CN105251484B - Three-dimensional structure redox graphene/nanometer metallic silver aeroge and preparation method - Google Patents
Three-dimensional structure redox graphene/nanometer metallic silver aeroge and preparation method Download PDFInfo
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Abstract
The present invention relates to a kind of three-dimensional structure redox graphene/nanometer metallic silver aeroge and preparation method thereof, described aeroge is the three-dimensional porous structure being made up of redox graphene lamella and uniform load in the polycrystalline Nano argent on redox graphene lamella, is prepared by the following method and forms：(1) silver soluble saline solution is well mixed with graphene oxide water solution, obtains precursor solution；(2) precursor solution is moved into reductant solution, reacts at room temperature, obtain three-dimensional grapheme/metal silver nano-grain hydrogel；(3) purpose product is obtained after three-dimensional grapheme/metal silver nano-grain hydrogel being taken out into cleaning, drying.Compared with prior art, the present invention has the advantages that preparation method is simple, and whole course of reaction is carried out at room temperature, without excessive additional energy consumption.
Description
Technical field
The present invention relates to nano-composite catalyst field, more particularly, to a kind of three-dimensional structure redox graphene/receive
Rice argent aeroge and preparation method thereof.
Background technology
Catalyst has a highly important effect in industrial production and environmental monitoring and in administering, about 2/3rds
Chemical products and 90 percent chemical production processes are directed to catalysis technique.Since the sixties in previous generation, when it is found that
Material can show Dielectric confinement effect, skin effect, macro quanta tunnel effect, small chi when being reduced in size to nanoscale
After the properties such as very little bulk effect, quantum size effect, nano material becomes the focus of scientific research, especially as height
Imitate the metal nano material of catalyst.The reduction of metal material size has two significant works in the application of catalytic field
With, first, as the reduction of size can increase chemical unsaturation and thermodynamically the surface-active atom of high-energy；The
Two, the increase that fermi level reduces with size can result in the reduction of reduction potential, and the two effects are to improve catalytic performance
Most critical factor.And silver nano-grain turns into it so that its is cheap, biocompatibility is high, is easy to the characteristics such as reduction, good conductivity
In one of member of greatest concern.But nano particle has the problem of easily reuniting, therefore find a kind of suitable substrate material
Material, enable nano particle it is highdensity it is good it is scattered be current focus.
Graphene has physics and electrochemical properties free from worldly cares, for example, high thermal stability, high-specific surface area, high conductivity,
High mechanical properties, it is easy to oxy radicals such as modification-COOH ,-OH etc., therefore is highly suitable as the carrier material of nano particle,
Particularly three-dimensional graphene-structured has higher specific surface area, can play more preferable peptizaiton.It is in situ at present to prepare
The method of three-dimensional grapheme/metal nanoparticle is generally CVD, hydro-thermal method, hot solution method etc., and these preparation methods are not only
Preparation process is complicated, and consumed energy is big.
Chinese patent 201010523363.5 discloses a kind of preparation method of graphene-loaded platinum nano catalyst, (1)
The preparation of graphene；(2) preparation of diallyl dimethyl ammoniumchloride (PDDA) functionalization graphene；(3) it is graphene-supported
The preparation of platinum nano catalyst.Although the standby catalyst of the patent system solves the problems, such as that metallic particles easily occurs itself and reunited,
The higher load factor of platinum nano catalyst is realized, but it is more numerous and diverse in preparation process, and react to need to be in and heat ring
Carried out in border so that power consumption is larger.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of three-dimensional structure reduces
Graphene oxide/nanometer metallic silver aeroge and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of three-dimensional structure redox graphene/nanometer metallic silver aeroge, the aeroge is by redox graphene
Lamella and uniform load are in the three-dimensional porous structure of the polycrystalline Nano argent composition on redox graphene lamella.
The particle diameter of described nanometer metallic silver is 25~40nm.
