CN106912499A - A kind of sterilized composite and preparation method thereof - Google Patents
A kind of sterilized composite and preparation method thereof Download PDFInfo
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- CN106912499A CN106912499A CN201710156170.2A CN201710156170A CN106912499A CN 106912499 A CN106912499 A CN 106912499A CN 201710156170 A CN201710156170 A CN 201710156170A CN 106912499 A CN106912499 A CN 106912499A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
Abstract
The present invention relates to a kind of Nano Silver/graphene aerogel composite that can be used for and sterilizing and preparation method thereof.The sterilized composite is synthesized under hydrothermal conditions by the mixture of methylamine, silver nitrate and graphene oxide solution.Wherein methylamine i.e. can be dispersed in the solution as the presoma of Nano Silver with silver ion formation silver ammino solution, is again the reducing agent to form Nano Silver.Using the inventive method, one-step synthesis, it is not necessary to double-steeping, prepared stability of material is good, pliability strong, silver ion release is extremely low.Nano Silver/the graphene aerogel that will be prepared is used for Escherichia coli inactivation experiments, as a result shows that this material has good bactericidal effect and can reuse, and the bactericidal effect being repeated 7 times remains unchanged as before.
Description
Technical field
The present invention relates to a kind of preparation of sterilized composite, a kind of specifically graphene aerogel load is received
Rice silver composite material and preparation method thereof, belongs to water-treatment technology field.
Background technology
With the continuous progress of science and technology, the mankind change natural ability and increasingly strengthen, with this come together except
The economic bonus of high speed development also has serious environmental problem.The factor of water pollution is caused except hazardous chemicals also has carefully
The pathogenic microorganisms such as bacterium, parasite, virus.Bacterium in how quick, effectively, inexpensive elimination water starts to cause scientist
Attention.Inorganic sterilizing methods main at present are to use silver nano-grain, and bactericidal nano-silver has efficient, lasting, low toxicity
Side effect, the advantages of drug resistance will not be produced.But Nano Silver is expensive, be difficult to reclaim the shortcomings of limit its reality should
With.
Graphene aerogel is the 3D carbon materials synthesized by Graphene, in addition to the advantage for inheriting Graphene, itself also gram
The stack effect between graphene sheet layer is taken.Because graphene aerogel has, porosity is high, specific surface area is big, density is small,
Mechanical performance is strong, stable chemical nature, it is nontoxic the advantages of, so it has advantageous advantage in terms of water process.
Therefore, germicidal applications prospect of the composite of graphene aerogel and Nano Silver in water environment is boundless.
The research of current nano-silver loaded graphene aerogel is rarely reported, and is either closed using Graphene and silver nitrate situ study
Silver nitrate two step synthetic method material is impregnated into again into composite or first synthesizing graphite alkene aeroge, it is preceding from terms of actual effect
Person's mechanical property of materials is poor, pliability is low, is not suitable for practical application, and the Nano Silver of the latter can only load to graphene aerogel
Surface, it is impossible to be dispersed in the entirety of material, this have impact on the bactericidal property of material.
The content of the invention
It is an object of the invention to be directed to the problem present on, there is provided a kind of synthesizing nano-silver/graphene aerogel is multiple
The straightforward procedure of condensation material, sterilized composite machinery intensity of the invention is high, nano-silver loaded is uniform, bactericidal effect
It is good.
The present invention is adopted the technical scheme that：A kind of sterilized composite, the sterilizing composite is by nanometer
Silver and graphene aerogel are constituted, and nano-Ag particles are homogeneously dispersed on graphene aerogel.
In the presence of composite, the sterilization rate in 30 minutes to Escherichia coli reaches 100%, after 7 repetitions are tested,
Composite remains unchanged can keep good bactericidal effect, sterilization rate to reach 100%.
In the present invention, it is preferred to, nano-Ag particles are evenly dispersed on graphene aerogel, and Argent grain is a diameter of
10-100 nm, Nano Silver is 0.2 ~ 0.7 with graphene aerogel mass ratio：1.
