CN106912499B - Efficient sterilization composite material and preparation method thereof - Google Patents
Efficient sterilization composite material and preparation method thereof Download PDFInfo
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- CN106912499B CN106912499B CN201710156170.2A CN201710156170A CN106912499B CN 106912499 B CN106912499 B CN 106912499B CN 201710156170 A CN201710156170 A CN 201710156170A CN 106912499 B CN106912499 B CN 106912499B
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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 invention relates to a nano-silver/graphene aerogel composite material for sterilization and a preparation method thereof. The efficient sterilization composite material is synthesized by a mixture of methylamine, silver nitrate and graphene oxide solution under a hydrothermal condition. The methylamine can form a silver ammonia solution with silver ions, and the silver ammonia solution is uniformly dispersed in the solution to serve as a precursor of the nano silver and is also a reducing agent for forming the nano silver. The method of the invention has one-step synthesis without secondary impregnation, and the prepared material has good stability, strong flexibility and extremely low silver ion release. The prepared nano silver/graphene aerogel is used for escherichia coli inactivation experiments, and results show that the material has a good sterilization effect and can be reused, and the sterilization effect after 7 times of repeated use is as before.
Description
Technical Field
The invention relates to preparation of an efficient sterilization composite material, in particular to a graphene aerogel supported nano-silver composite material and a preparation method thereof, and belongs to the technical field of water treatment.
Background
With the continuous progress of scientific technology, the ability of human beings to change nature is increasingly enhanced, and the accompanying situation has serious environmental problems in addition to economic dividends developed at a high speed. Factors causing water pollution include pathogenic microorganisms such as bacteria, parasites, viruses, and the like, in addition to dangerous chemicals. The rapid, effective and low-cost elimination of bacteria in water has attracted the attention of scientists. At present, the main inorganic sterilization method adopts silver nanoparticles, and the nano silver sterilization has the advantages of high efficiency, durability, low toxic and side effects, no drug resistance and the like. However, the practical application of the nano silver is limited by the defects of high price, difficult recovery and the like of the nano silver.
The graphene aerogel is a 3D carbon material synthesized from graphene, and besides inherits the advantages of graphene, the graphene aerogel overcomes the stacking effect among graphene sheet layers. The graphene aerogel has the advantages of high porosity, large specific surface area, small density, strong mechanical property, stable chemical property, no toxicity, no harm and the like, so the graphene aerogel has the unique advantage in the aspect of water treatment.
Therefore, the graphene aerogel and nano-silver composite material has a very wide sterilization application prospect in a water environment. At present, research on nano-silver loaded graphene aerogel is rarely reported, and no matter a composite material is synthesized by using graphene and silver nitrate in-situ one-step method or a material is synthesized by firstly synthesizing the graphene aerogel and then soaking the graphene aerogel into silver nitrate in a two-step method, the material has poor mechanical property and low flexibility and is not suitable for practical application from the viewpoint of practical effect, and the nano-silver of the material can only be loaded on the surface of the graphene aerogel and cannot be uniformly dispersed in the whole material, so that the sterilization performance of the material is influenced.
Disclosure of Invention
The invention aims to provide a simple method for synthesizing a nano-silver/graphene aerogel composite material aiming at the problems, and the efficient sterilization composite material has the advantages of high mechanical strength, uniform nano-silver load and good sterilization effect.
The technical scheme adopted by the invention is as follows: the efficient sterilization composite material consists of nano silver and graphene aerogel, wherein nano silver particles are uniformly dispersed on the graphene aerogel.
Under the action of the composite material, the sterilization rate of the composite material to escherichia coli reaches 100% within 30 minutes, and after 7 times of repeated experiments, the composite material still can keep a good sterilization effect, and the sterilization rate reaches 100%.
In the invention, preferably, the nano silver particles are uniformly dispersed on the graphene aerogel, the diameter of the silver particles is 10-100nm, and the mass ratio of the nano silver to the graphene aerogel is 0.2-0.7: 1.
further, the invention also provides a preparation method of the efficient sterilization composite material, which comprises the steps of adding methylamine and silver nitrate into the graphene oxide solution, uniformly stirring, synthesizing the composite material by a hydrothermal method, and finally obtaining the nano silver/graphene aerogel sterilization composite material by a freeze-drying method.
In the present invention, the graphene oxide is preferably used at a concentration of 5 mg/mL. In the present invention, it is preferable that the silver nitrate is used in a concentration of 8.3 mg/mL. In the present invention, preferably, methylamine is used at a concentration of 0.1 mmol/mL. In the invention, preferably, methylamine and silver nitrate are added into the graphene oxide solution, then the mixture is stirred for 2 hours, the hydrothermal reaction is carried out for 360 minutes at the temperature of 130 ℃, and finally the nano silver/graphene aerogel sterilization composite material is obtained by freeze drying for 48 hours at the temperature of-55 ℃ and under the condition of 1000 Pa.