A kind of preparation method of three-dimensional structure redox graphene/nanometer metallic silver aeroge, comprises the following steps：
(1) silver soluble saline solution is well mixed with graphene oxide water solution, obtains precursor solution；
(2) precursor solution is instilled in reductant solution, reacts at room temperature, obtain three-dimensional structure reduction-oxidation graphite
Alkene/metal silver nano-grain hydrogel；
(3) mesh is obtained after three-dimensional structure redox graphene/metal silver nano-grain hydrogel being taken out into cleaning, drying
Product.
The mass ratio of soluble silver salt and graphene oxide is (1~5) in precursor solution in step (1):1, it is described
The concentration of soluble silver salt is (10~50) mg/mL, and the concentration of graphene oxide water solution is (1~4) mg/mL.Silver soluble
Silver nitrate or silver-colored ammonia etc. may be selected in salt.
Described graphene oxide water solution is prepared by following steps：
(A) under 10 DEG C of water bath conditions, nitrate and crystalline flake graphite are added into the anhydrous concentrated sulfuric acid, heating stirring is reacted,
After the completion of reaction, room temperature is cooled to, after being diluted with water, drying is separated, obtains the first product；
(B) under 15 DEG C of water-baths, the anhydrous concentrated sulfuric acid and potassium permanganate are added in the first product obtained into step (A),
Heating is reacted；
(C) after reaction terminates, heating is stopped, addition deionized water is stirred, adds hydrogen peroxide solution, stood
At night, after washing and filtering, it is diluted with water and obtains requisite oxygen graphite aqueous solution.
In step (A)：Described nitrate is potassium nitrate or sodium nitrate, the anhydrous concentrated sulfuric acid, nitrate and crystalline flake graphite
The ratio between addition is (40~80) mL:(1~2) g:(2~4) g, the process conditions of heating stirring reaction are：At 10~15 DEG C
0.5h is stirred, then 3.5h is stirred at 15~60 DEG C；
In step (B)：In the anhydrous concentrated sulfuric acid, potassium permanganate and step (A) the ratio between addition of crystalline flake graphite for (40~
80)mL:(3~9) g:(2~4) g, the process conditions of heating stirring reaction are：It is warming up to 35-40 DEG C and keeps reaction 2h；
In step (C)：In deionized water, hydrogen peroxide solution and step (A) the ratio between addition of crystalline flake graphite for (40~
60)mL:(5~15) mL:(2~4) g, mixing time 1h, hydrogen peroxide solution are 30% hydrogen peroxide solution, the technique bar of washing
Part is：Repeatedly washed with 5% dilute nitric acid solution, the process conditions of filtering are：With the multiple centrifugal filtration of deionized water.
The volume ratio of the addition of reductant solution and precursor solution is (5~100) in step (2)：1, the reaction time
For 1~6h.
Described reductant solution is alkaline solution or the ascorbic acid solutions such as sodium hydroxide solution, potassium hydroxide solution.
Described reducing agent be concentration be 50~200mg/mL sodium hydroxide solution, 50~200mg/mL potassium hydroxide
The ascorbic acid solution of solution or 50~200mg/mL.
The drying of three-dimensional structure redox graphene/metal silver nano-grain hydrogel is freeze-drying in step (3)
Or supercritical drying.
Unlike the prior art, the present invention first mixes the mixed solution of graphene oxide and silver salt with reductant solution
It is even, and hydrogel can be self-assembled under conditions of room temperature.In the forming process of hydrogel, mixed solution is with fine droplet
Form is instilled in reductant solution, because drop is small, original form can be kept without molten in reducing agent by the effect of surface tension
Spread in liquid, reducing agent is entered inside droplet by space, and graphene oxide and silver salt are reduced, and finally directly forms water-setting
Glue.In order to make the surface tension of droplet maintain its original form enough, so as to which the aeroge of three-dimensional porous structure, oxygen be made
The concentration of graphite alkene can not be too low, i.e., certain active force is needed between graphene oxide layer to maintain droplet profile, together
When reducing agent reproducibility and concentration can not be too low, otherwise the recovery time can cause very much droplet diffusion into the surface long and structure is collapsed
Collapse.
