CN105251484A - Reduction-oxidation graphene/nanometer metallic silver aerogel with three-dimensional structure and preparation method - Google Patents
Reduction-oxidation graphene/nanometer metallic silver aerogel with three-dimensional structure and preparation method Download PDFInfo
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Abstract
The invention relates to a reduction-oxidation graphene/nanometer metallic silver aerogel with a three-dimensional structure and a preparation method thereof. The aerogel has a three-dimensional porous structure which is formed by a reduction-oxidation graphene slice layer and a polycrystal nanometer metallic sliver uniformly loaded on the reduction-oxidation graphene slice layer. The aerogel is prepared according to the preparation method which comprises the following steps: (1) uniformly mixing a soluble silver salt aqueous solution with a graphene oxide aqueous solution, thereby acquiring a pecursor solution; (2) transferring the pecursor solution into a reducing agent solution, reacting at room temperature, thereby acquiring a three-dimensional graphene/metallic silver nanometer grain hydrogel; and (3) taking out and cleaning the three-dimensional graphene/metallic silver nanometer grain hydrogel, drying, and then acquiring a target product. Compared with the prior art, the reduction-oxidation graphene/nanometer metallic silver aerogel has the advantages that the preparation method is simple, the whole reaction process is performed at a room temperature, no excessive extra energy consumption is required, and the like.
Description
Technical field
The present invention relates to nano-composite catalyst field, especially relate to a kind of three-dimensional structure redox graphene/nanometer metallic silver aeroge and preparation method thereof.
Background technology
Catalyst is in industrial production and environmental monitoring and have very important effect in administering, and the chemical products of nearly 2/3rds and the chemical production processes of 90 percent all relate to catalysis technique.Since the sixties in previous generation, the properties such as Dielectric confinement effect, skin effect, macro quanta tunnel effect, reduced size volume effect, quantum size effect can be shown when it is found that the size of material is reduced to nanoscale after, nano material becomes the focus of scientific research, especially as the metal nano material of effective catalyst.The reduction of metal material size has two effects significantly in the application of catalytic field, and the first, along with the reduction of size can increase high-octane surface-active atom on the unsaturated and thermodynamics of chemistry; The second, fermi level can cause the reduction of reduction potential along with the increase that size reduces, and these two effects are the most critical factors improving catalytic performance.And silver nano-grain is cheap with it, biocompatibility is high, be easy to the characteristics such as reduction, good conductivity, become one of member wherein of greatest concern.But there is the problem of easily reuniting in nano particle, therefore finds a kind of suitable base material, enable the highdensity dispersion well of nano particle be current focus.
Graphene has physics free from worldly cares and electrochemical properties, such as high thermal stability, high-specific surface area, high conductivity, high mechanical properties, be easy to modification-COOH, the oxy radicals etc. such as-OH, therefore the carrier material of nano particle is suitable as very much, particularly three-dimensional graphene-structured has higher specific area, can play better peptizaiton.The method that current original position prepares three-dimensional grapheme/metal nanoparticle is generally CVD, hydro-thermal method, hot solution method etc., and these preparation methods not only preparation process complexity, and consumed energy is large.
Chinese patent 201010523363.5 discloses a kind of preparation method of graphene-loaded platinum nano catalyst, the preparation of (1) Graphene; (2) preparation of diallyl dimethyl ammoniumchloride (PDDA) functionalization graphene; (3) preparation of graphene-loaded platinum nano catalyst.Although the standby catalyst of this patent system solves the problem that metallic particles easily occurs self to reunite, achieve the load factor that platinum nano catalyst is higher, it is comparatively numerous and diverse in preparation process, and reaction needed is in heating environment and carries out, and makes power consumption larger.
Summary of the invention
Object of the present invention be exactly in order to overcome above-mentioned prior art exist defect and a kind of three-dimensional structure redox graphene/nanometer metallic silver aeroge and preparation method thereof is provided.
Object of the present invention can be achieved through the following technical solutions:
A kind of three-dimensional structure redox graphene/nanometer metallic silver aeroge, this aeroge three-dimensional porous structure that the polycrystalline Nano argent on redox graphene lamella forms by redox graphene lamella and uniform load.
The particle diameter of described nanometer metallic silver is 25 ~ 40nm.
A preparation method for three-dimensional structure redox graphene/nanometer metallic silver aeroge, comprises the following steps:
(1) silver soluble saline solution is mixed with graphene oxide water solution, obtain precursor solution;
(2) precursor solution is instilled in reductant solution, react under room temperature, obtain three-dimensional structure redox graphene/argent nano particle hydrogel;
(3) object product is obtained after three-dimensional structure redox graphene/argent nano particle hydrogel being taken out cleaning, drying.
