CN102941348B - Method for preparing nano-silver hydrosol by using plant extract - Google Patents
Method for preparing nano-silver hydrosol by using plant extract Download PDFInfo
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- CN102941348B CN102941348B CN201210515270.7A CN201210515270A CN102941348B CN 102941348 B CN102941348 B CN 102941348B CN 201210515270 A CN201210515270 A CN 201210515270A CN 102941348 B CN102941348 B CN 102941348B
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Abstract
The invention discloses a method for preparing nano-silver hydrosol by using a plant extract. The method comprises the following steps of: dissolving or dispersing soluble amylose into deionized water, stirring until the soluble amylase is completely gelatinized; adding a Tollens solution and mixing to obtain a starch-Tollens compound solution; freezing the compound solution into ice blocks and smashing the ice blocks into colloidal particle ice powder; and adding the colloidal particle ice powder into an alkaline plant blade extract and fully mixing to obtain the nano-silver hydrosol with the particle size of 1 to 100 nm. By the method, a silver ion and protecting agent compound solution is frozen and smashed; the obtained ice powder carried with silver ions is activated and reduced to obtain nano silver; the method is simple, convenient and high in controllability; and the prepared nano-silver hydrosol is high in stability and has the advantages of small nano-silver particle size, uniform distribution, high antibacterial efficiency and the like and can be widely applied to the field of electrons, textile, catalysis, medical materials, medical treatment and public health and the like.
Description
Technical field
The present invention relates to a kind of method that plant extraction liquid prepares nano-silver hydrosol, belong to technical field of nano material.
Background technology
Nano material be a kind of by size at the molecular new material of the nanoparticle of 1 ~ 100nm, possess special skin effect, small-size effect, quantum size effect and macro quanta tunnel effect, present many unusual physicochemical properties being different from conventional material.Namely Nano Silver is that particle diameter is at nano level argent simple substance, nano silver material possesses the basic characteristics of nano material, especially in electronics, optics, antibacterial and catalysis etc., its performance advantage is obvious, catalyst material, battery electrode material, low temperature Heat Conduction Material, electrocondution slurry, anti-biotic material and medical material can be widely used in, have a extensive future, be just subject to paying close attention to widely and more deep research.
Traditional Nano Silver preparation method is mainly divided into physical method and chemical method, the two advantages, but also exists obviously not enough.Nano Silver purity prepared by physical method is high, active high, but product particle size distribution is wide, easily reunites; The Nano Silver that chemical method obtains then possesses good dispersiveness; narrow diameter distribution; pattern is relatively uniform; but material surface is often with impurity; and the reducing agent introduced in preparation process (boron hydride, hydrazine hydrate, dimethyl formamide etc.) or protective agent (polyvinylpyrrolidone, metaphosphate, dodecyl sodium sulfate etc.) strong toxicity even carcinogenic, have potential hazard to environmental and biological materials.By contrast, plant reduction method prepare Nano Silver then because its raw material sources are extensive, reaction condition is gentle, equipment requirement is low, product stable and the advantages such as environmental friendliness and receive much concern.
Prepare Nano Silver about plant reduction, report the earliest sees Gardea Torresde in 2002 etc. and finds that the root of clover can Ag in adsorbent solution
+, and be reduced to the nano-Ag particles of 2 ~ 3nm; The water cooking liquid of the geranium leaves such as Shankar, chinaberry leaf, emblic, mustard type rape, Jatropha curcas has prepared nano-Ag particles afterwards, and camphor leaf, ginkgo leaf and lily magnolia also have relevant report in addition.
Starch as a kind of polysaccharide reproducibility natural polymer, wide material sources, cheap.Soluble starch is amylose mainly, be by multiple glucose unit form containing the macromolecule enriching hydroxyl, by molecule and intermolecular hydrogen bond action form " capsule " of molecular level, for the growth of metal nanoparticle provides template.