Compared with prior art, redox graphene/nano metal of three-dimensional porous structure has been prepared in the present invention
Silver-colored aeroge, the small-sized density of silver nano-grain is very high and is evenly distributed on redox graphene lamella, improves
Reactivity area so that catalyst has more preferable catalytic performance.In addition, preparation method is to carry out at room temperature, it is not required to
Additionally to heat, and used reducing agent is nontoxic is easy to get, whole preparation technology is simple, particularly suitable for industrialized production.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of three-dimensional structure redox graphene/nanometer metallic silver aeroge produced by the present invention
Piece；
Fig. 2 is the transmission electron microscope picture of three-dimensional structure redox graphene/nanometer metallic silver aeroge produced by the present invention
Piece；
Fig. 3 is that the polycrystalline diffraction of three-dimensional structure redox graphene/nanometer metallic silver aeroge produced by the present invention is spent
Master drawing；
Fig. 4 is the X-ray diffractogram of three-dimensional structure redox graphene/nanometer metallic silver aeroge produced by the present invention
(XRD).
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
The first step, prefabricated graphene oxide, described graphene oxide are prepared in the following manner：10 DEG C of water-bath bars
Under part, 1g NaNO are added into 40ml concentrated sulfuric acid solutions3With 2g crystalline flake graphites；0.5h, 15 DEG C of stirring 3.5h are stirred at 10 DEG C；
Room temperature is cooled to, is diluted with deionized water, supernatant is separated after placing sedimentation, graphite is dried to obtain after centrifugal filtration；15 DEG C of water
Under bath, into above-mentioned dried graphite, the anhydrous concentrated sulfuric acids of addition 40ml and 3g potassium permanganate, it is warming up to 35 DEG C and keeps reaction
2h；Stop heating, add deionized water 40ml, stir 1h；The hydrogen peroxide solutions of 5ml 30% are added, are stood overnight；With 5% dilute nitre
Acid solution repeatedly washs, then with the multiple centrifugal filtration of deionized water, obtains required graphite oxide dispersion.
Second step, above-mentioned graphene oxide solution is diluted to 1mg/mL graphene oxide water solution, by a certain amount of nitre
Sour silver powder is dissolved in the water, and the concentration of silver nitrate aqueous solution is 10mg/mL, then silver nitrate and graphene oxide are pressed into 1:1
For quality than the mixed nitrate silver aqueous solution and graphene oxide water solution, ultrasonic 5min makes it well mixed, obtains mixed liquor.
3rd step, sodium hydroxide powder is dissolved in the water, and prepares 50mg/mL sodium hydroxide solution, by second step institute
State mixed liquor to be pipetted in 5 μ L, 25 μ L sodium hydroxide solutions of instillation with liquid-transfering gun, keep 1h at room temperature, obtain three-dimensional structure oxygen reduction
Graphite alkene/metal silver nano-grain hydrogel.
4th step, above-mentioned three-dimensional structure redox graphene/metal silver nano-grain hydrogel is being freeze-dried
After being dried in machine, three-dimensional structure redox graphene/metal silver nano-grain aeroge is obtained.
Obtained three-dimensional structure redox graphene/nanometer metallic silver aeroge is detected, Fig. 1 is it in difference
The scanning electron microscopic picture of aerogel material under resolution ratio, illustrate the structure and silver nano-grain of three-dimensional porous graphene oxide
Pattern；Fig. 2 shows the transmission electron microscope picture of aerogel material, it can be seen that the small-sized density of silver nano-grain it is very high and
It is evenly distributed on redox graphene lamella；Fig. 3 shows the polycrystalline diffraction pattern in a certain constituency in Fig. 2, and analysis can
Know that silver nano-grain constructs for polymorphic；The XRD of redox graphene lamella, Cong Zhongke in Fig. 4 aeroges for made from
To find out that the peak position corresponding to GO (001) crystal face in the present embodiment in XRD has been moved to the peak corresponding to rGO (002) crystal face
Position, illustrate that graphene oxide in this example (GO) becomes the redox graphene in 3D-rGO/AgNPs after carrying out reduction
(rGO).Three-dimensional structure redox graphene described in this example has higher specific surface area, can load more equal
Even scattered metal silver nano-grain, as a kind of catalyst, catalytic reaction activity point is effectively increased, improves catalytic
Energy.
