CN104439276B - A kind of quick method and product preparing hollow porous silica/argentum nano composite material - Google Patents

A kind of quick method and product preparing hollow porous silica/argentum nano composite material Download PDF

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CN104439276B
CN104439276B CN201410703691.1A CN201410703691A CN104439276B CN 104439276 B CN104439276 B CN 104439276B CN 201410703691 A CN201410703691 A CN 201410703691A CN 104439276 B CN104439276 B CN 104439276B
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hollow porous
porous silica
composite material
solution
nano composite
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CN104439276A (en
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欧宝立
李政峰
何聪
刘俊成
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Hunan University of Science and Technology
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Abstract

The present invention relates to a kind of quick method preparing hollow porous silica/argentum nano composite material: be placed on after being mixed with sodium silicate solution by molten for the glucose aqueous solution and heating and continuously in high pressure water heating kettle react to obtain carbonaceous ball silica shell recombination reaction thing, 3-8h is calcined in atmosphere, except carbon elimination core is to generate the how empty nanometer silicon dioxide particle of hollow by after centrifugal drying.Gained silica dioxide granule is fully dispersed in the mixed solution of softex kw (CTAB) aqueous solution and hydrazine hydrate, dropwise add dust technology silver solution, magnetic agitation sustained response, centrifugation products therefrom hollow porous silica/silver nano material.Namely the inventive method prepares hollow porous silica/Nano silver grain by one step hydro thermal method and the simple and easy two-step method of a stage reduction method, and one step hydro thermal method prepares hollow porous silicon dioxide nano particle, and its particle diameter has good Modulatory character; One stage reduction method reduction silver, manufacture craft easy reaction can realize large-scale industrial production rapidly.