In step (1), in precursor solution, the mass ratio of soluble silver salt and graphene oxide is (1 ~ 5): 1, the concentration of described soluble silver salt is (10 ~ 50) mg/mL, and the concentration of graphene oxide water solution is (1 ~ 4) mg/mL.Soluble silver salt can select silver nitrate or silver-colored ammonia etc.
Described graphene oxide water solution is prepared from by following steps:
(A) under 10 DEG C of water bath condition, in the anhydrous concentrated sulfuric acid, add nitrate and crystalline flake graphite, heating stirring reaction, after having reacted, is cooled to room temperature, after being diluted with water, being separated dry, obtaining the first product;
(B) under 15 DEG C of water-baths, add the anhydrous concentrated sulfuric acid and potassium permanganate in the first product obtained in step (A), heating is reacted;
(C) after reaction terminates, stop heating, add deionized water and stir, then add hydrogen peroxide solution, hold over night, after washing and filtering, be diluted with water and namely obtain required graphene oxide water solution.
In step (A): described nitrate is potassium nitrate or sodium nitrate, the ratio of the addition of the anhydrous concentrated sulfuric acid, nitrate and crystalline flake graphite is (40 ~ 80) mL:(1 ~ 2) g:(2 ~ 4) g, the process conditions of heating stirring reaction are: at 10 ~ 15 DEG C, stir 0.5h, then stir 3.5h at 15 ~ 60 DEG C;
In step (B): in the anhydrous concentrated sulfuric acid, potassium permanganate and step (A), the ratio of the addition of crystalline flake graphite is (40 ~ 80) mL:(3 ~ 9) g:(2 ~ 4) g, the process conditions of heating stirring reaction are: be warming up to 35-40 DEG C and keep reaction 2h;
In step (C): in deionized water, hydrogen peroxide solution and step (A), the ratio of the addition of crystalline flake graphite is (40 ~ 60) mL:(5 ~ 15) mL:(2 ~ 4) g, mixing time is 1h, hydrogen peroxide solution is 30% hydrogen peroxide solution, the process conditions of washing are: repeatedly wash with the dilute nitric acid solution of 5%, the process conditions of filtration are: with deionized water repeatedly centrifugal filtration.
In step (2), the volume ratio of the addition of reductant solution and precursor solution is (5 ~ 100): 1, and the reaction time is 1 ~ 6h.
Described reductant solution is the alkaline solution such as sodium hydroxide solution, potassium hydroxide solution or ascorbic acid solution.
The ascorbic acid solution of described reducing agent to be concentration the be sodium hydroxide solution of 50 ~ 200mg/mL, the potassium hydroxide solution of 50 ~ 200mg/mL or 50 ~ 200mg/mL.
In step (3), the drying of three-dimensional structure redox graphene/argent nano particle hydrogel is freeze drying or supercritical drying.
Unlike the prior art, the mixed solution of graphene oxide and silver salt first mixes with reductant solution by the present invention, and can be self-assembled into hydrogel under the condition of room temperature.In the forming process of hydrogel, mixed solution is with in the form of fine droplet instillation reductant solution, because drop is little, do not spread in reductant solution by capillary effect can keep original form, reducing agent enters droplet inside by space, by graphene oxide and silver salt reduction, finally directly form hydrogel.Its original form is enough maintained in order to the surface tension of droplet can be made, thus the aeroge of obtained three-dimensional porous structure, the concentration of graphene oxide can not be too low, namely graphene oxide sheet interlayer needs certain active force to maintain droplet profile, simultaneously the reproducibility of reducing agent and concentration can not be too low, otherwise the recovery time can cause droplet diffusion into the surface and structure collapses too for a long time.