Further, present invention also offers the preparation method of above-mentioned sterilized composite, methylamine, silver nitrate are added
Enter and stirred to after graphene oxide solution, then by hydro-thermal method synthetic composite material, finally obtained using freeze-drying
Nano Silver/graphene aerogel sterilizing composite.
In the present invention, it is preferred to, the concentration of the graphene oxide for using is 5 mg/mL.In the present invention, it is preferred to,
The concentration of the silver nitrate for using is 8.3 mg/mL.In the present invention, it is preferred to, the concentration of the methylamine for using is 0.1 mmol/
mL.In the present invention, it is preferred to, methylamine, silver nitrate are added to 2 h are stirred after graphene oxide solution, at 130 DEG C, water
The min of thermal response 360, finally the h of freeze-drying 48 obtains Nano Silver/graphene aerogel and goes out under the conditions of -55 DEG C, 1000 Pa
Bacterium composite.
The preparation method of above-mentioned sterilized composite specifically includes following steps：
1st, the preparation of graphene oxide：
(1) concentrated sulfuric acids of 50 mL 98% are measured to be added in 500 mL beakers, 0 ~ 5 DEG C of 5 min of stirring is kept.
(2) to 2 g graphite powders and 1 g sodium nitrate is added in beaker, 0 ~ 5 DEG C of 0.5 h of stirring is kept.
(3) to 6 g potassium permanganate are added in beaker, 0 ~ 5 DEG C of 2 h of stirring is kept.
(4) remove ice bath and be heated to 38 DEG C, stir 2 h.
(5) first to 50 mL ultra-pure waters are added in beaker, 88 DEG C are heated to, stir 0.5 h.
(6) hydrogen peroxide of 80 mL ultra-pure waters and 4 mL 30% is added in the backward beaker of stopping heating, reaction terminates.
(7) with 5% salt acid elution 4 times, plus ultrasonic 1.5 h after ultra-pure water constant volume adjusts pH value to neutrality, obtains oxidation stone
Black alkene dispersion liquid.
2nd, the preparation of Nano Silver/graphene aerogel：
(1) graphene oxide dispersion of 10 ~ 50 mL0.5 ~ 10 mg/mL is measured, 0.05 ~ 0.5 g silver nitrates are added thereto to
With 0.2 ~ 7.5 mmol methylamine solutions, 1 ~ 3 h is stirred.
(2) mixed liquor is poured into reactor, the min of hydro-thermal 150 ~ 600 at a temperature of being maintained at 90 ~ 180 DEG C.
(3) use milli-Q water 3 times again after the product freeze-drying after hydro-thermal, be put into drying in 60 DEG C of vacuum drying chambers
6 h are stand-by.
Compared with the graphene aerogel of conventional load Nano Silver, material use methylamine of the invention replace ammoniacal liquor and silver from
The silver ammino solution that son is formed can be uniformly dispersed in graphene oxide dispersion, and during hydro-thermal, methylamine has reduction
Property directly silver ammino solution be reduced into Nano Silver be distributed in whole graphene aerogel.
The present invention has the advantage that：
1st, Nano Silver can be uniformly dispersed in the entirety of graphene aerogel, including surface and internal layer.The Nano Silver of internal layer has
The stacking prevented between graphene sheet layer of effect, increased material overall mechanical performance and pliability, be the reality of material
Using and reuse provide may.
2nd, graphene aerogel provides " dwelling " for Nano Silver, overcomes after bactericidal nano-silver that easily collecting is difficult repeats to make
Shortcoming.Repeat sterilization experiment and show that the material can be reused 7 times, effect is not changed in substantially, it was demonstrated that material sheet
The stability of body.
3rd, materials synthesis simplicity, bactericidal effect are good, reuse drying after only used material need to be pulled out and can be used for
Next time uses.
Brief description of the drawings
Fig. 1 is the SEM figures of silver nano-grain (a), graphene aerogel (b), Nano Silver/graphene aerogel (c) (d).
Fig. 2 is silver nano-grain（Under）, graphene aerogel（In）, Nano Silver/graphene aerogel（On）XRD.
Fig. 3 be Argent grain, graphene aerogel, Nano Silver/graphene aerogel to the bactericidal effect figure of Escherichia coli and
The decline figure of Escherichia coli under the conditions of blank.
