CN103318945B - Preparation method of colloidal solution of nano-ZnO - Google Patents
Preparation method of colloidal solution of nano-ZnO Download PDFInfo
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- CN103318945B CN103318945B CN201310290910.3A CN201310290910A CN103318945B CN 103318945 B CN103318945 B CN 103318945B CN 201310290910 A CN201310290910 A CN 201310290910A CN 103318945 B CN103318945 B CN 103318945B
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- vltra tears
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Abstract
The invention discloses a preparation method of a colloidal solution of nano-ZnO. The method comprises the following steps: mixing an aqueous modified cellulose solution having a concentration of 0.001-100g/L with a zinc salt solution having a concentration of 0.01-100g/L according to a volume ration of 1:10-100:1, wherein the modified cellulose is dialdehyde hydehydroxypropyl methyl cellulose obtained through the selective oxidation of the secondary hydroxyl groups in the C2 and C3 positions of hydroxypropyl methyl cellulose; and slowly adding an alkaline solution for adjusting the pH value to 8.5-11.5, and stirring at 20-90DEG C for 1-600min until reaction completion in order to obtain the colloidal solution of nano-ZnO having an average particle size of 1-100nm. The prepared nano-ZnO has the advantages of ultrahigh stability, antibiosis and ultraviolet resistance, good biocompatibility and good biodegradability, and can be applied to the coat field, the textile field, the medical health field and the like.
Description
Technical field
The invention belongs to the preparing technical field of nano material, particularly relate to a kind of preparation method of colloidal solution of nano-ZnO.
Background technology
Nano zine oxide is a kind of Multifunction inorganic semiconductor material, and particle diameter is generally between 1 ~ 100nm.After zinc oxide particle diameter reaches Nano grade, special surface effects, volume effect, quantum size effect can be created, thus show special performance.Such as, nano zine oxide has outstanding non-migratory, fluorescence, absorption and scatters ultraviolet etc. compared with common zinc oxide, can be widely used in the fields such as electricity, optics, magnetics, chemical catalysis.Utilize nano zine oxide to the absorptive character of UV-light, ultraviolet detector, LED, LD and ultraviolet ray resistant textiles can be prepared.Utilize nanometer silver zinc oxide photocatalysis effectiveness, can be used for process organic waste water and the antibacterial finish to textiles.Utilize the piezoelectric properties that zinc oxide is good, can be used to prepare the isobaric electrical equipment material of acousto-optic modulator.In recent years, also someone utilizes nano zine oxide to develop solar cell, nanometer microgenerator etc., and these all illustrate that nano zine oxide has very outstanding character and wide application prospect.
The same with the preparation method of a lot of nano material, the preparation method of nano zine oxide is also divided into Physical and chemical method.Physical comprises magnetron sputtering, ball milled, pulsed laser deposition etc., and nano zine oxide prepared by aforesaid method has less particle diameter and size distribution, but higher to equipment requirements.In addition, for the nano zine oxide of some particular requirements, as the nano zine oxide of nucleocapsid structure, the nano zine oxide (nano wire, rod), co-doped nano zinc oxide etc. of special appearance, Physical is often helpless.Chemical method comprises coprecipitation method, hydro-thermal reaction method, sol-gel method method, electrochemical process etc.Above-mentioned preparation method is low for equipment requirements and can realize the specify of nano zine oxide, but chemical method often exists, and the control of particle diameter difficulty, size distribution are large, the easy problem such as reunions, this just higher to chemical method proposition requirement.
Nanometer silver zinc oxide has outstanding uv-absorbing and anti-microbial property because of it and is widely used in functionalization textile field.The treatment process of nano zine oxide textiles normally utilizes colloidal solution of nano-ZnO to carry out Final finishing to obtain to textiles.Nano zine oxide must meet following requirement in the application of functionalization textile field: Particle Size of Nanometer ZnO must uniformity and stability of solution is high; For disperseing and protecting the protective material of nano zine oxide must be nontoxic to human-body safety, and the specification (textiles Surfactant content there are strict requirements, therefore tensio-active agent be unfit to do protective material) of textiles about surface residue must be met; The nano zine oxide of protective material protection must have good binding ability with fabric, and has good weather resistance and washing fastness.Obviously the nano zine oxide meeting above-mentioned requirements is few.
