CN112753698A - Nano metal-reduced graphene oxide composite material and preparation method and application thereof - Google Patents
Nano metal-reduced graphene oxide composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a nano metal-reduced graphene oxide composite material and a preparation method and application thereof, wherein the method comprises the following steps: preparing a graphene oxide aqueous solution and adjusting the pH value to 8-13; preparing a metal salt aqueous solution, adding the metal salt aqueous solution into the graphene oxide aqueous solution with the pH value adjusted, and uniformly mixing to obtain a mixed solution; and adding a reducing agent into the mixed solution for reduction reaction to obtain the nano metal-reduced graphene oxide composite material. The method fully utilizes the structural characteristics of graphene oxide molecules, does not need to add additional dispersing agents, and can be used for large-scale industrial production. The obtained composite material has excellent antibacterial performance, can be used as an antibacterial material, and has good application prospect.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a nano metal-reduced graphene oxide composite material and a preparation method and application thereof.
Background
Graphene Oxide (Graphene Oxide), a single-layer material peeled off from graphite Oxide, can exist stably in aqueous solutions and polar solvents due to the introduction of a large number of oxygen-containing groups on the surface and edges. After oxidation treatment, the graphite oxide still maintains the layered structure of graphite, but a plurality of oxygen-based functional groups are introduced on each layer of graphene single sheet. The stable graphene oxide sheet layer can be used for carrying metal nanoparticles such as nano silver, nano gold and the like, and the obtained material has wide application prospect. At present, the preparation method of the graphene oxide-metal composite material is mainly an in-situ reduction method, however, a dispersant is mostly required to be added in the method to avoid agglomeration of metal nanoparticles, but the addition of the dispersant can affect the performance of the material, and the method is also limited in practical application.
It is noted that the information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and therefore it may contain information that does not constitute prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention aims to overcome at least one defect in the prior art, and provides a preparation method of a nano metal-reduced graphene oxide composite material and the composite material obtained by the method.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a nano metal-reduced graphene oxide composite material, which comprises the following steps: preparing a graphene oxide aqueous solution and adjusting the pH value to 8-13; preparing a metal salt aqueous solution, adding the metal salt aqueous solution into the graphene oxide aqueous solution with the pH value adjusted, and uniformly mixing to obtain a mixed solution; and adding a reducing agent into the mixed solution for reduction reaction to obtain the nano metal-reduced graphene oxide composite material, wherein the metal is one or more selected from gold, silver, platinum, iron, cobalt and nickel.
According to one embodiment of the invention, adjusting the pH comprises: adding soluble alkali into the graphene oxide aqueous solution, wherein the soluble alkali is selected from one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate and ammonia water.
According to one embodiment of the present invention, the concentration of graphene oxide in the graphene oxide aqueous solution is 50g/L to 500 g/L.
According to one embodiment of the invention, the metal is silver and the metal salt is selected from one or more of silver nitrate, silver acetate, silver citrate, silver methanesulfonate and silver ammonia solution.
According to one embodiment of the present invention, the mass ratio of graphene oxide to metal salt is 1: (0.1-5).
According to one embodiment of the invention, the reducing agent is selected from one or more of sodium citrate, glucose, ascorbic acid, sodium borohydride, hydrazine hydrate, polyvinylpyrrolidone, polyvinyl alcohol, ethylene glycol and formaldehyde.
According to one embodiment of the invention, the temperature of the reduction reaction is 30-100 ℃, and the reaction time of the reduction reaction is 0.1-48 h.
According to an embodiment of the invention, the method further comprises the steps of filtering, washing and drying the solution after the reduction reaction to obtain the nano metal-reduced graphene oxide composite material, wherein the drying comprises freeze drying or drying at 30-60 ℃.
The invention also provides a nano metal-reduced graphene oxide composite material which is obtained by adopting the preparation method.
The invention also provides application of the nano metal-reduced graphene oxide composite material as a bacteriostatic material, wherein the metal is silver.