Description

A kind of quick method and product preparing hollow porous silica/argentum nano composite material
Technical field
The invention belongs to inorganic non-metallic/metallic composite field, relate to hollow porous silica/argentum nano composite material and preparation method thereof.
Background technology
Hollow silicon dioxide nano particle (HSNPS) has hydrophily because of it, is easy to form colloidal suspension liquid and inside and outside wall and all has the characteristic of surface functionality and receive much concern.Hollow silicon dioxide carbon nano-particle has compared with high chemical stability and heat endurance and density is little, surface area is large, good air permeability, there is permeability and (JunjieYuan good in the compatibility of other materials, XiongZhang, HeQian, Anovelapproachtofabricationofsuperparamagnetitehollowsil ica/magneticcompositespheres.JournalofMagnetismandMagnet icMaterials, 2010,322:2172-2176).In Selective Separation, catalysis, the various fields such as dielectric substance have huge applications potentiality.Many chemistry and physico-chemical process have been applied to the making of hollow silica nanoparticles all, comprising chemical precipitation method, microemulsion method (J.J.Yuan, T.Zhou, H.T.Pu, Nano-sizedsilicahollowspheres:preparation, mechanismanalysisanditswaterretentionproperty.J.Phys. & Chem.Solids, 2010,71 (7): 1013-1019), sol-gal process, hydro-thermal method, chemical vapor Xiang Fa etc.
Some hollow metal oxides can be synthesized (M.M.Titirici, M.Antonietti, A.Thomas, Chem.Mater.2006,18,3808) with the water-heat process of carbon as sacrificial core through one by corresponding metallic oxide nanocrystal body.Wang Jiexin etc. take nano-calcium carbonate particles as the inorganic template agent of novelty, and sodium metasilicate is inorganic silicon source, forms CaCO by sol-gel process 3/ SiO 2nucleocapsid structure; Subsequently by high-temperature calcination, acid-soluble and dry process, ball shaped nano hollow silicon dioxide particle (Wang Jiexin, Wen Lixiong, peace, Chen Jianfeng, the novel ball nano-hollow SiO with high-specific surface area are synthesized 2template synthesis method research. chemical journal, 2005,63,1298-1302).The method is by sol-gel process synthesis preparation, and preparation technology is loaded down with trivial details, and the reaction time is longer, and nano-hollow silica dioxide granule size tunable is poor.
Silver has extremely strong sterilizing ability, and have nontoxic, antibiotic property, germicidal efficiency are high, not easily produce drug resistance, the feature such as difficult gathering in human body, so then show more significant performance in catalysis, broad spectrum antibiotic activity, biology and medical sensor etc.(the WangW such as Wang, AsherAS.Photochemicalincorporationofsilverquantumdotsinm onodisPersesilicacolloidsforPhotoniccrystalapplieations [J] .JournaloftheAmericanChemiealSoeiety, 2001,123 (50): 12528-12535) AgNO is used 3under cyclohexane, cyclohexanol, ammoniacal liquor existent condition, be obtained by reacting Ag quantum dot, then add ethyl orthosilicate, obtain the more uniform Ag/SiO of domain size distribution 2particle.But too loaded down with trivial details prepared by it, the particle diameter of Ag nano particle is little, under the impact of skin effect, chemical stability is poor, easily reunites, and therefore needs to carry out surface modification in preparation process, preparation cost is higher in addition, and raw materials used environmental pollution is larger.
Presently, the preparation method of hollow porous silica/argentum nano composite material, it is in cost of manufacture, process cycle and institute's product yield and on ambient influnence, and one or more aspects have defect.The present invention: a kind of preparation method of quick preparation hollow porous silica/argentum nano composite material, hollow porous silica/Nano silver grain is prepared by one step hydro thermal method and the simple and easy two-step method of a stage reduction method, one step hydro thermal method prepares hollow porous silicon dioxide nano particle, and its particle diameter has good Modulatory character; One stage reduction method reduction silver, manufacture craft easy reaction can realize large-scale industrial production rapidly, and environmental friendliness low power consuming.
Summary of the invention
The object of this research is that solution hollow porous silica/argentum nano composite material preparation technology is loaded down with trivial details, composite particle diameter is uncontrollable, time cost and cost of material higher, the problem that environmental pollution is larger, provides the method for a kind of hollow porous silica/argentum nano composite material.
For achieving the above object, the technical solution used in the present invention is: a kind of quick method preparing hollow porous silica/argentum nano composite material, comprises the following steps:
(1) D/W is mixed with sodium silicate solution, continuous heating 18-36h under 150-200 DEG C of condition.
(2) filtration of step (2) reaction gained solution centrifugal, drying are also calcined 3-8h, in atmosphere except carbon elimination core is to generate the how empty nanometer silicon dioxide particle of hollow.
(3) step (3) products therefrom is fully dispersed in the mixed solution of the softex kw aqueous solution and hydrazine hydrate, dropwise adds dust technology silver solution, magnetic agitation sustained response 5-20min.
(4) by the product centrifugation that step (3) obtains, vacuum drying obtains hollow porous silica/argentum nano composite material.