Embodiment 2
The first step, prefabricated graphene oxide, described graphene oxide are prepared in the following manner：10 DEG C of water-bath bars
Under part, 1.2g KNO are added into 45ml concentrated sulfuric acid solutions3With 2.4g crystalline flake graphites；0.5h, 24 DEG C of stirrings are stirred at 11 DEG C
3.5h；Room temperature is cooled to, is diluted with deionized water, supernatant is separated after placing sedimentation, graphite is dried to obtain after centrifugal filtration；15
Under DEG C water-bath, into above-mentioned dried graphite, the anhydrous concentrated sulfuric acids of addition 45ml and 4g potassium permanganate, it is warming up to 36 DEG C and keeps anti-
Answer 2h；Stop heating, add deionized water 44ml, stir 1h；The hydrogen peroxide solutions of 7ml 30% are added, are stood overnight；With 5% it is dilute
Salpeter solution repeatedly washs, then with the multiple centrifugal filtration of deionized water, obtains required graphite oxide dispersion.
Second step, above-mentioned graphene oxide solution is diluted to 2mg/mL graphene oxide water solution, by a certain amount of nitre
Sour silver powder is dissolved in the water, and the concentration of silver nitrate aqueous solution is 20mg/mL, then silver nitrate and graphene oxide are pressed into 2:1
For quality than the mixed nitrate silver aqueous solution and graphene oxide water solution, ultrasonic 20min makes it well mixed, obtains mixed liquor.
3rd step, potassium hydroxide powder is dissolved in the water, and prepares 80mg/mL potassium hydroxide solution, by second institute
State mixed liquor to be pipetted in 4 μ L, 40 μ L potassium hydroxide solutions of instillation with liquid-transfering gun, keep 2h at room temperature, obtain three-dimensional structure oxygen reduction
Graphite alkene/metal silver nano-grain hydrogel.
4th step, above-mentioned three-dimensional structure redox graphene/metal silver nano-grain hydrogel is being freeze-dried
After being dried in machine, three-dimensional structure redox graphene/metal silver nano-grain aeroge is obtained.
Three-dimensional structure redox graphene made from detection and analysis/metal silver nano-grain aeroge, it is known that it has
Three-dimensional porous structure, silver nano-grain size are evenly distributed on redox graphene lamella in 30nm or so.
Embodiment 3
The first step, prefabricated graphene oxide, described graphene oxide are prepared in the following manner：10 DEG C of water-bath bars
Under part, 1.4g KNO are added into 50ml concentrated sulfuric acid solutions3With 2.8g crystalline flake graphites；0.5h, 33 DEG C of stirrings are stirred at 12 DEG C
3.5h；Room temperature is cooled to, is diluted with deionized water, supernatant is separated after placing sedimentation, graphite is dried to obtain after centrifugal filtration；15
Under DEG C water-bath, into above-mentioned dried graphite, the anhydrous concentrated sulfuric acid solutions of addition 50ml and 6g potassium permanganate, 37 DEG C of guarantors are warming up to
Hold reaction 2h；Stop heating, add deionized water 48ml, stir 1h；The hydrogen peroxide solutions of 9ml 30% are added, are stood overnight；With 5%
Dilute nitric acid solution repeatedly wash, then with the multiple centrifugal filtration of deionized water, obtain required graphite oxide dispersion.
Second step, above-mentioned graphene oxide solution is diluted to 4mg/mL graphene oxide water solution, by a certain amount of nitre
Sour silver powder is dissolved in the water, and the concentration of silver nitrate aqueous solution is 50mg/mL, then silver nitrate and graphene oxide are pressed into 3:1
For quality than the mixed nitrate silver aqueous solution and graphene oxide water solution, ultrasonic 30min makes it well mixed, obtains mixed liquor.