Fig. 4 is the bactericidal effect figure that Nano Silver/graphene aerogel reuses 7 times.
Fig. 5 is the concentration of silver ions discharged in water after the sterilization of Nano Silver/graphene aerogel.
Specific embodiment
Further the present invention is illustrated with reference to embodiment and accompanying drawing, but this patent protects content to be not limited to institute
Illustrate content.
Embodiment 1：The preparation of Nano Silver/graphene aerogel composite
The preparation of graphene oxide：
(1) concentrated sulfuric acids of 50 mL 98% are measured to be added in 500 mL beakers, 0 ~ 5 DEG C of 5 min of stirring is kept.
(2) to 2 g graphite powders and 1 g sodium nitrate is added in beaker, 0 ~ 5 DEG C of 0.5 h of stirring is kept.
(3) to 6 g potassium permanganate are added in beaker, 0 ~ 5 DEG C of 2 h of stirring is kept.
(4) remove ice bath and be heated to 38 DEG C, stir 2 h.
(5) first to 50 mL ultra-pure waters are added in beaker, 88 DEG C are heated to, stir 0.5 h.
(6) hydrogen peroxide of 80 mL ultra-pure waters and 4 mL 30% is added in the backward beaker of stopping heating, reaction terminates.
(7) with 5% salt acid elution 4 times, plus ultrasonic 1.5 h after ultra-pure water constant volume adjusts pH value to neutrality, obtains oxidation stone
Black alkene dispersion liquid.
The preparation of Nano Silver/graphene aerogel：
(1) graphene oxide dispersion of 30 mL5 mg/mL is measured, 0.25 g silver nitrates and 500 μ L methylamines are added thereto to
Solution, stirs 2 h.
(2) mixed liquor is poured into reactor, the min of hydro-thermal 360 at a temperature of being maintained at 130 DEG C.
(3) use milli-Q water 3 times again after the product freeze-drying after hydro-thermal, be put into drying in 60 DEG C of vacuum drying chambers
6 h are stand-by.
Argent grain is reunited together in the Fig. 1 (a) that be can see without graphene aerogel as carrier from SEM figures, shadow
Its bactericidal effect is rung.There is finely dispersed Argent grain compared with Fig. 1 (b), in Fig. 1 (c).Can be substantially from Fig. 1 (d)
The size for going out silver is both less than 100 nanometers substantially, belongs to nano material.It can be seen that Nano Silver/Graphene gas from the XRD of Fig. 2
XRD characteristic peak of the gel comprising silver（2θ = 38.1°、 44.3°、67.4°、77.4°）, wherein the graphite peaks near 25 ° disappear
It is probably because Nano Silver prevents the stack effect of graphene sheet layer.
Embodiment 2：Nano Silver/graphene aerogel composite sterilizing experiment
Specific experiment step is as follows：
4 centrifuge tube numberings 1,2,3,4 are taken, it is each thereto to add 50 mL 108The Escherichia coli bacteria liquid of CFU/mL, then distinguish
To add in 2,3,4 150 mg Nano Silvers, the graphene aerogel of 170 mg, 310 mg Nano Silver/graphene aerogel simultaneously
And stand.Take 0.1 mL liquid respectively from 4 centrifuge tubes at regular intervals to be added drop-wise on LB culture agar, coated plate and 37
24 h are cultivated at DEG C.As shown in figure 3, Nano Silver/graphene aerogel had good bactericidal effect, sterilization rate in 30 minutes
Reach 100%.And other 2 material bactericidal effects are not obvious.
Dried after Nano Silver after sterilization/graphene aerogel tweezers are pulled out, carry out repeated sterilized test, such as schemed
Shown in 4, after 7 repetitions are tested, Nano Silver/graphene aerogel remains unchanged can keep good bactericidal effect, sterilization rate to reach
100%。
As shown in figure 5,6 release concentration average values of silver ion are 0.099 mg/L.In 50 mL water, Nano Silver/stone
The Nano Silver of black alkene aeroge sterilization average loss 0.0005 mg every time, this with whole material in 150 mg Nano Silver phase
Than that can ignore completely.So the property of Nano Silver/graphene aerogel is highly stable.