Summary of the invention
The object of the invention is to the deficiency overcoming prior art existence, the colloidal solution of nano-ZnO that a kind of security is high, stability of solution is high is provided.
In order to solve the problems of the technologies described above better, technical scheme of the present invention, for providing a kind of preparation method of colloidal solution of nano-ZnO, comprises the steps:
(1) zinc salt solution be the modified-cellulose aqueous solution and the concentration of 0.001g/L ~ 100g/L by concentration being 0.01 ~ 100g/L mixes with the volume ratio of 1:10 ~ 100:1, obtains mixing solutions; Described modified-cellulose is to Vltra tears C
2, C
3secondary hydroxyl on position carries out the dialdehyde-based Vltra tears that selective oxidation obtains;
(2) be slowly added drop-wise in mixing solutions by basic solution, control ph is 8.5 ~ 11.5, under the temperature condition of 20 DEG C ~ 90 DEG C, stir 1 ~ 600min, and namely obtaining median size is the colloidal solution of nano-ZnO of 1 ~ 100nm.
The molecular weight of Vltra tears of the present invention is 1000 ~ 100000.Described zinc salt solution is Zn (NO
3)
2, ZnCl
2, ZnSO
4or Zn (CH
3cOO)
2the aqueous solution in one.Described basic solution is NH
3, NaOH, KOH, NH
2the aqueous solution.
Dialdehyde-based method for preparing hydroxypropylmethylcellulose of the present invention see document " aggregated structure of selective oxidized cotton fiber " (Xu Yunhui, Lin Hong, Chen Yuyue. [J]. textile journal, 2006,27 (11): 1-5).
Compared with prior art, advantage of the present invention is:
1, the full-bodied aqueous solution is formed in Vltra tears water soluble solution, thus not good to zinc oxide protective value.The present invention utilizes sodium periodate to Vltra tears C
2, C
3secondary hydroxyl on position carries out the dialdehyde-based Vltra tears that selective oxidation obtains, and obtains a large amount of aldehyde groups, causes the water-soluble viscosity that greatly strengthens greatly to reduce; Meanwhile, aldehyde groups has highly active conjugated electrons cloud, effectively can limit zincite crystal and increases and effectively can be combined in crystal surface of ZnO thus the object reaching protection and disperse.
2, the present invention is directed to textile field, utilize and have the modified-cellulose of good safety, biocompatibility and biological degradability, a kind of highly stable and colloidal solution of nano-ZnO to human-body safety has been prepared in design.Dialdehyde-based Vltra tears has good biocompatibility and biological degradability, and its security can be fully guaranteed.
3, prepared colloidal solution of nano-ZnO cost is low, technique is simple, good stability, nanometer silver uniform particle sizes, and has good uvioresistant, antibacterial effect, can extensively apply with the field such as coating, weaving, health care.
Accompanying drawing explanation
Fig. 1 be provided by the invention before modified after the infrared spectrogram of Vltra tears;
Fig. 2 is the prepared nano zine oxide Zeta potential figure that the embodiment of the present invention provides;
Fig. 3 is the XRD spectra of the nano zine oxide that the embodiment of the present invention provides;
Fig. 4 is the SEM figure of the nano zine oxide that the embodiment of the present invention provides.
Embodiment
Content of the present invention is illustrated below in conjunction with drawings and Examples.