3rd step, anti-sepsis acid powder is dissolved in the water, prepares 120mg/mL ascorbic acid solution, by second institute
State mixed liquor to be pipetted in 3 μ L, 60 μ L ascorbic acid solutions of instillation with liquid-transfering gun, keep 3h at room temperature, obtain three-dimensional structure oxygen reduction
Graphite alkene/metal silver nano-grain hydrogel.
4th step, above-mentioned three-dimensional structure redox graphene/metal silver nano-grain hydrogel is being freeze-dried
After being dried in machine, three-dimensional structure redox graphene/metal silver nano-grain aeroge is obtained.
Three-dimensional structure redox graphene made from detection and analysis/metal silver nano-grain aeroge, it is known that it has
Three-dimensional porous structure, silver nano-grain size are evenly distributed on redox graphene lamella in 30nm or so.
Embodiment 4
The first step, prefabricated graphene oxide water solution, step are as follows：Under 10 DEG C of water bath conditions, toward the anhydrous dense sulphur of 60mL
1.6g potassium nitrate and 3.2g crystalline flake graphites are added in acid, 0.5h is stirred at first 13 DEG C, then 3.5h are stirred at 42 DEG C, is cooled to room
Temperature, diluted with deionized water, supernatant is separated after placing sedimentation, dried after centrifugal filtration, obtain graphite products；In 15 DEG C of water-baths
Under, the anhydrous concentrated sulfuric acids of 60mL and 7g potassium permanganate are added into graphite products, 38 DEG C is warming up to and keeps reaction 2h；Stop heating,
52mL deionized waters are added, 1h is stirred, adds the hydrogen peroxide solutions of 11mL 30%, stand overnight, with 5% dilute nitric acid solution
Repeatedly after washing, then with the multiple centrifugal filtration of deionized water, it is diluted with water the graphene oxide water solution for obtaining 50mg/mL；
Second step, compound concentration are 10mg/mL silver ammino solution, then silver-colored ammonia and graphene oxide are pressed into 1:1 mass ratio
Combined silver ammonia spirit and graphene oxide water solution obtained above, ultrasonic 5min are well mixed, and obtain precursor solution；
3rd step, sodium hydroxide is dissolved in the water, and prepares 150mg/mL sodium hydroxide solution, described mixed by second
Close liquid to be pipetted in 5 μ L, 200 μ L sodium hydroxide solutions of instillation with liquid-transfering gun, keep 4h at room temperature, obtain three-dimensional structure reduction-oxidation
Graphene/metal silver nano-grain hydrogel.
4th step, by above-mentioned three-dimensional structure redox graphene/metal silver nano-grain hydrogel in supercritical drying
After being dried in dry machine, three-dimensional structure redox graphene/metal silver nano-grain aeroge is obtained.
Three-dimensional structure redox graphene made from detection and analysis/metal silver nano-grain aeroge, it is known that it has
Three-dimensional porous structure, silver nano-grain size are evenly distributed on redox graphene lamella in 40nm or so.
