COO)
22H
2O, heating water bath to 80 ° C, mechanical agitation is to obtaining clear solution; Under room temperature, take 1.6g NaOH, be dissolved in the 100ml absolute ethyl alcohol, magnetic agitation is dissolved it fully.Under under 70 ° of C water-baths of gained sodium hydroxide solution, slowly be added drop-wise in zinc acetate solution.Be added dropwise to complete rear continuation and stir 30min.Products therefrom is cooled to room temperature, and ultrasonic dispersion 30min, obtain zinc oxide colloidal sol.
Take 3g diatomite and immerse in 20ml gained zinc oxide colloidal sol, stir 2min, filter deionized water washed product 3 times; Then product is immersed in the polyacrylic acid aqueous solution that 20ml concentration is 0.01mmol/L, stir 2min, filter, deionized water washed product 3 times, obtain the zinc oxide/diatomite material of one deck self assembly, then at 60 ℃ of dry 5h, calcine 5h under 400 ℃, obtain zinc oxide/diatomite sample.
Fig. 1 is the zinc oxide colloidal sol of the present embodiment preparation obtains after gel, drying, sintering Zinc oxide powder X-ray diffractogram, reference standard XRD collection of illustrative plates, diffraction maximum in figure shows, this nano-powder is the zinc oxide of six side's phases, and the Scherrer formula calculates crystallite dimension in ZnO colloidal sol and is about 15nm.
Fig. 2 is one deck self-assembling ZnO/diatomite sample and diatomaceous X-ray diffractogram of the present embodiment preparation.Fig. 3 is one deck self-assembling ZnO of preparing in the present embodiment/diatomite sample and diatomaceous field emission scanning electron microscope figure, in Fig. 2 the diffraction maximum of zinc oxide a little less than, but still have highest peak and time strong peak of ZnO, the load number of plies of this and ZnO is few, load capacity is less relevant, figure also can find out from the emission of Fig. 3 field, and the diatomite surface only has the seldom particle of amount to adhere to.
Embodiment 2
Under room temperature, measure the 150ml absolute ethyl alcohol in there-necked flask, add 2.82g Zn (CH
3COO)
22H
2O, heating water bath to 80 ° C, mechanical agitation is to obtaining clear solution; Under room temperature, take 1.6g NaOH, be dissolved in the 100ml absolute ethyl alcohol, magnetic agitation is dissolved it fully.Under under 70 ° of C water-baths of gained sodium hydroxide solution, slowly be added drop-wise in zinc acetate solution.Be added dropwise to complete rear continuation and stir 30min.Products therefrom is cooled to room temperature, and ultrasonic dispersion 30min, obtain zinc oxide colloidal sol.
Take 3g diatomite and immerse in 20ml gained zinc oxide colloidal sol, stir 2min, filter deionized water washed product 3 times; Then product is immersed in the polyacrylic acid aqueous solution that 20ml concentration is 0.01mmol/L, stir 2min, filter, deionized water washed product 3 times, repeat said process 4 times, obtain the zinc oxide/diatomite of five layers of self assembly, then at the dry 5h of 60 ° of C, calcine 5h under 400 ° of C, obtain zinc oxide/diatomite sample.
Fig. 4 is five layers of self-assembly zinc oxide/diatomite sample and diatomaceous X-ray diffractogram of the present embodiment preparation, can obviously see the characteristic diffraction peak of zinc oxide in figure.Fig. 5 is five layers of self-assembly zinc oxide preparing in the present embodiment/diatomite sample and diatomite field emission scanning electron microscope figure, can obviously see and distribution of particles be arranged on the diatomite surface in figure, and even particle distribution.
Claims (8)
- One kind layer by layer self-assembly method prepare the method for zinc oxide/diatomite nano composite, comprising:(1) zinc acetate is dissolved in the lower alcohol of C1-C4, stirs until obtain the zinc acetate alcoholic solution under 70～80 ℃; At room temperature, inorganic strong alkali is dissolved in the lower alcohol of C1-C4, stirs it is dissolved fully, obtain alkali alcosol; Above-mentioned alkali alcosol slowly is added drop-wise in the zinc acetate alcoholic solution, and the mol ratio of zinc acetate and inorganic strong alkali is 1:10～1:1, is added dropwise to complete rear continuation and stirs 30～60min, and ultrasonic dispersion 30～60min obtains ZnO colloidal sol;(2) diatomite is immersed in above-mentioned ZnO colloidal sol, stirring, filtration, deionized water washing, then immerse in electronegative polyelectrolyte solution, stirs, filters, and deionized water is washed, and obtains the ZnO/ diatomite material of one deck self assembly; Repeat said process n time, obtain the ZnO/ diatomite material of n+1 layer self assembly, wherein 0≤n≤10; Wherein electronegative polyelectrolyte is kayexalate, polyvinyl sulfuric acid salt, asuro or polyacrylic acid;(3) product that step (2) is obtained is dried under 40～60 ℃, drying time is 5～12h, then calcines 3～6h under 300～500 ℃, obtains ZnO/ diatomite nano composite.