Embodiment 1:
1, the technical scheme provided by document " aggregated structure of selective oxidized cotton fiber " prepares dialdehyde-based hydroxypropylcellulose, its preparation method is: be first dissolved in deionized water by Vltra tears and obtain the Gonak that mass percent is 1%, then be that the 1% sodium periodate aqueous solution is progressively added dropwise in above-mentioned solution by massfraction, both volume ratios are 1:1 ~ 50:1.Setting temperature of reaction is 50 DEG C, and under light protected environment, mechanical stirring is fully reacted, and after reaction 30min, reaction solution is cooled to room temperature.Then above-mentioned soln using dialysis molecular weight be 5000 dialysis tubing dialyse 24 hours, pure dialdehyde-based Vltra tears can be obtained.See accompanying drawing 1, it be the present embodiment provide before modified after the infrared spectrogram of Vltra tears, in figure, curve a is Vltra tears, and curve b is dialdehyde-based Vltra tears; Fig. 1 result shows, and after sodium periodate oxidation, Vltra tears is at 1737cm
-1there is the charateristic avsorption band of aldehyde radical, shown that this reaction can successfully prepare dialdehyde-based Vltra tears.In the present embodiment, get 0.10g dialdehyde-based Vltra tears and be dissolved in 100mL deionized water, obtain the aqueous solution of the dialdehyde-based Vltra tears of concentration 1g/L;
2, the zinc nitrate getting 0.727g is dissolved in 100mL deionized water, obtains the zinc nitrate solution of concentration 7.27g/L;
3, the sodium hydroxide getting 5.00g is dissolved in 100mL deionized water, obtains the aqueous sodium hydroxide solution of concentration 50g/L;
4, the dialdehyde-based Vltra tears aqueous solution of 1g/L and the zinc nitrate aqueous solution of 7.87g/L are mixed with the volume ratio of 4:1, drip the aqueous solution (mass ratio of zinc nitrate and sodium hydroxide is 189:80) of the sodium hydroxide of 50g/L under at the uniform velocity stirring at 70 DEG C, after reaction 2h, the colloidal solution of nano-ZnO that particle diameter is 10 ~ 60nm can be obtained.
See accompanying drawing 2, it is the Zeta potential figure of the colloidal solution of nano-ZnO that the present embodiment provides; Zeta current potential is the important indicator characterizing colloidal dispersion stability.The size of Zeta current potential absolute value is its stability size of reflection, and absolute value is larger, and stability is better.Generally, the absolute value of Zeta current potential shows more than 30 mV the stability that sample is higher.Prepared surface of nanometer zinc oxide Zeta potential is-58.6mV (zinc oxide colloidal solution pH is 9.0) as seen from the figure, and so high surface potential describes prepared colloidal solution of nano-ZnO and has higher stability.This surface potential is obviously the result of dialdehyde-based Vltra tears decorated nanometer zinc oxide surface, and this causes its surface containing a large amount of hydroxyls and aldehyde radical.And these groups can not only considerably increase the current potential of surface of nanometer zinc oxide, also serve the effect of effective charge space steric hindrance simultaneously.
See accompanying drawing 3, it is the XRD spectra of the Nano silver solution that the present embodiment provides; As seen from the figure, contrast with standard card JCPDS No.89-0511, its XRD diffraction peak is completely corresponding with zinc oxide XRD standard spectrogram, the diffraction peak of 9 diffraction peaks (100), (002), (101) of corresponding zinc oxide, (102), (110), (103), (112), (200) and (201) crystal face respectively.
See accompanying drawing 4, it is the SEM figure of the nano-Ag particles that the present embodiment provides, and magnification is 60,000 times.Nano zine oxide is that standard is spherical as seen from the figure, and size is 10 ~ 60nm, and size distribution is more even.
Embodiment 2:
1, dialdehyde-based Vltra tears is prepared by embodiment 1 technical scheme.Get 0.20g dialdehyde-based Vltra tears to be dissolved in 100mL deionized water, obtain the dialdehyde-based Vltra tears aqueous solution of concentration 2g/L;
2, the zinc nitrate getting 0.727g is dissolved in 100mL deionized water, obtains the zinc nitrate solution of concentration 7.27g/L;
3, the sodium hydroxide getting 5g is dissolved in 100mL deionized water, obtains the aqueous sodium hydroxide solution of concentration 50g/L;
4, the zinc nitrate aqueous solution being 7.87g/L by the dialdehyde-based Vltra tears aqueous solution of 2g/L and massfraction mixes with the volume ratio of 4:1, drip the aqueous solution (mass ratio of zinc nitrate and sodium hydroxide is 189:80) of the sodium hydroxide of 50g/L under at the uniform velocity stirring at 70 DEG C, after reaction 2h, the colloidal solution of nano-ZnO that particle diameter is 10 ~ 60nm can be obtained.