Summary of the invention
The object of this invention is to provide a kind of with low cost, easy and simple to handle, controllability is strong, and the preparation method of the nano-silver hydrosol of environmental protection, it adopts the preparation method of plant extraction liquid, the nano-silver hydrosol good stability obtained, and is uniformly dispersed.
The technical scheme realizing the object of the invention is to provide a kind of method that plant extraction liquid prepares nano-silver hydrosol, comprises the steps:
(1) soluble Amylose is dissolved or dispersed in deionized water, at 60 ~ 100 DEG C, is stirred to its complete gelatinization, obtain the starch solution that concentration is 0.01 ~ 2wt%;
(2) silver ammino solution that starch solution and concentration are 0.01 ~ 1wt% mixes by 1:6 ~ 1:1 by volume, obtains starch-Yin ammonia composite solution;
(3) be frozen into ice cube under composite solution being placed in-20 ~-5 DEG C of conditions, after pulverizing, obtain the colloidal particle ice powder that particle diameter is 1 ~ 3mm;
(4) process is carried out to plant leaf blade and obtain plant leaf blade extract, extract is dispersed or dissolved in deionized water, obtain the plant leaf blade solution of extract that concentration is 1 ~ 100wt%, regulate pH to 9 ~ 11 by NaOH solution, obtain alkaline soil plant leaf extract;
(5) colloidal particle ice powder is added in alkaline soil plant leaf extract mix by weight 1:5 ~ 1:20, under being placed in 20 ~ 50 DEG C of conditions, stir 0.5 ~ 12h, obtain the sodium rice silver hydrosol prepared with plant extraction liquid that particle diameter is 1 ~ 100nm.
Soluble Amylose of the present invention, comprise in cornstarch, wheat kind of starch, tapioca, starch from sweet potato, sweet potato starch, farina, Lotus Root Starch, water caltrop starch and Chinese Water Chestnut Starch one or more.
Described plant leaf blade is the one in the Aloe under Liliaceae or the Opuntia under Cactaceae, or their any combination.Plant leaf blade extract is extract solution from aloe or cactus extraction, and preparation method comprises: aloe or cactus vanes deionized water cleaned, obtain inner bag after peeling, then through stripping and slicing, pulverize, filter, be separated, purify, obtain extract solution from aloe or cactus extraction.
Described silver ammino solution is silver nitrate or silver sulfate, the complex compound formed after mixing with amino-compound; Described amino-compound is ammoniacal liquor.
Starch be by multiple glucose unit form containing the macromolecule enriching hydroxyl, by molecule and intermolecular hydrogen bond action form " capsule " of molecular level, for the growth of metal nanoparticle provides template; Soluble starch-Yin ammonia composite solution through freezing processing can realize starch polymer to silver ion dispersed, attachment parcel or even complexing fix, thus guarantee silver ion stable existence, a kind of colloidal particle of stable and uniform of Ag-bearing ion then can be obtained again, convenient preservation through pulverization process; Be rich in polysaccharide, the aloe of amino acid isoreactivity material or cactus extraction when this granule is scattered in, the rapid solution of ice powder and the activation of silver ion can be realized under condition of heating and stirring, a large amount of active group (-OH ,-NH in plant extraction liquid
2,-COOH etc.) effect under, homodisperse silver ion is reduced to Nano Silver, and under the protective effect of starch, nano-Ag particles Absorbable organic halogens exists.
Compared with prior art, the invention has the beneficial effects as follows:
1, select soluble starch as the dispersant of silver ion and protective agent; plant leaf blade extract serves as agent for capturing and reducing agent; prepare Nano Silver; avoid the introducing of toxic reagent; possess raw material extensively, reaction temperature and, the advantage such as asepsis environment-protecting, meet the theory of " Green Chemistry " completely.
2, by making freezing, pulverization process in advance to silver ion and protectant complex liquid, then activate the ice powder of gained Ag-bearing ion, reduce and prepare Nano Silver, the method is simply effective, controllability is strong.
