CN103028737B - Method for preparing graphene-metal nano particle composite material - Google Patents
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- CN103028737B CN103028737B CN201210563031.9A CN201210563031A CN103028737B CN 103028737 B CN103028737 B CN 103028737B CN 201210563031 A CN201210563031 A CN 201210563031A CN 103028737 B CN103028737 B CN 103028737B
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Abstract
The invention provides a method for preparing graphene-metal nano particle composite material. The method comprises the following steps of: preparing polystyrene-polyvinyl pyridine PS-PVP micelle for loading metal salt; adhering the PS-PVP micelle for loading the metal salt on a substrate with a catalyst; and placing the substrate adhered with the PS-PVP micelle for loading the metal salt in a reaction vessel, resolving the PS-PVP micelle under a reducing atmosphere, generating a graphene film on the surface of the substrate, and reducing the metal salt loaded on the PS-PVP micelle as metal nano particles and uniformly dispersing the metal nano particles on the graphene film, so as to obtain the graphene-metal nano particle composite material. By the method, the graphene-metal nano particle composite material can be simply and high-efficiently formed.
Description
Technical field
The present invention relates to materials science field, relate in particular to a kind of method of preparing Graphene-metal nano particle composite material.
Background technology
Graphene is a kind of New Two Dimensional material with carbon element just having risen in recent years.Since grapheme material has caused the extensive concern of scientific circles since 2004 Nian Britain are found, this is due to Graphene, to have the character of many excellences, for example high carrier mobility, good conduction property, higher light transmission rate, engineering properties etc. preferably, thereby make it have application prospect widely.Preparation about grapheme material at present has developed a lot of methods, such as mechanical stripping method, chemical vapour deposition technique, graphite oxide reducing process etc.Wherein, utilize chemical vapour deposition technique, at Cu, the method of the metallic catalyst superficial growth Graphenes such as Ni is owing to obtaining large area, continuous graphene film, and graphene film defect is few, the number of plies is few, quality is better, it is a kind of method of the tool advantage of large-scale industrial production grapheme material, especially utilize chemical vapor depsotition equipment, method by solid-state carbon source (as various polymer) at metallic catalyst superficial growth Graphene, because of its high-quality, relative low temperature, the advantages such as raw material range of choice is wide and cheap, become the important channel of preparing high-quality graphene.
Graphene-metal nano-particle complexes is a kind of novel nanostructured.Metal nanoparticle and Graphene are combined, can regulate and control the work function of Graphene, significantly improve the photoelectric property of Graphene, the advantageous property of Graphene can also be combined to improve the performance of the devices such as graphene-based solar cell, light emitting diode, photo-detector with the plasma properties of metal nanoparticle excellence.Therefore the preparation and property research of, carrying out Graphene-metal nano particle composite material has very important significance.
Preparing at present Graphene-metal nano particle composite material is mainly to prepare in the process of Graphene in graphite oxide reducing process, by mixing nano particle to realize the preparation of Graphene and metal nano particle composite material in graphite oxide.But Graphene prepared by graphite oxide reducing process exists that electrical properties is poor, the number of plies is relatively many and inhomogeneous, and is difficult to make the shortcomings such as large area continuous film, thereby can not embody the advantageous property of Graphene completely.Although utilize the method for chemical vapour deposition (CVD) can access high-quality Graphene, because this method is direct growth grapheme material on substrate, can not obtain the composite of Graphene and metal nanoparticle.
Summary of the invention
(1) technical problem that will solve
For solving above-mentioned one or more problems, the invention provides a kind of method of preparing Graphene-metal nano particle composite material.
(2) technical scheme
According to an aspect of the present invention, provide a kind of method of preparing Graphene-metal nano particle composite material.The method comprises: the polystyrene-poly vinylpyridine PS-PVP micella of preparing loading metal-salt; The PS-PVP micella of loading metal-salt is attached on the substrate with catalyst; And the substrate that adheres to the PS-PVP micella of loading metal-salt is put into reaction vessel, under reducing atmosphere, make PS-PVP micella decompose, on metallic catalyst surface, produce graphene film, the slaine simultaneously loading in micella is reduced into as metal nanoparticle and is dispersed on described graphene film, thereby obtains Graphene and metal nano particle composite material.
(3) beneficial effect
From technique scheme, can find out, the method that the present invention prepares Graphene-metal nano particle composite material not only can form Graphene and metal nano particle composite material simply efficiently, can retain the advantage that CVD method is prepared Graphene, obtain high-quality film simultaneously.
Accompanying drawing explanation
Fig. 1 is for preparing the flow process of Graphene-metal nano particle composite material method according to the embodiment of the present invention;
Fig. 2 A is that the PS-PVP micella of loading metal-salt is spin-coated on the generalized section after Copper Foil;
Fig. 2 B is the generalized section that the PS-PVP micella of loading metal-salt is spin-coated on the Sapphire Substrate of deposited copper film.