Compared with prior art, the present invention has prepared the redox graphene/nanometer metallic silver aeroge of three-dimensional porous structure, the small-sized density of silver nano-grain is very high and be evenly distributed on redox graphene lamella, improve reactivity area, make catalyst have better catalytic performance.In addition, preparation method at room temperature carries out, and does not need extra heating, and the reducing agent used is nontoxic is easy to get, and whole preparation technology is simple, is particularly suitable for suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscopic picture of three-dimensional structure redox graphene/nanometer metallic silver aeroge that the present invention obtains;
Fig. 2 is the transmission electron microscope picture of three-dimensional structure redox graphene/nanometer metallic silver aeroge that the present invention obtains;
Fig. 3 is the polycrystalline diffraction pattern figure of three-dimensional structure redox graphene/nanometer metallic silver aeroge that the present invention obtains;
Fig. 4 is the X-ray diffractogram (XRD figure) of three-dimensional structure redox graphene/nanometer metallic silver aeroge that the present invention obtains.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
The first step, prefabricated graphene oxide, described graphene oxide prepares in the following manner: under 10 DEG C of water bath condition, in 40ml concentrated sulfuric acid solution, add 1gNaNO
3with 2g crystalline flake graphite; Stir 0.5h at 10 DEG C, 15 DEG C are stirred 3.5h; Be cooled to room temperature, by deionized water dilution, separation of supernatant after placement sedimentation, after centrifugal filtration, drying obtains graphite; Under 15 DEG C of water-baths, in above-mentioned dried graphite, add the anhydrous concentrated sulfuric acid of 40ml and 3g potassium permanganate, be warming up to 35 DEG C and keep reaction 2h; Stop heating, add deionized water 40ml, stir 1h; Add 5ml30% hydrogen peroxide solution, hold over night; Repeatedly wash with the dilute nitric acid solution of 5%, then with deionized water repeatedly centrifugal filtration, obtain required graphite oxide dispersion.
Second step, above-mentioned graphene oxide solution is diluted to the graphene oxide water solution of 1mg/mL, a certain amount of silver nitrate powder is dissolved in the water, the concentration of silver nitrate aqueous solution is 10mg/mL, the quality of again silver nitrate and graphene oxide being pressed 1:1 is than the silver-colored aqueous solution of mixed nitrate and graphene oxide water solution, ultrasonic 5min makes it mix, and obtains mixed liquor.
3rd step, sodium hydroxide powder be dissolved in the water, the sodium hydroxide solution of preparation 50mg/mL, pipettes 5 μ L and instills in 25 μ L sodium hydroxide solutions by mixed liquor liquid-transfering gun described in second step, keep 1h under room temperature, obtain three-dimensional structure redox graphene/argent nano particle hydrogel.
4th step, after drying, obtains three-dimensional structure redox graphene/argent nano particle aeroge by above-mentioned three-dimensional structure redox graphene/argent nano particle hydrogel in freeze drier.
Detect obtained three-dimensional structure redox graphene/nanometer metallic silver aeroge, Fig. 1 is the scanning electron microscopic picture of its aerogel material under different resolution, illustrates the structure of three-dimensional porous graphene oxide and the pattern of silver nano-grain; Fig. 2 shows the transmission electron microscope picture of aerogel material, can see that the small-sized density of silver nano-grain is very high and be evenly distributed on redox graphene lamella; Fig. 3 shows the polycrystalline diffraction pattern in a certain constituency in Fig. 2, and analyzing known silver nano-grain is polymorphic structure; Fig. 4 is the XRD figure of redox graphene lamella in obtained aeroge, therefrom can find out that the peak position corresponding to GO (001) crystal face in the present embodiment in XRD figure has moved on to the position corresponding to the peak of rGO (002) crystal face, illustrate that graphene oxide in this example (GO) becomes the redox graphene (rGO) in 3D-rGO/AgNPs after reduction.Three-dimensional structure redox graphene described in this example has higher specific area, can the more homodisperse argent nano particle of load, as a kind of catalyst, effectively increases catalytic reaction activity point, improves catalytic performance.
Embodiment 2
The first step, prefabricated graphene oxide, described graphene oxide prepares in the following manner: under 10 DEG C of water bath condition, in 45ml concentrated sulfuric acid solution, add 1.2gKNO
3with 2.4g crystalline flake graphite; Stir 0.5h at 11 DEG C, 24 DEG C are stirred 3.5h; Be cooled to room temperature, by deionized water dilution, separation of supernatant after placement sedimentation, after centrifugal filtration, drying obtains graphite; Under 15 DEG C of water-baths, in above-mentioned dried graphite, add the anhydrous concentrated sulfuric acid of 45ml and 4g potassium permanganate, be warming up to 36 DEG C and keep reaction 2h; Stop heating, add deionized water 44ml, stir 1h; Add 7ml30% hydrogen peroxide solution, hold over night; Repeatedly wash with the dilute nitric acid solution of 5%, then with deionized water repeatedly centrifugal filtration, obtain required graphite oxide dispersion.
Second step, above-mentioned graphene oxide solution is diluted to the graphene oxide water solution of 2mg/mL, a certain amount of silver nitrate powder is dissolved in the water, the concentration of silver nitrate aqueous solution is 20mg/mL, the quality of again silver nitrate and graphene oxide being pressed 2:1 is than the silver-colored aqueous solution of mixed nitrate and graphene oxide water solution, ultrasonic 20min makes it mix, and obtains mixed liquor.