3, the nano-silver hydrosol prepared possesses good stability, and Nano Silver particle diameter is little, be evenly distributed, and antimicrobial efficiency advantages of higher, can be widely used in the fields such as electronics, weaving, catalysis, medical material and health care.
Accompanying drawing explanation
Fig. 1 is the uv-visible absorption spectra figure (UV-Vis figure) of the nano-silver hydrosol that the embodiment of the present invention provides;
Fig. 2 is that the nano-silver hydrosol that provides of the embodiment of the present invention is through the observable Nano Silver aspect graph of transmission electron microscope (TEM);
Fig. 3 is that the nano-silver hydrosol that the embodiment of the present invention provides records wherein Nano Silver domain size distribution result figure through laser particle instrument (DLS).
Detailed description of the invention
Below in conjunction with drawings and Examples, technical solution of the present invention is described in detail.
Embodiment 1:
Getting 0.1g cornstarch is scattered in 10ml deionized water, be stirred to gelatinization at 80 DEG C and obtain starch solution, being added into 20ml concentration is mix in the silver ammino solution of 1wt%, described silver ammino solution is the complex compound formed after silver nitrate mixes with ammoniacal liquor, obtain starch-silver ion composite solution, composite solution is placed in freezing processing under-20 DEG C of conditions, after it freezes, makes pulverization process, obtaining particle diameter is that the ice powder of 1 ~ 3mm is about 30g.
By aloe leaf through deionized water clean, peeling after obtain aloe inner bag, again through stripping and slicing, pulverize, filter, separating-purifying obtains aloe leaf extract, be scattered in deionized water, preparation 300ml concentration is the aloe leaf extract aqueous solution of 10 wt %, and NaOH solution regulates its pH to 11 to obtain alkaline aloe leaf extract; Be added into by above-mentioned ice powder in alkaline aloe leaf extract, 40 DEG C are stirred 300min, obtain the sodium rice silver hydrosol of particle diameter at 2 ~ 25nm.
Embodiment 2:
Getting 0.05g tapioca is scattered in 5ml deionized water, be stirred to gelatinization at 90 DEG C and obtain starch solution, being added into 20ml concentration is mix in the silver ammino solution of 0.5wt%, described silver ammino solution is the complex compound formed after silver sulfate mixes with ammoniacal liquor, obtain starch-silver ion composite solution, composite solution is placed in freezing processing under-10 DEG C of conditions, after it freezes, makes pulverization process, obtaining particle diameter is that the ice powder of 1 ~ 3mm is about 25g.
By cactus through deionized water clean, peeling after obtain inner bag, again through stripping and slicing, pulverize, filter, be separated, purify and obtain cactus extraction, be scattered in deionized water, preparation 175ml concentration is the cactus leaf extract aqueous solution of 40 wt %, and NaOH solution regulates its pH to 10.7 to obtain alkaline cactus leaf extract; Be added into by obtained ice powder in alkaline cactus leaf extract, 30 DEG C are stirred 300min, obtain the sodium rice silver hydrosol.
See accompanying drawing 1, as seen from Figure 1, there is typical Nano Silver characteristic absorption peak, proved to generate nano-Ag particles in product water colloidal sol in the uv-visible absorption spectra figure (UV-Vis figure) of the nano-silver hydrosol that it provides for the present embodiment at 408nm place.
See accompanying drawing 2, the nano-silver hydrosol that it provides for the present embodiment is through the observable Nano Silver aspect graph of transmission electron microscope (TEM), and can be seen by Fig. 2, the Nano Silver in the hydrosol is spheric granules.
See accompanying drawing 3, the nano-silver hydrosol that it provides for the present embodiment records wherein Nano Silver domain size distribution result figure through laser particle instrument (DLS), and can be seen by Fig. 3, Nano Silver particle diameter is at 10 ~ 40nm.