Embodiment 3:
1, get 0.20g dialdehyde-based Vltra tears to be dissolved in 100mL deionized water, obtain the dialdehyde-based Vltra tears aqueous solution of concentration 2g/L;
2, the zinc nitrate getting 0.727g is dissolved in 100mL deionized water, obtains the zinc nitrate solution of concentration 7.27g/L;
3, get 5mL ammoniacal liquor to be dissolved in 95mL deionized water, obtain ammonia aqueous solution;
4, the zinc nitrate aqueous solution being 7.87g/L by the dialdehyde-based Vltra tears aqueous solution of 2g/L and massfraction mixes with the volume ratio of 4:1, drip ammonia aqueous solution (mass ratio of zinc nitrate and ammoniacal liquor is 189:20) under at the uniform velocity stirring at 70 DEG C, after reaction 2h, the colloidal solution of nano-ZnO that particle diameter is 10 ~ 60nm can be obtained.
Claims (3)
1. a preparation method for colloidal solution of nano-ZnO, is characterized in that comprising the steps:
(1) zinc salt solution be the modified-cellulose aqueous solution and the concentration of 0.001g/L ~ 100g/L by concentration being 0.01 ~ 100g/L mixes with the volume ratio of 1:10 ~ 100:1, obtains mixing solutions; Described modified-cellulose is to Vltra tears C
2, C
3secondary hydroxyl on position carries out the dialdehyde-based Vltra tears that selective oxidation obtains; Described Vltra tears molecular weight is 1000 ~ 100000;
(2) be slowly added drop-wise in mixing solutions by basic solution, control ph is 8.5 ~ 11.5, then under the temperature condition of 20 DEG C ~ 90 DEG C, stirs 1 ~ 600min, and namely obtaining median size is the colloidal solution of nano-ZnO of 1 ~ 100nm.
2. the preparation method of a kind of colloidal solution of nano-ZnO according to claim 1, is characterized in that: described zinc salt solution is Zn (NO
3)
2, ZnCl
2, ZnSO
4or Zn (CH
3cOO)
2the aqueous solution in one.
3. the preparation method of a kind of colloidal solution of nano-ZnO according to claim 1, is characterized in that: described basic solution is NH
3, NaOH or KOH the aqueous solution.
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| CN104941537B (en) * | 2015-05-28 | 2017-08-01 | 南京林业大学 | A kind of preparation method of strip nano-ZnO/cellulose gel glue material |
| CN104892961B (en) * | 2015-05-28 | 2017-12-08 | 南京林业大学 | A kind of preparation method of fibre strip element gel mesoporous material |
| CN104941540B (en) * | 2015-05-28 | 2017-10-20 | 南京林业大学 | A kind of nano-ZnO/cellulose gel particle and preparation method thereof |
| CN104941683B (en) * | 2015-06-09 | 2017-03-01 | 南京林业大学 | One kind receives micro- ZnO/ compound cellulose strip material and preparation method thereof |
| CN105594739B (en) * | 2015-12-22 | 2018-07-27 | 广东迪美生物技术有限公司 | A kind of visible light catalytic composite antibacterial material and preparation method thereof |
| CN106006709B (en) * | 2016-05-18 | 2018-05-08 | 南京林业大学 | A kind of cellulose liquor zinci chloridi prepares the preparation method of nano ZnO powder |
| CN106046423B (en) * | 2016-05-25 | 2018-08-17 | 南京林业大学 | A kind of preparation method of nano-ZnO/cellulose composite material |
| CN107324286A (en) * | 2017-06-12 | 2017-11-07 | 电子科技大学 | A kind of method of stable dispersion metal oxide nanoparticles in aqueous phase |
| CN109721094A (en) * | 2019-02-27 | 2019-05-07 | 西南科技大学 | A kind of preparation method preparing zinc-oxide nano colloidal solution |
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| US4410446A (en) * | 1979-06-07 | 1983-10-18 | Petrolite Corporation | Zinc oxide dispersions by decomposition of zinc acetate |
| DE19907704A1 (en) * | 1999-02-23 | 2000-08-24 | Bayer Ag | Nano-scale precipitating zinc oxide used e.g. for protecting UV-sensitive organic polymers consists of particles having an average specified primary particle diameter |
| CN103101963A (en) * | 2011-11-11 | 2013-05-15 | 贵州省纳米材料工程中心 | Method of preparing and purifying transparent nano-zinc oxide sol |
| CN102936032B (en) * | 2012-11-30 | 2014-11-05 | 苏州大学 | Preparation method of nano-zinc oxide aqueous solution |
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