CN103271942B - Method for preparing nano silver-kaolinite compound by using hydrated kaolinite as carrier - Google Patents
Method for preparing nano silver-kaolinite compound by using hydrated kaolinite as carrier Download PDFInfo
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- CN103271942B CN103271942B CN201310200686.4A CN201310200686A CN103271942B CN 103271942 B CN103271942 B CN 103271942B CN 201310200686 A CN201310200686 A CN 201310200686A CN 103271942 B CN103271942 B CN 103271942B
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Abstract
The invention discloses a method for preparing a nano silver-kaolinite compound by using hydrated kaolinite as a carrier, which comprises the following steps: mixing every 1g of hydrated kaolinite with 200ml of 0.01-0.03 mol/L nano silver solution, stirring at room temperature-60 DEG C for 48-24 hours, centrifuging the mixture, and washing with water to obtain the nano silver-kaolinite compound of which the surface is loaded with nano silver. Nano silver particles in the nano silver-kaolinite compound prepared by the invention are distributed on the surface of the kaolinite; the particle size is mainly distributed in a range of 2-25nm; and nano silver particles of 7-9nm approximately account for 40% or so. The nano silver-kaolinite compound can serve as a composite material combining haemostatic property of kaolinite and antimicrobial property of nano silver. According to the invention, the preparation process is simple, high in speed, low in cost and easy to realize.
Description
Technical field
The present invention relates to a kind of method preparing nanometer silver-kaolinite complex, especially relate to a kind of with 0.84nm hydration kaolinite for carrier, prepare the method for nanometer silver-kaolinite complex.
Background technology
Losing blood excessive is the major reason being subject to open wound personnel death.Traditional Hemostasis is as pressurization, dressing filling and tourniquet etc., and be all stopped blooding by pressure, the mode of this Pressur hemostatic can cause remote organization's ischemia and Developmental and Metabolic Disorder to cause serious complication.And use hemorrhage, as fibrin sealant (FD dressing), poly IV-acetylglucosamine dressing (RDH) etc., how due to expensive or character is unstable and have impact on application prospect.American National naval medical centre have developed a kind of kaolinite derivates nanometer granule with quick-acting haemostatic powder effect, and its main component is zeolite, and commodity are called QuikClot (QC).The hemostatic mechanism of zeolite is that it has larger specific surface area and inner highfield, has very strong physisorption, blood constituent is concentrated, improve the relative concentration of hemorrhage local thrombin to hydrone isopolarity molecule.But zeolite releases a large amount of heat in the process of water suction, easily causes the secondary of wound to be burnt.In recent years, research finds that kaolinite also has the haemostatic effect of working as with zeolite facies, such as, after anhydrous QC hemorrhage mixes with blood, the time needed for blood coagulation is about 2 h, and after kaolinite mixes with blood, blood coagulation required time is about 2.25 h, suitable with QC hemorrhage.But kaolinic hemostatic mechanism is different, and research is thought: (1) kaolinite is electronegative at pH value of blood lower surface, can activate the process of setting of blood with contacting blood.(2) water content is very little on the impact of kaolinite anthemorrhagic performance, and moisture kaolinic coagulant property has almost no change.(3) surface area and the impact of particle size on kaolinite anthemorrhagic performance little.(4) kaolinite contacts with water and releases heat hardly.These performances, especially contact not exothermic advantage and make kaolinite may become a kind of outstanding hemorrhage with water.
Research in recent years finds that silver ion is one of bactericidal the strongest active metal ion, and nanometer silver is by the carry out slow releasing of its surface to silver ion, has excellent antibacterial characteristics, becomes the most potential anti-biotic material.Nanometer silver is implanted in binder by existing research, uses as anti-biotic material.The anti-microbial property of nanometer silver is very large by the impact of nano-particle pattern, improves the raising that surface area is conducive to anti-microbial property, but due to the stability of nanometer silver not high, easily reunite, have impact on its application.In order to prevent nano-Ag particles from reuniting, research finds, by nano-silver loaded at clay mineral surface or insertion layer silicate mineral interlayer, can prevent it from reuniting.Research finds, nanometer silver-silicate mineral has certain inhibition to bacillus pyocyaneus, S. aureus L-forms and escherichia coli.Obviously, if by nanometer silver and hydration kaolinite compound, then can obtain that there is antibacterial and multifunctional nanocomposites that is anthemorrhagic performance.