Embodiment 3:
Getting 0.05g wheaten starch is scattered in 10ml deionized water, be stirred to gelatinization at 90 DEG C and obtain starch solution, being added into 20ml concentration is mix in the silver ammino solution of 0.2wt%, described silver ammino solution is the complex compound formed after silver sulfate mixes with ammoniacal liquor, obtain starch-silver ion composite solution, composite solution is placed in freezing processing under-10 DEG C of conditions, after it freezes, makes pulverization process, obtaining particle diameter is that the ice powder of 1 ~ 3mm is about 30g.
Aloe leaf extract and cactus extraction is prepared by embodiment 1 and 2 technical scheme.Be the aloe leaf extract aqueous solution of 20 wt % and 250ml concentration by 200ml concentration be that 30 wt % cactus leaf extract aqueous solution are even, NaOH solution regulate its pH to 10.7 alkaline soil plant leaf extract; Be added in alkaline soil plant leaf extract by above-mentioned ice powder, 50 DEG C are stirred 120min, obtain the sodium rice silver hydrosol of particle diameter at 5 ~ 20nm.
Claims (6)
1. prepare a method for nano-silver hydrosol with plant extraction liquid, it is characterized in that comprising the steps:
(1) soluble Amylose is dissolved or dispersed in deionized water, at 60 ~ 100 DEG C, is stirred to its complete gelatinization, obtain the starch solution that concentration is 0.01 ~ 2wt%;
(2) silver ammino solution that starch solution and concentration are 0.01 ~ 1wt% mixes by 1:6 ~ 1:1 by volume, obtains starch-Yin ammonia composite solution;
(3) be frozen into ice cube under composite solution being placed in-20 ~-5 DEG C of conditions, after pulverizing, obtain the colloidal particle ice powder that particle diameter is 1 ~ 3mm;
(4) process is carried out to plant leaf blade and obtain plant leaf blade extract, extract is dispersed or dissolved in deionized water, obtain the plant leaf blade solution of extract that concentration is 1 ~ 40wt%, regulate pH to 9 ~ 11 by NaOH solution, obtain alkaline soil plant leaf extract;
(5) colloidal particle ice powder is added in alkaline soil plant leaf extract mix by weight 1:5 ~ 1:20, under being placed in 20 ~ 50 DEG C of conditions, stir 0.5 ~ 12h, obtain the sodium rice silver hydrosol prepared with plant extraction liquid that particle diameter is 1 ~ 100nm.
2. a kind of plant extraction liquid according to claim 1 prepares the method for nano-silver hydrosol, it is characterized in that: described soluble Amylose, comprise in cornstarch, wheat kind of starch, tapioca, starch from sweet potato, sweet potato starch, farina, Lotus Root Starch, water caltrop starch and Chinese Water Chestnut Starch one or more.
3. a kind of plant extraction liquid according to claim 1 prepares the method for nano-silver hydrosol, it is characterized in that: described plant leaf blade is the one in the Aloe under Liliaceae or the Opuntia under Cactaceae, or their any combination.
4. a kind of plant extraction liquid according to claim 1 prepares the method for nano-silver hydrosol, it is characterized in that: described plant leaf blade extract is extract solution from aloe or cactus extraction, preparation method comprises: aloe or cactus vanes deionized water cleaned, obtain inner bag after peeling, again through stripping and slicing, pulverize, filter, be separated, purify, obtain extract solution from aloe or cactus extraction.
5. a kind of plant extraction liquid according to claim 1 prepares the method for nano-silver hydrosol, it is characterized in that: described silver ammino solution is silver nitrate or silver sulfate, the complex compound formed after mixing with amino-compound.
6. a kind of plant extraction liquid according to claim 5 prepares the method for nano-silver hydrosol, it is characterized in that: described amino-compound is ammoniacal liquor.
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| CN105037750A (en) * | 2015-08-26 | 2015-11-11 | 界首市天鸿新材料股份有限公司 | Method for preparing hydrosol by using modified starch |
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