Fig. 3 A is that the Graphene that obtains of growth and metal nano particle composite material are transferred to surface and have the optical microscope photograph after the silicon chip surface of 300nm thermal oxide layer on Copper Foil;
Fig. 3 B is the electron scanning micrograph of silicon chip surface shown in Fig. 3 A.
The specific embodiment
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with specific embodiment, and with reference to accompanying drawing, the present invention is described in more detail.
It should be noted that, in accompanying drawing or description description, similar or identical part is all used identical figure number.The implementation that does not illustrate in accompanying drawing or describe is form known to a person of ordinary skill in the art in affiliated technical field.In addition, although the demonstration of the parameter that comprises particular value can be provided herein, should be appreciated that, parameter is without definitely equaling corresponding value, but can in acceptable error margin or design constraint, be similar to corresponding value.
The load that utilization of the present invention is coated in metallic catalyst substrate surface has block copolymer polystyrene-poly vinylpyridine (PS-PVP) micella of slaine as the carbon source of Graphene growth, at metallic catalyst superficial growth graphene film, in the process of Graphene growth, slaine is reduced into metal nanoparticle and is retained in equably on the film of generation, thereby obtains Graphene-metal nano particle composite material.
In one exemplary embodiment of the present invention, provide a kind of method of preparing Graphene-metal nano particle composite material.As shown in Figure 1, the method comprises:
Steps A: prepare loading metal-salt HAuCl
4pS-PVP micella;
This steps A can comprise again:
Sub-step A1, is dissolved in PS-PVP in toluene, to form reverse micelle by the concentration of 5mg/ml;
Except toluene, can also adopt the p-poly-phenyl ethene PS blocks such as meta-xylene and polyvinylpyridine PVP block to have different deliquescent solvents to prepare reverse micelle, those skilled in the art can select the concentration of PS-PVP as required, generally between between 1mg/ml to 20mg/ml.
Sub-step A2 adds the HAuCl of preset concentration in reverse micelle
4, this preset concentration is depending on the concentration of metal nanoparticle.
Step B: by load HAuCl
4the spin coating of PS-PVP micella or dip-coating have on the substrate of catalyst;
Due to the booster action of the growth needs metallic catalyst (as Cu, Ni) of Graphene, so the substrate of Graphene-metal nano particle composite material growth is preferably the metal substrate of this catalyst material or the nonmetal substrate of plated metal catalyst film on nonmetal substrate.This nonmetal substrate is such as being sapphire, quartz, silicon etc., and the method for plated metal catalyst film can be the film plating process such as evaporation or sputter.
Please refer to Fig. 2 A and Fig. 2 B.Wherein, the PS-PVP micella that Fig. 2 A is loading metal-salt is spin-coated on the generalized section after Copper Foil.Fig. 2 B is the generalized section that the PS-PVP micella of loading metal-salt is spin-coated on the Sapphire Substrate of deposited copper film.
Step C: the substrate of the PS-PVP micella of spin coating or dip-coating loading metal-salt is put into CVD reacting furnace and calcine, at Ar/H
2under atmosphere, PS-PVP micella decomposes, on metallic catalyst surface, produce graphene film, the slaine simultaneously loading in micella is reduced into as metal nanoparticle and is dispersed on the graphene film of generation, obtains Graphene and metal nano-particle complexes.
In this step, the growth apparatus of growing graphene and metal nano particle composite material is chemical vapour deposition (CVD) (CVD) reaction system, and growth temperature is 800-1000 ℃, and growth atmosphere is the mist of argon gas and hydrogen or the reducibility gas of other types.Growth time is 10-30min, depending on the thickness of graphene film.
In this step, before to reacting furnace heating, need to first to reacting furnace, vacuumize, then pass into again argon gas and hydrogen, thereby realize Ar/H
2atmosphere.
Step D, after reacting completely and carrying out, lowers the temperature to reacting furnace, keeps Ar/H in temperature-fall period always
2reducing atmosphere;
Step e: Graphene and metal nano-particle complexes are shifted from substrate.
In this step, shift Graphene consistent with the method for existing transfer CVD Graphene with the method for metal nano-particle complexes, for example adopt turning shifting method of hot stripping tape, or adopt method of PDMS rubber impression etc., these methods by wide coverage, repeat no more in the prior art herein.
So far, the method that the present embodiment is prepared Graphene-metal nano particle composite material is introduced complete.
Fig. 3 A is that the Graphene that obtains of growth and metal nano particle composite material are transferred to surface and have the optical microscope photograph after the silicon chip surface of 300nm thermal oxide layer on Copper Foil, and Fig. 3 B is the electron scanning micrograph of silicon chip surface shown in Fig. 3 A.Then, after being transferred in target substrate according to above-mentioned steps growing graphene and metal nano-particle complexes on metallic catalyst, can in target substrate, leave a layer graphene and metal nano-particle complexes film.