The method of reducing nano-silver comprises: use chemical reducing agent, uses irradiation under ultraviolet ray reactant, and uses thermal reduction etc., and these Measures compare are complicated, higher to the requirement of reaction condition.In addition, kaolinite intercalation presoma and silver nitrate is utilized to react, silver ion can be incorporated into kaolinite interlayer, in this approach, the Organic substance prepared used by intercalation presoma has certain toxicity as dimethyl sulfoxide (DMSO) etc., also limit the use of nanometer silver-kaolinite complex.If can the step of simplified reduction nanometer silver, and avoid noxious substance to be incorporated in complex, will the using value of nanometer silver-kaolinite complex be improved.The big first-class people that shuts out studies the 0.84nm hydration kaolinite (patent, application number 201210195865.9) having prepared a kind of environmental protection, and in the kaolinic process of preparation hydration, first kaolinite is heat-treated under certain condition with hydrazine hydrate and defined hydration kaolinite.Due to the reproducibility that hydrazine hydrate is stronger, the Al-OH group on this hydration kaolinite surface prepared, can with Al-OH with certain negative electricity
-form exist, the also Al-OH on i.e. hydration kaolinite surface
-and there is the ability of certain reduction reaction between the material with oxidisability.This programme utilizes the reproducibility on this real-time kaolinic surface of preparation hydration just, direct and silver nitrate solution reacts, do not need additional reduction step, successfully achieve the reduction of silver ion, prepare nanometer silver-kaolinite complex, and preparation technology is simple, in the complex obtained, itself is not containing noxious substance.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, a kind of method preparing nanometer silver-kaolinite complex with hydration kaolinite is provided.The present invention utilizes a kind of surface to have the d of certain reproducibility
001=0.84nm hydration kaolinite, will have the silver ion reduction of oxidisability in silver nitrate solution, and then at hydration kaolinite area load nano-Ag particles, obtains nanometer silver-kaolinite complex.
The object of the invention is to be achieved through the following technical solutions: a kind of with hydration kaolinite for carrier prepares the method for nanometer silver-kaolinite complex, comprise the following steps:
(1) silver nitrate crystal is placed in water, lucifuge stirring and dissolving, obtain pure clear silver nitrate aqueous solution, wherein solution concentration controls between 0.01 ~ 0.03 mol/L.
(2) be d by interlamellar spacing
001the silver nitrate aqueous solution that hydration kaolinite and the step 1 of=0.84nm obtain mixes, and obtains silver nitrate and the kaolinic reaction solution of hydration, and the mass volume ratio of hydration kaolinite and silver nitrate aqueous solution is 1:200(g/mL),
(3) silver nitrate and the kaolinic reaction solution of hydration continuous stirring at room temperature ~ 60 DEG C, after 24 ~ 48 hours, is obtained reaction product mixed solution.
(4) by mixture solution through centrifugalize, remove liquid phase, obtain nanometer silver-kaolinite composite powder.The equal lucifuge of whole course of reaction.
Further, described interlamellar spacing is d
001the hydration height ridge of=0.84nm is prepared by following sub-step:
(2.1) with kaolinite 0.5 ~ 1.5g, corresponding hydrazine hydrate 20ml, puts into airtight glass container and mixes, and stirs 24 ~ 48h, obtain the mixture of hydrazine/Kaolinite/organic Intercalation Compounds and hydrazine hydrate under room temperature (~ 25 DEG C).
(2.2) by mixture first through centrifugal, then remove supernatant liquid; Add dehydrated alcohol again, after mix homogeneously, recentrifuge; Finally repeat previous step again add ethanol purge and through centrifugalize, wash away unnecessary hydrazine hydrate, obtain hydrazine/Kaolinite/organic Intercalation Compounds;
(2.3) hydrazine/Kaolinite/organic Intercalation Compounds is processed 8 ~ 1h at 40 ~ 80 DEG C, make interlayer hydrazine hydrate Direct Resolution obtain d
001the kaolinic powder of=0.84nm hydration.
The beneficial effect that the present invention has compared with background technology is:
1, with hydration kaolinite as carrier, react with silver nitrate solution, because hydration kaolinite is nontoxic, the range of application of nanometer silver-kaolinite complex in medical can be improved.
2, the Al-OH on hydration kaolinite surface
-have reproducibility, can react by the silver ion directly and in silver nitrate solution, go out nanometer silver at kaolinite surface reduction, do not need the step increasing reducing nano-silver, preparation condition is simple.
3, nanometer silver-kaolinite complex of preparing of the present invention, in preparation process, there is no to introduce the molecule had human body and environmental toxic evil, do not need the step of extra reduction silver ion, preparation technology is simple, the anti-microbial property of kaolinic anthemorrhagic performance and nanometer silver can be had concurrently, there is in medical the value of investigation and application.
4, nanometer silver-kaolinite complex of preparing of the present invention, wherein nano-Ag particles is distributed in kaolinite surface, and particle size is mainly distributed between 2 ~ 25 nm, and wherein the nano-Ag particles of 7 ~ 9 nm accounts for about 40%.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture that the silver nitrate solution of hydration kaolinite and variable concentrations processes that different time obtains nanometer silver-kaolinite complex at different temperatures.