The preparation method of the high-efficiency sterilization composite material specifically comprises the following steps:
1. preparing graphene oxide:
(1) 50mL of 98% concentrated sulfuric acid is measured and added into a 500 mL beaker, and the temperature is kept between 0 and 5 ℃ and stirred for 5 min.
(2) Adding 2 g of graphite powder and 1 g of sodium nitrate into a beaker, keeping the temperature of 0-5 ℃, and stirring for 0.5 h.
(3) Adding 6 g of potassium permanganate into the beaker, and stirring for 2 hours at the temperature of 0-5 ℃.
(4) The ice bath was removed and the mixture was heated to 38 ℃ and stirred for 2 h.
(5) 50mL of ultrapure water was added to the beaker, heated to 88 ℃ and stirred for 0.5 h.
(6) After the heating was stopped, 80 mL of ultrapure water and 4 mL of 30% hydrogen peroxide were added to the beaker, and the reaction was completed.
(7) Washing with 5% hydrochloric acid for 4 times, adding ultrapure water to a constant volume, performing ultrasonic treatment for 1.5 h, and adjusting the pH value to be neutral to obtain the graphene oxide dispersion liquid.
2. Preparing nano silver/graphene aerogel:
(1) weighing 10-50 mL0.5-10 mg/mL of graphene oxide dispersion liquid, adding 0.05-0.5 g of silver nitrate and 0.2-7.5 mmol of methylamine solution, and stirring for 1-3 h.
(2) Pouring the mixed solution into a reaction kettle, and keeping the temperature of 90-180 ℃ for hydrothermal treatment for 150-600 min.
(3) And (3) after the hydrothermal product is subjected to freeze drying, washing the product for 3 times by using ultrapure water, and drying the product for 6 hours in a vacuum drying oven at the temperature of 60 ℃ for later use.
Compared with the traditional graphene aerogel loaded with nano silver, the material disclosed by the invention has the advantages that the methylamine is used for replacing ammonia water and silver ions to form a silver-ammonia solution which can be uniformly dispersed in the graphene oxide dispersion liquid, and in the hydrothermal process, the methylamine has reducibility to directly reduce the silver-ammonia solution into nano silver which is distributed in the whole graphene aerogel.
The invention has the advantages that:
1. the nano silver can be uniformly dispersed in the whole graphene aerogel, including the surface and the inner layer. The nano-silver of the inner layer effectively prevents the graphene sheet layers from being stacked, the integral mechanical property and flexibility of the material are improved, and the possibility is provided for the practical application and the repeated use of the material.
2. The graphene aerogel provides a 'residence' for the nano-silver, and overcomes the defect that the nano-silver is difficult to collect and difficult to reuse after being sterilized. Repeated sterilization experiments show that the material can be repeatedly used for 7 times, the effect is basically unchanged, and the stability of the material is proved.
3. The material is simple and convenient to synthesize, has good sterilization effect, and can be used for next use only by fishing out the used material and drying the material after repeated use.
Drawings
Fig. 1 is an SEM image of silver nanoparticles (a), graphene aerogel (b), nanosilver/graphene aerogel (c) (d).
Fig. 2 is an XRD pattern of silver nanoparticles (bottom), graphene aerogel (middle), and nano-silver/graphene aerogel (top).
Fig. 3 is a graph of the bactericidal effect of the silver particles, the graphene aerogel and the nano silver/graphene aerogel on escherichia coli and an apoptosis graph of escherichia coli under a blank condition.
Fig. 4 is a graph of bactericidal effect of the nano silver/graphene aerogel repeatedly used 7 times.
Fig. 5 is the concentration of silver ions released in water after nano silver/graphene aerogel sterilization.
Detailed Description
The invention is further elucidated with reference to the embodiments and the drawings, without the contents of the patent protection being restricted thereto.
Example 1: preparation of nano-silver/graphene aerogel composite material
Preparing graphene oxide:
(1) 50mL of 98% concentrated sulfuric acid is measured and added into a 500 mL beaker, and the temperature is kept between 0 and 5 ℃ and stirred for 5 min.
(2) Adding 2 g of graphite powder and 1 g of sodium nitrate into a beaker, keeping the temperature of 0-5 ℃, and stirring for 0.5 h.
(3) Adding 6 g of potassium permanganate into the beaker, and stirring for 2 hours at the temperature of 0-5 ℃.
(4) The ice bath was removed and the mixture was heated to 38 ℃ and stirred for 2 h.
(5) 50mL of ultrapure water was added to the beaker, heated to 88 ℃ and stirred for 0.5 h.
(6) After the heating was stopped, 80 mL of ultrapure water and 4 mL of 30% hydrogen peroxide were added to the beaker, and the reaction was completed.
(7) Washing with 5% hydrochloric acid for 4 times, adding ultrapure water to a constant volume, performing ultrasonic treatment for 1.5 h, and adjusting the pH value to be neutral to obtain the graphene oxide dispersion liquid.