As preferably, in step (1), D/W concentration is 1.5-2.0 × 10 -2gmL -1, sodium silicate solution mesosilicic acid sodium content is 20-30%; The volume ratio of sodium silicate solution and the molten aqueous solution of glucose is 1:500.
As preferably, the centrifugation rate in step (2) during centrifugation is 5000-9000r, and the time is 5-30min, and during vacuum drying, temperature is 80-100 DEG C, and the time is 6-10h.Calcination temperature is 500-600 DEG C in atmosphere, and heating rate is 4-8 DEG C of min -1, calcination time is 4h; Centrifugation rate in step (4) during centrifugation is 2000-4000r, and the time is 5-10min, and during vacuum drying, temperature is 80-100 DEG C, and the time is 6-10h.
As preferably, the softex kw aqueous solution in step (3), liquor argenti nitratis ophthalmicus are 1:2:40-50, CTAB concentration of aqueous solution with the ratio of hydrazine hydrate solution volume is 3.5-4.0 × 10 -4gmL -1, liquor argenti nitratis ophthalmicus concentration is 0.05M, concentration of hydrazine hydrate is 0.1M.
A kind of hollow porous silica/argentum nano composite material obtained as the preparation method as described in arbitrary in claim 1-4.
Principle of the present invention is:
The present invention adopts one step hydro thermal method and stage reduction method preparation, and in the preparation process of hollow porous nano silica particle, by regulating agents useful for same dosage and ratio can change particle diameter size easily, thus it is controlled to realize invention composite.
In two step preparation process in the present invention, reaction principle is succinctly clear, and reaction rate is very fast, raw materials used common nontoxic, meets Green Sustainable theory.Invention product property is stablized, and function admirable, can reach sterilization, catalysis, the various fields practical application standards such as biology sensor.
Beneficial effect of the present invention:
1. prepare nano composite material by two-step method in the present invention, technique be simple and easy, preparation is rapid, low power consuming and low stain, be applicable to suitability for industrialized production.
2. in the present invention, prepared silica nanosphere has hollow loose structure, its stable performance, good dispersion.
3. in the present invention, prepared its particle size of nano composite material is controlled, regulates by change reactant concentration and ratio.
4. prepared nano composite material function admirable in the present invention, multicomponent composite materials the present invention compared with single component material prepares composite and has obvious bactericidal effect, using staphylococcus aureus as object module bacterium, add the prepared hollow porous silica/Nano silver grain of invention, study its deactivation time, observe the damage mechanisms of sterilization process bacterial cell, we find that prepared hollow porous silica/argentum nano composite material has obvious antibacterial ability simultaneously.Composite application prospect is extensive, have unique optical, electrical, magnetic, etc. physico-chemical property, the fields such as coating, display material, stealth material, catalysis material, microelectronic component, biology sensor, magnetic thermo-sensitive material can be widely used in.
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph that the present invention prepares hollow porous silicon dioxide nano particle.
Fig. 2 is the stereoscan photograph that the present invention prepares hollow porous silica/silver nano particle composite material.
Fig. 3 is the X-ray diffractogram that the present invention prepares hollow porous silicon dioxide nano particle.
Detailed description of the invention
Embodiment 1:
1.7100g glucose is dissolved in 100mL distilled water, adds the sodium silicate solution that 0.4mL silica concentration is 20% wherein, fully after mixing, to be placed in high pressure water heating kettle continuous heating 24h under 180 DEG C of conditions.Reaction gained solution distilled water repeatedly cleans, and centrifugal 10min under the centrifugation rate of 6000r also filters.Repeatedly cleaning after in 80 DEG C of vacuum dried overnight.By products therefrom with 4 DEG C of min -1heating rate under 600 DEG C of conditions, calcine 6h, except carbon elimination core is to generate the how empty nanometer silicon dioxide particle of hollow.It is fully dispersed to 200mL4.0 × 10 -4gmL -1the softex kw aqueous solution in, the hydrazine hydrate adding 2.5mL0.1M fully mixes, rotating speed be 300r condition lower magnetic force stir dropwise add 5mL0.05M dust technology silver solution, sustained response 5min.Cleaned by the product obtained, centrifugal 5min under the centrifugation rate of 2000r also filters.At 80 DEG C of vacuum drying 6h after repeatedly cleaning, obtain hollow porous silica/silver nano particle composite material.The scanning electron microscope (SEM) photograph preparing the preparation hollow porous silicon dioxide nano particle of gained is shown in Fig. 1.Products therefrom hollow porous silicon dioxide nano particle diameter is even as can be observed from Figure, is about 100nm.
Embodiment 2:
1.7100g glucose is dissolved in 100mL distilled water, adds the sodium silicate solution that 0.4mL silica concentration is 20% wherein, fully after mixing, to be placed in high pressure water heating kettle continuous heating 24h under 180 DEG C of conditions.Reaction gained solution distilled water cleans, and centrifugal 10min under the centrifugation rate of 6000r also filters.Repeatedly cleaning after in 80 DEG C of vacuum dried overnight.By products therefrom with 4 DEG C of min -1heating rate under 500 DEG C of conditions, calcine 4h, except carbon elimination core is to generate the how empty nanometer silicon dioxide particle of hollow.Products therefrom is fully dispersed to 200mL3.5 × 10 -4gmL -1the softex kw aqueous solution in, the hydrazine hydrate adding 3.0mL0.1M fully mixes, rotating speed be 300r condition lower magnetic force stir dropwise add 5mL0.05M dust technology silver solution, sustained response 10min.Cleaned by the product obtained, centrifugal 5min under the centrifugation rate of 2000r also filters.At 80 DEG C of vacuum drying 6h after repeatedly cleaning, hollow porous silica/silver nano particle composite material is successfully prepared.Composite particles particle diameter is about 80nm, and load silver thickness of the shell increases.The scanning electron microscope (SEM) photograph preparing the hollow porous silica/silver nano particle composite material of gained is shown in Fig. 2.Products therefrom hollow porous silica/silver nano particle composite material uniform particle sizes, is about 120nm as can be observed from Figure, profile rule.
Embodiment 3:
1.3680g glucose is dissolved in 100mL distilled water, adds the sodium silicate solution that 0.4mL silica concentration is 20% wherein, fully after mixing, to be placed in high pressure water heating kettle continuous heating 24h under 180 DEG C of conditions.Reaction gained solution distilled water repeatedly cleans, and centrifugal 10min under the centrifugation rate of 6000r also filters.Repeatedly cleaning after in 80 DEG C of vacuum dried overnight.By products therefrom with 4 DEG C of min -1heating rate under 550 DEG C of conditions, calcine 4h, except carbon elimination core is to generate the how empty nanometer silicon dioxide particle of hollow.Products therefrom is fully dispersed to 200mL4.0 × 10 -4gmL -1the softex kw aqueous solution in, the hydrazine hydrate adding 2.5mL0.1M fully mixes, rotating speed be 300r condition lower magnetic force stir dropwise add 5mL0.05M dust technology silver solution, sustained response 15min.Cleaned by the product obtained, centrifugal 5min under the centrifugation rate of 2000r also filters.At 80 DEG C of vacuum drying 6h after repeatedly cleaning, hollow porous silica/silver nano particle composite material is successfully prepared, and composite particles particle diameter is about 80nm.The X-ray diffractogram preparing the preparation hollow porous silicon dioxide nano particle of gained is shown in Fig. 3.In 2 θ=21.79 there is obvious diffraction maximum in a ° place as can be observed from Figure, shows amorphous SiO 2particle is successfully prepared.
Embodiment 4:
1.7100g glucose is dissolved in 100mL distilled water, adds the sodium silicate solution that 0.2mL silica concentration is 20% wherein, fully after mixing, to be placed in high pressure water heating kettle continuous heating 12h under 180 DEG C of conditions.Reaction gained solution distilled water repeatedly cleans, and centrifugal 10min under the centrifugation rate of 6000r also filters.Repeatedly cleaning after in 80 DEG C of vacuum dried overnight.By products therefrom with 4 DEG C of min -1heating rate under 600 DEG C of conditions, calcine 6h, except carbon elimination core is to generate the how empty nanometer silicon dioxide particle of hollow.Products therefrom is fully dispersed to 200mL4.0 × 10 -4gmL -1the softex kw aqueous solution in, the hydrazine hydrate adding 2.5mL0.1M fully mixes, rotating speed be 300r condition lower magnetic force stir dropwise add 5mL0.05M dust technology silver solution, sustained response 5-20min.Cleaned by the product obtained, centrifugal 5min under the centrifugation rate of 2000r also filters.At 80 DEG C of vacuum drying 6h after repeatedly cleaning, obtain hollow porous silica/silver nano particle composite material, composite particles particle diameter is about 70nm, and sodium silicate solution reagent dosage reduces, and prepared composite particles particle diameter reduces.
Embodiment 5:
2.2300g glucose is dissolved in 100mL distilled water, adds the sodium silicate solution that 0.2mL silica concentration is 20% wherein, fully after mixing, to be placed in high pressure water heating kettle continuous heating 12h under 180 DEG C of conditions.Reaction gained solution distilled water repeatedly cleans, and centrifugal 10min under the centrifugation rate of 6000r also filters.Repeatedly cleaning after in 80 DEG C of vacuum dried overnight.By products therefrom with 4 DEG C of min -1heating rate under 580 DEG C of conditions, calcine 6h, except carbon elimination core is to generate the how empty nanometer silicon dioxide particle of hollow.Products therefrom is fully dispersed to 200mL3.8 × 10 -4gmL -1the softex kw aqueous solution in, the hydrazine hydrate adding 2.5mL0.1M fully mixes, rotating speed be 300r condition lower magnetic force stir dropwise add 5mL0.05M dust technology silver solution, sustained response 20min.Cleaned by the product obtained, centrifugal 5min under the centrifugation rate of 2000r also filters.At 80 DEG C of vacuum drying 6h after repeatedly cleaning, obtain hollow porous silica/silver nano particle composite material, composite particles particle diameter is about 120nm, and glucose concentration increases, and prepared composite particles particle diameter increases.
Above-described embodiment is implemented under premised on technical solution of the present invention, given detailed embodiment and process, is to further illustrate of the present invention, instead of limits the scope of the invention.