Detailed description of the invention
The present invention, comprises the following steps for carrier prepares the method for nanometer silver-kaolinite complex with hydration kaolinite:
1, silver nitrate crystal is placed in water, lucifuge stirring and dissolving, obtain pure clear silver nitrate aqueous solution, wherein solution concentration controls between 0.01 ~ 0.03 mol/L.
2, be d by interlamellar spacing
001the silver nitrate aqueous solution that hydration kaolinite and the step 1 of=0.84nm obtain mixes, and obtains silver nitrate and the kaolinic reaction solution of hydration, and the mass volume ratio of hydration kaolinite and silver nitrate aqueous solution is 1:200(g/mL), described interlamellar spacing is d
001the patent of invention that the denomination of invention that the hydration height ridge of=0.84nm can be applied on June 14th, 2012 by applicant is " hydrazine hydrate-Kaolinite/organic Intercalation Compounds prepares the kaolinic method of 0.84nm hydration ", application number is 201210195865.9 prepares.Specifically, prepared by following sub-step.
2.1, with kaolinite 0.5 ~ 1.5g, corresponding hydrazine hydrate 20ml, puts into airtight glass container and mixes, and stirs 24 ~ 48h, obtain the mixture of hydrazine/Kaolinite/organic Intercalation Compounds and hydrazine hydrate under room temperature (~ 25 DEG C).
2.2, by mixture first through centrifugal, then remove supernatant liquid; Add dehydrated alcohol again, after mix homogeneously, recentrifuge; Finally repeat previous step again add ethanol purge and through centrifugalize, wash away unnecessary hydrazine hydrate, obtain hydrazine/Kaolinite/organic Intercalation Compounds;
2.3, hydrazine/Kaolinite/organic Intercalation Compounds is processed 8 ~ 1h at 40 ~ 80 DEG C, make interlayer hydrazine hydrate Direct Resolution obtain d
001the kaolinic powder of=0.84nm hydration.
3, silver nitrate and the kaolinic reaction solution of hydration continuous stirring at room temperature ~ 60 DEG C, after 24 ~ 48 hours, is obtained reaction product mixed solution.
4, by mixture solution through centrifugalize, remove liquid phase, obtain nanometer silver-kaolinite composite powder.The equal lucifuge of whole course of reaction.
Hydration kaolinite surface prepared by step 2 has reproducibility, and silver ion has been reduced into nanometer silver on hydration kaolinite surface, and the distribution of sizes of nano-Ag particles is between 2 ~ 25 nm, and wherein the nano-Ag particles of 7 ~ 9 nm accounts for about 40%.The nanometer silver prepared-kaolinite complex can stable in the airly exist.
Describe the present invention in detail according to drawings and embodiments below, object of the present invention and effect will become more obvious.
embodiment 1
A silver nitrate crystal is placed in water by (), lucifuge stirring and dissolving, and obtain pure clear silver nitrate aqueous solution (1), wherein solution concentration controls at 0.01 mol/L.
B () adds the hydration kaolinite that 1g prepares through the patent of invention that application number is 201210195865.9 in 200 ml silver nitrate aqueous solutions (1), obtain silver nitrate and the kaolinic reaction solution of hydration (2).
C () controls reaction system (2) and reacts at 60 DEG C, through continuous stirring after 48 hours, obtain reaction product mixed solution (3).
D mixture solution (3) through centrifugalize, is removed liquid phase, is finally obtained nanometer silver-kaolinite composite powder by ().The equal lucifuge of whole course of reaction.
In the transmission electron microscope picture of the nanometer silver prepared by above-mentioned steps-kaolinite complex, nano-Ag particles is distributed in kaolinite surface, and particle size is mainly distributed between 2 ~ 25 nm, and wherein the nano-Ag particles of 7 ~ 9 nm accounts for about 40%
embodiment 2
A silver nitrate crystal is placed in water by (), lucifuge stirring and dissolving, and obtain pure clear silver nitrate aqueous solution (1), wherein solution concentration controls at 0.02 mol/L.
The 1g hydration kaolinite that the patent of invention that b () adds through application number in 200 ml silver nitrate aqueous solutions (1) is 201210195865.9 prepares, obtains silver nitrate and the kaolinic reaction solution of hydration (2).
C () controls reaction system (2) and reacts at 40 DEG C, through continuous stirring after 36 hours, obtain reaction product mixed solution (3).
D mixture solution (3) through centrifugalize, is removed liquid phase, is finally obtained nanometer silver-kaolinite composite powder by ().The equal lucifuge of whole course of reaction.