Preparing nano silver/graphene aerogel:
(1) 30 mL of 5 mg/mL graphene oxide dispersion liquid was measured, 0.25 g of silver nitrate and 500. mu.L of methylamine solution were added thereto, and stirring was carried out for 2 hours.
(2) Pouring the mixed solution into a reaction kettle, and keeping the temperature of 130 ℃ for hydrothermal treatment for 360 min.
(3) And (3) after the hydrothermal product is subjected to freeze drying, washing the product for 3 times by using ultrapure water, and drying the product for 6 hours in a vacuum drying oven at the temperature of 60 ℃ for later use.
From the SEM image, it can be seen that the silver particles in fig. 1 (a) without the graphene aerogel as the carrier are agglomerated together, affecting its bactericidal effect. In contrast to fig. 1 (b), there are uniformly dispersed silver particles in fig. 1 (c). It is apparent from fig. 1 (d) that the silver is substantially smaller than 100nm in size, and belongs to a nanomaterial. From the XRD of fig. 2, it can be seen that the characteristic XRD peaks (2 θ = 38.1 °, 44.3 °, 67.4 °, 77.4 °) of the nanosilver/graphene aerogel include silver, where the disappearance of the graphite peak near 25 ° is probably due to the nanosilver preventing the stacking effect of the graphene sheet layers.
Example 2: nano-silver/graphene aerogel composite material sterilization experiment
The specific experimental steps are as follows:
taking 4 centrifuge tubes numbered 1, 2, 3 and 4, adding 50mL 108And adding 150 mg of nano-silver, 170 mg of graphene aerogel and 310 mg of nano-silver/graphene aerogel into the CFU/mL escherichia coli liquid, 2, 3 and 4 respectively, and standing. 0.1 mL of each of the solutions was dropped from 4 centrifuge tubes at intervals onto LB agar, plated and incubated at 37 ℃ for 24 hours. As shown in fig. 3, the nano-silver/graphene aerogel has a good sterilization effect within 30 minutes, and the sterilization rate reaches 100%. And the sterilizing effect of other 2 materials is not obvious.
The sterilized nano silver/graphene aerogel is fished out by using tweezers and then dried, and a repeated sterilization test is carried out, as shown in fig. 4, after 7 repeated experiments, the nano silver/graphene aerogel still can keep a good sterilization effect, and the sterilization rate reaches 100%.
As shown in FIG. 5, the average of the 6-time release concentrations of silver ions was 0.099 mg/L. In 50mL of water, the average loss of nanosilver per sterilization of nanosilver/graphene aerogel was 0.0005 mg per sterilization, which is completely negligible compared to 150 mg nanosilver in the whole material. The nano silver/graphene aerogel is very stable in properties.
Claims (5)
1. The preparation method of the high-efficiency sterilization composite material is characterized by comprising the following steps: adding methylamine and silver nitrate into the graphene oxide solution, uniformly stirring, synthesizing a composite material by a hydrothermal method, and finally obtaining a nano-silver/graphene aerogel finished product by a freeze-drying method;
the concentration of the graphene oxide is 0.5-10 mg/mL;
the concentration of the silver nitrate is 1-20 mg/mL;
the concentration of the methylamine is 0.0065-0.25 mmol/mL;
the temperature of the hydrothermal reaction is 90-180 ℃, and the reaction time is 150-600 min;
the sterilization composite material is composed of nano silver and graphene aerogel, and nano silver particles are uniformly dispersed on the graphene aerogel.
2. The method for preparing a high-efficiency sterilization composite material as claimed in claim 1, wherein the method comprises the following steps: the nano-silver particles are uniformly dispersed on the graphene aerogel, the diameter of the silver particles is 10-100nm, and the mass ratio of the nano-silver to the graphene aerogel is 0.2-0.7: 1.
3. the method for preparing the high-efficiency sterilization composite material as claimed in claim 1, which is characterized by comprising the following steps: the adopted graphene oxide is synthesized by a Hummers method, and the prepared graphene oxide is in a liquid state for later use without separation, drying, direct volume fixing, ultrasonic treatment and pH adjustment.
4. The method for preparing the high-efficiency sterilization composite material as claimed in claim 1, which is characterized by comprising the following steps: the stirring time is 1-3 h.
5. The method for preparing the high-efficiency sterilization composite material as claimed in claim 1, which is characterized by comprising the following steps: the freeze drying temperature, the vacuum degree and the drying time are respectively-20 to-70 ℃, 100 to 6000Pa and 10 to 100 hours.
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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 |
| CN105032354A (en) * | 2015-07-29 | 2015-11-11 | 北京石油化工学院 | Silver nanowire/graphene composite elastic aerogel, and preparation method and application thereof |
| 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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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105032354A (en) * | 2015-07-29 | 2015-11-11 | 北京石油化工学院 | Silver nanowire/graphene composite elastic aerogel, and preparation method and application thereof |
| 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 |
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