- 2. a kind of self-assembly method layer by layer according to claim 1 prepares the method for zinc oxide/diatomite nano composite, it is characterized in that: Zn in the described zinc acetate alcoholic solution of step (1) 2+Concentration range be 0.01～0.15mol/L.
- 3. a kind of self-assembly method layer by layer according to claim 1 prepares the method for zinc oxide/diatomite nano composite, it is characterized in that: the lower alcohol of the described C1-C4 of step (1) is methyl alcohol, ethanol, isopropyl alcohol or n-butanol.
- 4. a kind of self-assembly method layer by layer according to claim 1 prepares the method for zinc oxide/diatomite nano composite, it is characterized in that: the described inorganic strong alkali of step (1) is one or more in NaOH, potassium hydroxide or lithium hydroxide.
- 5. a kind of self-assembly method layer by layer according to claim 1 prepares the method for zinc oxide/diatomite nano composite, it is characterized in that: in the described alkali alcosol of step (1), the concentration range of alkali is 0.2～1.0mol/L.
- 6. a kind of self-assembly method layer by layer according to claim 1 prepares the method for zinc oxide/diatomite nano composite, it is characterized in that: in the ZnO colloidal sol that step (1) obtains, zinc oxide grain is of a size of 8～25nm.
- 7. a kind of self-assembly method layer by layer according to claim 1 prepares the method for zinc oxide/diatomite nano composite, it is characterized in that: the mixing time of the stirring described in step (2) is 1～5min, and the deionized water washing is washing 3～5 times.
- 8. a kind of self-assembly method layer by layer according to claim 1 prepares the method for zinc oxide/diatomite nano composite, it is characterized in that: in the electronegative polyelectrolyte solution described in step (2), the concentration of polyelectrolyte is 0.002～0.2mmol/L.
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| CN104162681B (en) * | 2014-07-30 | 2016-01-27 | 青岛科技大学 | A kind of preparation method of silver-ZnO nano composite structure |
| CN105494429B (en) * | 2015-12-09 | 2020-08-18 | 中国建筑材料科学研究总院 | Antibacterial mildew preventive, preparation method thereof and antibacterial mildew preventive method |
| CN106186042B (en) * | 2016-07-15 | 2018-04-06 | 东莞市民益生物科技有限公司 | A kind of feed three-dimensional multistage hole nano zine oxide and preparation method thereof |
| CN107793581B (en) * | 2017-10-26 | 2020-07-31 | 温岭市林氏鞋业有限公司 | Efficient antibacterial master batch and preparation method thereof |
| CN108043400B (en) * | 2017-12-08 | 2019-10-18 | 浙江工业大学 | A kind of Au-Bi2MoO6/ diatomite composite material and the preparation method and application thereof |
| CN112221436B (en) * | 2019-12-10 | 2022-08-12 | 天津科技大学 | Preparation method of silver/silver chloride composite cubic nanoparticle self-assembled microspheres |
| CN114920540A (en) * | 2022-05-17 | 2022-08-19 | 孙影影 | Environment-friendly antibacterial domestic ceramic and preparation method thereof |
| CN114988456B (en) * | 2022-06-21 | 2023-10-03 | 深圳市尚维高科有限公司 | Zinc oxide composite particle, preparation method and application thereof in virus splitting in nucleic acid detection |
| CN115245815A (en) * | 2022-07-21 | 2022-10-28 | 中南大学 | Adsorbing material based on electrostatic assembly and preparation method and application thereof |
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| US4312931A (en) * | 1980-09-02 | 1982-01-26 | General Motors Corporation | Zinc electrode containing porous calcium silicate |
| CN101245260A (en) * | 2008-02-20 | 2008-08-20 | 宋金文 | Method for producing ultra-low-sulfur oil |
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| JP2003081725A (en) * | 2001-09-13 | 2003-03-19 | Tadashi Inoue | Method for regenerating inorganic antimicrobial agent |
| KR101068998B1 (en) * | 2008-08-11 | 2011-09-30 | 금호석유화학 주식회사 | Method for preparation of the N-substitution maleimide |
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| US4312931A (en) * | 1980-09-02 | 1982-01-26 | General Motors Corporation | Zinc electrode containing porous calcium silicate |
| CN101245260A (en) * | 2008-02-20 | 2008-08-20 | 宋金文 | Method for producing ultra-low-sulfur oil |
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