In the transmission electron microscope picture of the nanometer silver prepared by above-mentioned steps-kaolinite complex, nano-Ag particles is distributed in kaolinite surface, and particle size is mainly distributed between 2 ~ 25 nm, and wherein the nano-Ag particles of 7 ~ 9 nm accounts for about 40%.
embodiment 3
A silver nitrate crystal is placed in water by (), lucifuge stirring and dissolving, and obtain pure clear silver nitrate aqueous solution (1), wherein solution concentration controls at 0.03 mol/L.
The 1g hydration kaolinite that the patent of invention that b () adds through application number in 200 ml silver nitrate aqueous solutions (1) is 201210195865.9 prepares, obtains silver nitrate and the kaolinic reaction solution of hydration (2).
C () controls reaction system (2) and at room temperature reacts, through continuous stirring after 24 hours, obtain reaction product mixed solution (3).
D mixture solution (3) through centrifugalize, is removed liquid phase, is finally obtained nanometer silver-kaolinite composite powder by ().The equal lucifuge of whole course of reaction.
In the transmission electron microscope picture of the nanometer silver prepared by above-mentioned steps-kaolinite complex, nano-Ag particles is distributed in kaolinite surface, and particle size is mainly distributed between 2 ~ 25 nm, and wherein the nano-Ag particles of 7 ~ 9 nm accounts for about 40%.
Above-described embodiment is used for explaining and the present invention is described, instead of limits the invention, and in the protection domain of spirit of the present invention and claim, any amendment make the present invention and change, all fall into protection scope of the present invention.
Claims (2)
1. with hydration kaolinite for carrier prepares the method for nanometer silver-kaolinite complex, comprise the following steps:
(1) silver nitrate crystal is placed in water, lucifuge stirring and dissolving, obtains pure clear silver nitrate aqueous solution, wherein solution concentration controls between 0.01 ~ 0.03 mol/L;
(2) be d by interlamellar spacing
001the silver nitrate aqueous solution that hydration kaolinite and the step 1 of=0.84nm obtain mixes, and obtains silver nitrate and the kaolinic reaction solution of hydration, and the mass volume ratio of hydration kaolinite and silver nitrate aqueous solution is 1:200(g/mL),
(3) silver nitrate and the kaolinic reaction solution of hydration continuous stirring at room temperature ~ 60 DEG C, after 24 ~ 48 hours, is obtained reaction product mixed solution;
(4) mixture solution step 3 obtained, through centrifugalize, is removed liquid phase, is obtained nanometer silver-kaolinite composite powder; The equal lucifuge of whole course of reaction.
2. according to claim 1 with hydration kaolinite for carrier prepares the method for nanometer silver-kaolinite complex, it is characterized in that, described interlamellar spacing is d
001the hydration height ridge of=0.84nm is prepared by following sub-step;
(2.1) with kaolinite 0.5 ~ 1.5g, corresponding hydrazine hydrate 20ml, puts into airtight glass container and mixes, at room temperature stir 24 ~ 48h, obtain the mixture of hydrazine/Kaolinite/organic Intercalation Compounds and hydrazine hydrate, and described room temperature is 25 DEG C;
(2.2) by mixture first through centrifugal, then remove supernatant liquid; Add dehydrated alcohol again, after mix homogeneously, recentrifuge; Finally repeat previous step again add ethanol purge and through centrifugalize, wash away unnecessary hydrazine hydrate, obtain hydrazine/Kaolinite/organic Intercalation Compounds;
(2.3) hydrazine/Kaolinite/organic Intercalation Compounds is processed 8 ~ 1h at 40 ~ 80 DEG C, make interlayer hydrazine hydrate Direct Resolution obtain d
001the kaolinic powder of=0.84nm hydration.
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| CN106732335A (en) * | 2016-12-21 | 2017-05-31 | 佛山市因诺维生物科技有限公司 | A kind of kaolinite for the treatment of field of Environment Protection water body and preparation method thereof |
| CN108160991B (en) * | 2018-01-11 | 2019-08-23 | 中国矿业大学 | Antibacterial composite granule, antibacterial functionalized composite material and preparation method |
| CN110526255A (en) * | 2019-09-29 | 2019-12-03 | 福州大学 | A method of dickite/nano-ag composite is prepared using intercalation |
| CN111603605B (en) * | 2020-06-22 | 2022-06-21 | 湘潭大学 | Inorganic rapid hemostatic material and preparation method thereof |
| CN112451734A (en) * | 2020-11-25 | 2021-03-09 | 联科华技术有限公司 | Application of monatomic catalyst as hemostatic agent |
| CN116285592A (en) * | 2023-04-25 | 2023-06-23 | 陕西科技大学 | Basalt nano-sheet-based high-performance insulating paint and preparation method thereof |
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| CN102701229A (en) * | 2012-06-14 | 2012-10-03 | 浙江大学 | Method for preparing 0.84 nm kaolinite hydrate by hydrazine hydrate-kaolinite intercalation complex |
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