Embodiment 5
A kind of preparation method of three-dimensional structure graphene/nanometer argent aeroge, comprises the following steps：
The first step, prefabricated graphene oxide water solution, step are as follows：Under 10 DEG C of water bath conditions, toward the anhydrous dense sulphur of 70mL
1.8g sodium nitrate and 3.6g crystalline flake graphites are added in acid, 0.5h is stirred at first 14 DEG C, then 3.5h are stirred at 51 DEG C, is cooled to room
Temperature, diluted with deionized water, supernatant is separated after placing sedimentation, dried after centrifugal filtration, obtain graphite products；In 15 DEG C of water-baths
Under, the anhydrous concentrated sulfuric acids of 70mL and 8g potassium permanganate are added into graphite products, 39 DEG C is warming up to and keeps reaction 2h；Stop heating,
56mL deionized waters are added, 1h is stirred, adds the hydrogen peroxide solutions of 13mL 30%, stand overnight, with 5% dilute nitric acid solution
Repeatedly after washing, then with the multiple centrifugal filtration of deionized water, it is diluted with water the graphene oxide water solution for obtaining 200mg/mL；
Second step, compound concentration are 20mg/mL silver ammino solution, then silver-colored ammonia and graphene oxide are pressed into 2:1 mass ratio
Combined silver ammonia spirit and graphene oxide water solution obtained above, ultrasonic 10min are well mixed, and obtain precursor solution；
3rd step, potassium hydroxide is dissolved in the water, and prepares 180mg/mL potassium hydroxide solution, described mixed by second
Close liquid to be pipetted in 4 μ L, 300 μ L potassium hydroxide solutions of instillation with liquid-transfering gun, keep 5h at room temperature, obtain three-dimensional structure reduction-oxidation
Graphene/metal silver nano-grain hydrogel.
4th step, above-mentioned three-dimensional structure redox graphene/metal silver nano-grain hydrogel is being freeze-dried
After being dried in machine, three-dimensional structure redox graphene/metal silver nano-grain aeroge is obtained.
Three-dimensional structure redox graphene made from detection and analysis/metal silver nano-grain aeroge, it is known that it has
Three-dimensional porous structure, silver nano-grain size are evenly distributed on redox graphene lamella in 35nm or so.
Embodiment 6
The first step, prefabricated graphene oxide water solution, step are as follows：Under 10 DEG C of water bath conditions, toward the anhydrous dense sulphur of 80mL
2.0g potassium nitrate and 4.0g crystalline flake graphites are added in acid, 0.5h is stirred at first 15 DEG C, then 3.5h are stirred at 60 DEG C, is cooled to room
Temperature, diluted with deionized water, supernatant is separated after placing sedimentation, dried after centrifugal filtration, obtain graphite products；In 15 DEG C of water-baths
Under, the anhydrous concentrated sulfuric acids of 80mL and 9g potassium permanganate are added into graphite products, 40 DEG C is warming up to and keeps reaction 2h；Stop heating,
60mL deionized waters are added, 1h is stirred, adds the hydrogen peroxide solutions of 15mL 30%, stand overnight, with 5% dilute nitric acid solution
Repeatedly after washing, then with the multiple centrifugal filtration of deionized water, it is diluted with water the graphene oxide water solution for obtaining 120mg/mL；
Second step, compound concentration are 50mg/mL silver ammino solution, then silver-colored ammonia and graphene oxide are pressed into 5:1 mass ratio
Combined silver ammonia spirit and graphene oxide water solution obtained above, ultrasonic 20min are well mixed, and obtain precursor solution；
3rd step, by dissolution of ascorbic acid in water, 200mg/mL ascorbic acid solution is prepared, it is described mixed by second
Close liquid to be pipetted in 3 μ L, 300 μ L ascorbic acid solutions of instillation with liquid-transfering gun, keep 6h at room temperature, obtain three-dimensional structure reduction-oxidation
Graphene/metal silver nano-grain hydrogel.
4th step, by above-mentioned three-dimensional structure redox graphene/metal silver nano-grain hydrogel in supercritical drying
After being dried in dry machine, three-dimensional structure redox graphene/metal silver nano-grain aeroge is obtained.
Three-dimensional structure redox graphene made from detection and analysis/metal silver nano-grain aeroge, it is known that it has
Three-dimensional porous structure, silver nano-grain size are evenly distributed on redox graphene lamella in 40nm or so.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using invention.
Person skilled in the art obviously can easily make various modifications to these embodiments, and described herein general
Principle is applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to above-described embodiment, ability
Field technique personnel do not depart from improvement that scope made and modification all should be the present invention's according to the announcement of the present invention
Within protection domain.