Claims (10)
1. a kind of sterilized composite, it is characterised in that：The sterilizing composite is by Nano Silver and Graphene airsetting
Glue is constituted, and nano-Ag particles are homogeneously dispersed on graphene aerogel.
2. a kind of sterilized composite as claimed in claim 1, it is characterised in that：Nano-Ag particles are evenly dispersed in
On graphene aerogel, a diameter of 10-100 nm of Argent grain, Nano Silver is 0.2 ~ 0.7 with graphene aerogel mass ratio：1.
3. a kind of preparation method of sterilized composite material nanometer silver/graphite alkene aeroge as claimed in claim 1, its system
It is standby to be characterised by：Stirred after methylamine, silver nitrate are added into graphene oxide solution, then composite wood is synthesized by hydro-thermal method
Material, finally obtains Nano Silver/graphene aerogel finished product using freeze-drying.
4. a kind of sterilized composite material and preparation method thereof as claimed in claim 3, its preparation is characterised by：The oxygen for being used
Graphite alkene is synthesized by Hummers methods, and prepared graphene oxide is without separation, dry, direct constant volume, ultrasound, tune pH
Liquid condition is stand-by afterwards.
5. a kind of sterilized composite material and preparation method thereof as claimed in claim 3, its preparation is characterised by：Graphene oxide
Concentration be 0.5 ~ 10 mg/mL.
6. a kind of sterilized composite material and preparation method thereof as claimed in claim 3, its preparation is characterised by：Silver nitrate it is dense
It is 1 ~ 20 mg/mL to spend.
7. as claimed in claim 3, its preparation is characterised by：The concentration of methylamine is 0.0065 ~ 0.25 mmol/mL.
8. as claimed in claim 3, its preparation is characterised by：Mixing time is 1 ~ 3 h.
9. as claimed in claim 3, its preparation is characterised by：The temperature of hydro-thermal reaction be 90 ~ 180 DEG C, the reaction time be 150 ~
600 min。
10. as claimed in claim 3, its preparation is characterised by：Freeze-drying temperature, vacuum and drying time are respectively -20
~ -70 DEG C, 100 ~ 6000 Pa and 10 ~ 100 h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710156170.2A CN106912499B (en) | 2017-03-16 | 2017-03-16 | Efficient sterilization composite material and preparation method thereof |
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| CN201710156170.2A CN106912499B (en) | 2017-03-16 | 2017-03-16 | Efficient sterilization composite material and preparation method thereof |
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| CN106912499A true CN106912499A (en) | 2017-07-04 |
| CN106912499B CN106912499B (en) | 2020-05-22 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113122190A (en) * | 2021-03-24 | 2021-07-16 | 武汉工程大学 | Aerogel composite material and preparation method thereof |
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| CN106006620A (en) * | 2016-05-27 | 2016-10-12 | 中国科学院城市环境研究所 | Graphene oxide aerogel and graphene aerogel, as well as preparation methods and environmental application of graphene oxide aerogel and graphene aerogel |
| CN106031857A (en) * | 2015-03-19 | 2016-10-19 | 中国科学院上海应用物理研究所 | Graphene-inorganic nanometer particle composite hydrogel and aerogel as well as preparation methods and applications thereof |
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| CN104250005A (en) * | 2014-09-11 | 2014-12-31 | 中国科学院上海应用物理研究所 | Graphene aerogel as well as preparation method and application thereof |
| CN104587918A (en) * | 2015-01-30 | 2015-05-06 | 河海大学 | Silver nano-particle modified carbon ball/graphene composite aero-gel material as well as preparation method and application of material |
| CN106031857A (en) * | 2015-03-19 | 2016-10-19 | 中国科学院上海应用物理研究所 | Graphene-inorganic nanometer particle composite hydrogel and aerogel as well as preparation methods and applications thereof |
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| CN113122190A (en) * | 2021-03-24 | 2021-07-16 | 武汉工程大学 | Aerogel composite material and preparation method thereof |
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