Claims (5)

1. prepare a method for hollow porous silica/argentum nano composite material fast, it is characterized in that, comprise the following steps:
(1) D/W is fully mixed with sodium silicate solution, continuous heating 18-36h under 150-200 DEG C of condition;
(2) filtration of step (1) reaction gained solution centrifugal, drying are also calcined 3-8h, in atmosphere except carbon elimination core is to generate hollow porous nanosilica particles;
(3) step (2) products therefrom is fully dispersed in the mixed solution of the softex kw aqueous solution and hydrazine hydrate, dropwise adds dust technology silver solution, magnetic agitation sustained response 5-20min;
(4) by step (3) products therefrom centrifugation, vacuum drying obtains hollow porous silica/argentum nano composite material.
2. a kind of quick method preparing hollow porous silica/argentum nano composite material as claimed in claim 1, is characterized in that, in step (1), D/W concentration is 1.5-2.0 × 10 -2gmL -1, sodium silicate solution mesosilicic acid sodium content is 15-30%, and the volume ratio of sodium silicate solution and D/W is 1:400-600.
3. a kind of quick method preparing hollow porous silica/argentum nano composite material as claimed in claim 1, it is characterized in that, the centrifugation rate in step (2) during centrifugation is 5000-9000r, and the time is 5-30min, during vacuum drying, temperature is 80-100 DEG C, and the time is 6-10h; Calcining heat is 400-600 DEG C, and heating rate is 2-4 DEG C of min -1, calcination time is 3-8h; Centrifugation rate in step (4) during centrifugation is 2000-4000r, and the time is 5-10min, and during vacuum drying, temperature is 80-100 DEG C, and the time is 6-10h.
4. a kind of quick method preparing hollow porous silica/silver nano particle composite material as claimed in claim 1, it is characterized in that, in step (3), the softex kw aqueous solution, liquor argenti nitratis ophthalmicus are 1:2:40-50 with the ratio of hydrazine hydrate solution volume, and softex kw concentration of aqueous solution is 3.5-4.0 × 10 -4gmL -1, liquor argenti nitratis ophthalmicus concentration is 0.05M, concentration of hydrazine hydrate is 0.1M.
5. the hollow porous silica/argentum nano composite material obtained as the preparation method as described in arbitrary in claim 1-4.
CN201410703691.1A 2014-11-30 2014-11-30 A kind of quick method and product preparing hollow porous silica/argentum nano composite material Expired - Fee Related CN104439276B (en)

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CN106814111A (en) * 2017-02-13 2017-06-09 山东旭晟东阳新材料科技有限公司 A kind of hollow porous SnO2Micro-pipe gas sensor and preparation method thereof
CN107189585A (en) * 2017-06-28 2017-09-22 福州大学 A kind of SiO 2 supported nanometer silver water anti-bacteria coating and preparation method thereof
CN107598184A (en) * 2017-08-18 2018-01-19 江西师范大学 Preparation method of silver nanoparticle coated silicon dioxide microsphere powder
CN109850910B (en) * 2019-01-25 2020-09-25 西北工业大学 Preparation method of hierarchical porous silicon oxide
CN111804927A (en) * 2019-04-10 2020-10-23 近镒生技股份有限公司 Nano silver particle, porous material composition and preparation method thereof

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CN102019431B (en) * 2010-09-30 2013-06-05 大连理工大学 Metallic nano cluster/silicon dioxide hollow nuclear shell structured nanoparticles and preparation method thereof
CN102613244B (en) * 2012-03-11 2014-03-19 浙江大学 Preparation method of mesoporous hollow spherical silver-loaded silicon dioxide antimicrobial
CN103231072B (en) * 2013-04-09 2015-06-03 昆明理工大学 Preparation method of silicon dioxide/silver core-shell composite powder for high temperature electronic paste
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