It should be noted that, the present embodiment be take and prepared Graphene-gold nano grain composite and describe as example, but the present invention is not limited to prepare this kind of composite, Graphene-magnesium-yttrium-transition metal the nano particle composite material that can also prepare other types, for example: can also adopt loading metal-salt AgNO
3pS-PVP micella prepare Graphene-silver nano-grain composite; Adopt loading metal-salt FeCl
3pS-PVP micella prepare Graphene-iron nano-particle composite; Adopt loading metal-salt H
2ptCl
6pS-PVP micella prepare Graphene-Pt nanoparticle composite etc.That is to say, the type of this slaine is the type decided of metal nanoparticle that need to be compound in Graphene, and this slaine should be easy to reduction under hot environment.Method and the present embodiment that it is prepared are similar.No longer describe in detail herein.
In sum, the present invention prepares Graphene-metal nano particle composite material method and has not only retained the advantage that CVD method is prepared Graphene, the composite that simultaneously makes original position prepare Graphene and metal nanoparticle becomes possibility, for further studying and apply this material, lays a good foundation.The advantages such as compare with the method for metal nano-particle complexes with the Graphene of preparing of reporting in document, it is simple efficient that the method has, and the good and cost of film quality is lower are a kind of effective ways of directly preparing Graphene and metal nano particle composite material.
Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any modification of making, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. a method of preparing Graphene-metal nano particle composite material, is characterized in that, comprising:
The polystyrene-poly vinylpyridine PS-PVP micella of preparing loading metal-salt;
The PS-PVP micella of described loading metal-salt is attached on the substrate with catalyst; And
The described substrate that adheres to the PS-PVP micella of loading metal-salt is put into reaction vessel, under reducing atmosphere, make described PS-PVP micella decompose, at substrate surface, produce graphene film, the slaine simultaneously loading in PS-PVP micella is reduced into as metal nanoparticle and is dispersed on described graphene film, thereby obtains Graphene and metal nano particle composite material.
2. method according to claim 1, is characterized in that, the described step of preparing the PS-PVP micella of loading metal-salt comprises:
PS-PVP is dissolved in to p-poly-phenyl ethene PS block to be had different and forms reverse micelle in deliquescent solvent with polyvinylpyridine PVP block; And
The slaine that adds preset concentration in reverse micelle, this preset concentration is depending on the concentration of metal nanoparticle.
3. method according to claim 2, is characterized in that, it is toluene or dimethylbenzene that described p-poly-phenyl ethene PS block has different deliquescent solvent with polyvinylpyridine PVP block.
4. method according to claim 1, is characterized in that, adopts the method for spin coating or dip-coating that the PS-PVP micella of loading metal-salt is attached on the substrate with catalyst.
5. method according to claim 4, is characterized in that, described in there is metal substrate that the substrate of catalyst is catalyst material or the nonmetal substrate of deposited catalyst film on nonmetal substrate.
6. method according to claim 5, is characterized in that:
Described catalyst is Cu or Ni;
Described nonmetal substrate is sapphire, quartz or silicon, and the method for described plated metal catalyst film is evaporation or sputter.
7. method according to claim 1, is characterized in that, described the substrate that adheres to the PS-PVP micella of loading metal-salt is put into reaction vessel, makes in step that PS-PVP micella decomposes, and described reaction temperature is between 800 ℃ to 1000 ℃; Reaction time is between between 10min to 30min; Reaction atmosphere is Ar/H
2atmosphere.
8. method according to claim 7, is characterized in that, described reaction vessel is CVD reacting furnace.
9. method according to claim 7, is characterized in that, described in obtain also comprising after the step of Graphene and metal nano particle composite material:
Graphene and metal nano-particle complexes are shifted from substrate, and the method for this transfer is that hot stripping tape turns shifting method, or PDMS rubber method for stamping.
10. according to the method described in any one in claim 1 to 9, it is characterized in that, described slaine is looked the kind of metallic element to be composite and is determined, wherein:
Described metal nanoparticle is Au particle, and described slaine is HAuCl
4;
Described metal nanoparticle is Fe particle, and described slaine is FeCl
3; Or
Described metal nanoparticle is Pt particle, and described slaine is H
2ptCl
6.
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| CN106442464B (en) * | 2016-09-19 | 2019-03-08 | 宁波大学 | A kind of preparation method of silicon wafer/reduced graphene/Jenner's nano composite material |
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| CN109449262B (en) * | 2018-09-26 | 2020-12-04 | 华南师范大学 | Visible light communication device capable of improving light efficiency based on Cu-doped graphene and preparation method thereof |
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| CN110790264B (en) * | 2019-12-10 | 2022-05-06 | 中国科学院金属研究所 | Graphene powder with controllable form and preparation method thereof |
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