According to the technical scheme, the invention has the beneficial effects that:
according to the preparation method of the nano metal-reduced graphene oxide composite material, no additional dispersing agent is needed, the graphene oxide can be directly used as the dispersing agent and the carrier of the nano metal by adjusting the pH value of the solution, the structural characteristics of graphene oxide molecules are fully utilized, the preparation process is simple, the cost is low, and the obtained composite material has excellent antibacterial performance and is suitable for large-scale industrial production.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
Fig. 1a and 1b are scanning electron micrographs of the nano silver-reduced graphene oxide composite material of example 2 at different magnifications, respectively;
fig. 2a and 2b are scanning electron micrographs of the nano silver-reduced graphene oxide composite material of comparative example 1 at different magnifications, respectively;
FIGS. 3a and 3b are graphs of E.coli and S.aureus growth after the addition of different masses of the composite material of example 2, respectively.
Detailed Description
The following presents various embodiments or examples in order to enable those skilled in the art to practice the invention with reference to the description herein. These are, of course, merely examples and are not intended to limit the invention. The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of a nano metal-reduced graphene oxide composite material. As mentioned above, the current preparation method of graphene oxide-metal composite material is mainly an in-situ reduction method, however, in this method, a dispersant is often added to avoid agglomeration of metal nanoparticles, but the addition of the dispersant will affect the performance of the material, and is also very limited in practical application. Therefore, the composite material of the nano metal composite reduced graphene oxide can be obtained without using a dispersing agent by controlling the reaction conditions.
The following method for producing a composite material is described as an example of application to nano silver. It will be readily understood by those skilled in the art that various modifications, additions, substitutions, deletions, or other changes may be made to the embodiments described below in order to apply the method of the present invention to other types of transition metals, such as gold, platinum, iron, cobalt, nickel, etc., and still fall within the scope of the principles of the method for preparing a nanometal-reduced graphene oxide composite material according to the present invention.
Specifically, the method of the present invention comprises the steps of:
firstly, preparing a graphene oxide aqueous solution and adjusting the pH value to 8-13, preferably 9-10; specifically, graphene oxide is added into water, after the graphene oxide is uniformly stirred, ultrasonic treatment is carried out for 0.5-4 hours, preferably 1-2 hours, and then the pH value is adjusted to 8-13, preferably 9-10. Wherein adjusting the pH comprises: adding a soluble base to the graphene oxide aqueous solution to bring the pH value to a corresponding value, wherein the soluble base includes, but is not limited to, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate, ammonia water, and the like, but the present invention is not limited thereto. In some embodiments, the concentration of graphene oxide in the aqueous graphene oxide solution is 50g/L to 500 g/L. Preferably, it is 100g/L to 300 g/L.
And then preparing a silver salt aqueous solution, namely adding soluble silver salt into water and uniformly stirring, wherein the silver salt is selected from one or more of silver nitrate, silver acetate, silver citrate, silver methanesulfonate and silver ammonia solution. The mass ratio of the graphene oxide to the silver salt is 1: (0.1 to 5), preferably 1: (0.5 to 3). After the preparation is finished, adding a silver salt aqueous solution into the graphene oxide aqueous solution, stirring and optionally carrying out ultrasonic treatment to uniformly mix the solution to obtain a mixed solution. Wherein the stirring time is 0.5 h-2 h, and the ultrasonic time is 10 min-60 min.
And then, adding a reducing agent into the uniformly mixed solution in a stirring state for reduction reaction, wherein the reaction temperature is 30-100 ℃, the reaction time can be changed according to the used reducing agent, generally ranges from 0.1h to 48h, and the silver salt and the graphene oxide are reduced into nano silver and reduced graphene oxide respectively. In some embodiments, the aforementioned reducing agent is selected from one or more of sodium citrate, glucose, ascorbic acid, sodium borohydride, hydrazine hydrate, polyvinylpyrrolidone, polyvinyl alcohol, ethylene glycol, and formaldehyde.
According to the invention, the graphene oxide is of a lamellar structure containing multiple aromatic rings, hydroxyl groups, carbonyl groups and carboxyl functional groups, under an alkaline condition, the graphene oxide is negatively charged, the repulsion among the lamellar is increased, the distance among the lamellar is larger, silver salt can enter the lamellar, the empty orbit of silver ions and the multiple aromatic rings, the hydroxyl groups and the carbonyl groups of the graphene oxide interact to form pi-type aromatic ring-metal ions and oxygen-containing group-metal ions, so that the silver ions are adsorbed on the lamellar; in addition, silver salt has positive charge, and carboxyl and silver ions can be combined under the electrostatic action, so that the silver ions are firmly attached to the graphene oxide sheet layer, and the graphene oxide can be used as a dispersing agent for the silver ions. After silver ions are reduced, electron transfer occurs between the generated nano silver and an aromatic ring of the reduced graphene oxide, so that the nano silver is attached to a reduced graphene oxide lamella, and the nano silver particles are prevented from growing or agglomerating; moreover, the lamellar structure can limit the migration of the nano silver. On the other hand, after the graphene oxide is reduced, the nano-silver can prevent the reduction of the graphene oxide sheet layer stack from regenerating a graphite structure.