Claims (5)
1. a kind of three-dimensional structure redox graphene/nanometer metallic silver aeroge, it is characterised in that the aeroge is by reducing
Graphene oxide layer and uniform load are in the three-dimensional porous of the polycrystalline Nano argent composition on redox graphene lamella
Structure；
The aeroge is made by the following method：
（1）Silver soluble saline solution is well mixed with graphene oxide water solution, obtains precursor solution；
（2）Precursor solution is instilled in reductant solution, reacts at room temperature, obtains three-dimensional structure redox graphene/gold
Belong to silver nano-grain hydrogel；
（3）Purpose production is obtained after three-dimensional structure redox graphene/metal silver nano-grain hydrogel is taken out into cleaning, drying
Thing；
Step（1）The mass ratio of soluble silver salt and graphene oxide is in middle precursor solution（1~5）:1, described solubility
The concentration of silver salt is（10~50）Mg/mL, the concentration of graphene oxide water solution are（1~4）mg/mL；
Step（2）The volume ratio of the addition of middle reductant solution and precursor solution is（5~100）：1, the reaction time be 1 ~
6h；
Described reducing agent is that the sodium hydroxide solution that concentration is 50 ~ 200 mg/mL or 50 ~ 200 mg/mL potassium hydroxide are molten
Liquid.
2. a kind of three-dimensional structure redox graphene/nanometer metallic silver aeroge according to claim 1, its feature exist
In the particle diameter of described nanometer metallic silver is 25 ~ 40nm.
3. a kind of three-dimensional structure redox graphene/nanometer metallic silver aeroge according to claim 1, its feature exist
In described graphene oxide water solution is prepared by following steps：
（A）Under 10 DEG C of water bath conditions, nitrate and crystalline flake graphite, heating stirring reaction, reaction are added into the anhydrous concentrated sulfuric acid
After the completion of, room temperature is cooled to, after being diluted with water, drying is separated, obtains the first product；
（B）Under 15 DEG C of water-baths, toward step（A）In add the anhydrous concentrated sulfuric acid and potassium permanganate in obtained the first product, heat
Reacted；
（C）After reaction terminates, stop heating, addition deionized water is stirred, adds hydrogen peroxide solution, stand overnight, wash
After washing filtering, it is diluted with water and obtains requisite oxygen graphite aqueous solution.
4. a kind of three-dimensional structure redox graphene/nanometer metallic silver aeroge according to claim 3, its feature exist
In step（A）In：Described nitrate is potassium nitrate or sodium nitrate, the addition of the anhydrous concentrated sulfuric acid, nitrate and crystalline flake graphite
The ratio between be（40~80）mL:（1~2）g:（2~4）G, the process conditions of heating stirring reaction are：0.5h is stirred at 10 ~ 15 DEG C, then
3.5h is stirred at 15 ~ 60 DEG C；
Step（B）In：The anhydrous concentrated sulfuric acid, potassium permanganate and step（A）The ratio between addition of middle crystalline flake graphite is（40~80）mL:
（3~9）g:（2~4）G, the process conditions of heating stirring reaction are：It is warming up to 35-40 DEG C and keeps reaction 2h；
Step（C）In：Deionized water, hydrogen peroxide solution and step（A）The ratio between addition of middle crystalline flake graphite is（40~60）mL:
（5~15）mL:（2~4）G, mixing time 1h, hydrogen peroxide solution are 30% hydrogen peroxide solution, and the process conditions of washing are：With 5%
Dilute nitric acid solution repeatedly wash, the process conditions of filtering are：With the multiple centrifugal filtration of deionized water.
5. a kind of three-dimensional structure redox graphene/nanometer metallic silver aeroge according to claim 1, its feature exist
In step（3）The drying of middle three-dimensional structure redox graphene/metal silver nano-grain hydrogel is faced to be freeze-dried or surpassing
Dry on boundary.
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| CN104355302B (en) * | 2014-10-21 | 2016-04-20 | 复旦大学 | The preparation method of a kind of Graphene/polyimide-based carbon aerogels |
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