Further, the method also comprises the step of filtering, washing and drying the solution after the reduction reaction to obtain the black powder nano silver-reduced graphene oxide composite material. The drying method of the composite material is preferably drying by a vacuum oven at 30-60 ℃ or freeze-drying by a freeze-drying method, but the invention is not limited thereto.
The invention makes full use of the self structural characteristics of the composite material by regulating and controlling the reaction conditions, does not need to add other dispersing agents in the preparation process, saves the reaction process and the preparation cost, simultaneously has good performance, and is suitable for large-scale industrial production.
The nano silver has broad-spectrum antibacterial property, can kill about 650 kinds of bacteria, does not generate drug resistance, and is a good bacteriostatic agent. The bacteriostatic effect of the nano-silver is directly related to the particle size of the nano-silver, and the smaller the particle size is, the better the bacteriostatic effect is. However, the surface energy of the small-particle nano silver is large, the small-particle nano silver is easy to agglomerate, and a dispersing agent is required to be added to be dispersed in a solution or loaded on a carrier. Compared with pure nano silver, the nano silver-reduced graphene oxide composite material obtained by the method has a good antibacterial effect, and can be used as an antibacterial material.
The invention will be further illustrated by the following examples, but is not to be construed as being limited thereto.
Example 1
This example is provided to illustrate the preparation of the nano silver-reduced graphene oxide composite material according to the present invention.
1) 1g of graphene oxide (manufacturer: suzhou carbon feng science and technology, type: thin-layer graphene oxide with the pH value of 3-4) is dispersed in 500ml of water solution, the mixture is stirred uniformly, ultrasonic treatment is carried out for 1h, and sodium hydroxide water solution is added to adjust the pH value to 13, so as to obtain graphene oxide water solution;
2) dissolving 1g of silver nitrate in 100ml of water, then dropwise adding the silver nitrate into the graphene oxide aqueous solution, fully stirring, and performing ultrasonic treatment for 20min to obtain a mixed solution;
3) heating to 80 ℃, dropwise adding 20ml of 20% sodium citrate aqueous solution into the mixed solution, and reacting for 1h after dropwise adding. Cooling to normal temperature, filtering, washing, and vacuum drying at 40 ℃ to obtain the black solid powder nano silver-reduced graphene oxide composite material.
Example 2
1) 500mg of graphene oxide (manufacturer: suzhou carbon feng science and technology, type: thin-layer graphene oxide with the pH value of 3-4) is dispersed in 200ml of aqueous solution, the mixture is uniformly stirred and subjected to ultrasonic treatment for 2 hours, and sodium carbonate aqueous solution is added to adjust the pH value to 10, so that graphene oxide aqueous solution is obtained;
2) dissolving 0.2g of silver acetate in 50ml of hot water, then dropwise adding the solution into the graphene oxide aqueous solution, and fully stirring the solution to obtain a mixed solution;
3) heating to 60 ℃, dropwise adding 10ml of ascorbic acid aqueous solution with the concentration of 25% into the mixed solution, and reacting for 1h after the dropwise adding. And cooling to normal temperature, filtering, washing, freezing and drying to obtain the black solid powder nano silver/reduced graphene oxide composite material. Fig. 1a and 1b respectively show scanning electron microscope images of the nano silver-reduced graphene oxide composite material at different magnifications, and as can be seen from fig. 1a and 1b, nano silver is uniformly distributed on the reduced graphene oxide sheet layer, and the particle size is about 10-30 nm.
Comparative example 1
The reagents and procedure were the same as in example 1, except that in step 1), the pH of the aqueous graphene oxide solution was not adjusted. And after the reaction is finished, the reduced graphene oxide is still dispersed in water and cannot be filtered, the solution is centrifuged at 9000-10000 r/min, the supernatant is poured out, the lower black solid is added with clear water and uniformly mixed, the mixture is centrifuged, the washing is repeated for 2-3 times in the way, and the black flaky solid nano silver-reduced graphene oxide composite material is obtained after vacuum drying at 40 ℃. Fig. 2a and 2b show scanning electron micrographs of the nanocomposite, respectively. As can be seen from fig. 2a and 2b, the nano silver is not uniformly distributed on the reduced graphene oxide, some rGO sheets have nano silver, some rGO sheets have almost no nano silver, and the particle size distribution range of the nano silver is very wide, which indirectly indicates that the bacteriostatic effect of the material is not very good.
Application example 1
Resuscitating Escherichia coli (gram negative bacteria) and Staphylococcus aureus (gram positive bacteria) stored in 80 deg.C-80 deg.C refrigerator, shake culturing with LB culture medium at 37 deg.C at 220r/min to logarithmic phase, measuring OD value (optical density value) at 600nm wavelength with ultraviolet-visible spectrophotometer, adjusting OD value to 1, and adding 900 μ L into 150ml LB for culturing.
Weighing 1.8mg, 1.5mg, 1.2mg and 0.9mg of the nano-silver-reduced graphene oxide composite material (AgNPs/rGO) of the embodiment 2 respectively, adding the nano-silver-reduced graphene oxide composite material (AgNPs/rGO) of the embodiment 2 into a culture medium containing escherichia coli, weighing 10.5mg, 8mg and 7.5mg of the nano-silver-reduced graphene oxide composite material (AgNPs/rGO) of the embodiment 2, adding a culture medium containing staphylococcus aureus, culturing at 37 ℃ and 220r/min by a shaking table, measuring OD values at 600nm wavelength at intervals, and drawing bacterial growth curves, which are respectively shown in fig. 3a and fig. 3 b. The minimum inhibitory concentration of the composite material on escherichia coli (e.coli) is 12mg/L as shown in fig. 3a, and the minimum inhibitory concentration on staphylococcus aureus (s.aureus) is 70mg/L as shown in fig. 3 b. Therefore, the nano silver-reduced graphene oxide composite material prepared by the method has a good antibacterial effect.
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.
Claims (10)
1. A preparation method of a nano metal-reduced graphene oxide composite material is characterized by comprising the following steps:
preparing a graphene oxide aqueous solution and adjusting the pH value to 8-13;
preparing a metal salt aqueous solution, adding the metal salt aqueous solution into the graphene oxide aqueous solution with the adjusted pH value, and uniformly mixing to obtain a mixed solution;
and adding a reducing agent into the mixed solution for reduction reaction to obtain the nano metal-reduced graphene oxide composite material, wherein the metal is one or more selected from gold, silver, platinum, iron, cobalt and nickel.
2. The method of claim 1, wherein the adjusting the pH comprises: adding soluble alkali into the graphene oxide aqueous solution, wherein the soluble alkali is selected from one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate and ammonia water.
3. The method according to claim 1, wherein the concentration of graphene oxide in the aqueous graphene oxide solution is 50 to 500 g/L.
4. The method according to claim 1, wherein the metal is silver, and the metal salt is one or more selected from the group consisting of silver nitrate, silver acetate, silver citrate, silver methanesulfonate, and silver ammonia solution.
5. The preparation method according to claim 1, wherein the mass ratio of the graphene oxide to the metal salt is 1: (0.1-5).
6. The method according to claim 1, wherein the reducing agent is selected from one or more of sodium citrate, glucose, ascorbic acid, sodium borohydride, hydrazine hydrate, polyvinylpyrrolidone, polyvinyl alcohol, ethylene glycol, and formaldehyde.
7. The preparation method according to claim 1, wherein the temperature of the reduction reaction is 30 ℃ to 100 ℃, and the reaction time of the reduction reaction is 0.1h to 48 h.
8. The preparation method according to claim 1, further comprising filtering, washing and drying the solution after the reduction reaction to obtain the nano metal-reduced graphene oxide composite material, wherein the drying comprises freeze drying or drying at 30-60 ℃.
9. A nano metal-reduced graphene oxide composite material obtained by the preparation method of any one of claims 1 to 8.
10. The use of the nanometal-reduced graphene oxide composite according to claim 9 as a bacteriostatic material, wherein the nanometal is nanosilver.
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