3rd step, be dissolved in the water by potassium hydroxide powder, the potassium hydroxide solution of preparation 80mg/mL, pipettes 4 μ L and instills in 40 μ L potassium hydroxide solutions by second described mixed liquor liquid-transfering gun, keep 2h under room temperature, obtain three-dimensional structure redox graphene/argent nano particle hydrogel.
4th step, after drying, obtains three-dimensional structure redox graphene/argent nano particle aeroge by above-mentioned three-dimensional structure redox graphene/argent nano particle hydrogel in freeze drier.
Detect and analyze obtained three-dimensional structure redox graphene/argent nano particle aeroge, known its has three-dimensional porous structure, and silver nano-grain size, at about 30nm, is evenly distributed on redox graphene lamella.
Embodiment 3
The first step, prefabricated graphene oxide, described graphene oxide prepares in the following manner: under 10 DEG C of water bath condition, in 50ml concentrated sulfuric acid solution, add 1.4gKNO
3with 2.8g crystalline flake graphite; Stir 0.5h at 12 DEG C, 33 DEG C are stirred 3.5h; Be cooled to room temperature, by deionized water dilution, separation of supernatant after placement sedimentation, after centrifugal filtration, drying obtains graphite; Under 15 DEG C of water-baths, in above-mentioned dried graphite, add the anhydrous concentrated sulfuric acid solution of 50ml and 6g potassium permanganate, be warming up to 37 DEG C and keep reaction 2h; Stop heating, add deionized water 48ml, stir 1h; Add 9ml30% hydrogen peroxide solution, hold over night; Repeatedly wash with the dilute nitric acid solution of 5%, then with deionized water repeatedly centrifugal filtration, obtain required graphite oxide dispersion.
Second step, above-mentioned graphene oxide solution is diluted to the graphene oxide water solution of 4mg/mL, a certain amount of silver nitrate powder is dissolved in the water, the concentration of silver nitrate aqueous solution is 50mg/mL, the quality of again silver nitrate and graphene oxide being pressed 3:1 is than the silver-colored aqueous solution of mixed nitrate and graphene oxide water solution, ultrasonic 30min makes it mix, and obtains mixed liquor.
3rd step, by anti-sepsis acid powder dissolution in water, the ascorbic acid solution of preparation 120mg/mL, pipettes 3 μ L and instills in 60 μ L ascorbic acid solutions by second described mixed liquor liquid-transfering gun, keep 3h under room temperature, obtain three-dimensional structure redox graphene/argent nano particle hydrogel.
4th step, after drying, obtains three-dimensional structure redox graphene/argent nano particle aeroge by above-mentioned three-dimensional structure redox graphene/argent nano particle hydrogel in freeze drier.
Detect and analyze obtained three-dimensional structure redox graphene/argent nano particle aeroge, known its has three-dimensional porous structure, and silver nano-grain size, at about 30nm, is evenly distributed on redox graphene lamella.
Embodiment 4
The first step, prefabricated graphene oxide water solution, step is as follows: under 10 DEG C of water bath condition, in the anhydrous concentrated sulfuric acid of 60mL, add 1.6g potassium nitrate and 3.2g crystalline flake graphite, stirs 0.5h at first 13 DEG C, 3.5h is stirred again at 42 DEG C, be cooled to room temperature, with deionized water dilution, separation of supernatant after placement sedimentation, dry after centrifugal filtration, obtain graphite products; Under 15 DEG C of water-baths, in graphite products, add the anhydrous concentrated sulfuric acid of 60mL and 7g potassium permanganate, be warming up to 38 DEG C and keep reaction 2h; Stop heating, add 52mL deionized water, stir 1h, add 11mL30% hydrogen peroxide solution again, hold over night, after the dilute nitric acid solution with 5% repeatedly washs, again with deionized water repeatedly centrifugal filtration, be diluted with water the graphene oxide water solution namely obtaining 50mg/mL;
Second step, compound concentration is the silver ammino solution of 10mg/mL, then the quality of silver-colored ammonia and graphene oxide being pressed 1:1 is than combined silver ammonia spirit and above-mentioned obtained graphene oxide water solution, and ultrasonic 5min mixes, and obtains precursor solution;
3rd step, be dissolved in the water by NaOH, the sodium hydroxide solution of preparation 150mg/mL, pipettes 5 μ L and instills in 200 μ L sodium hydroxide solutions by second described mixed liquor liquid-transfering gun, keep 4h under room temperature, obtain three-dimensional structure redox graphene/argent nano particle hydrogel.
4th step, after drying, obtains three-dimensional structure redox graphene/argent nano particle aeroge by above-mentioned three-dimensional structure redox graphene/argent nano particle hydrogel in supercritical dryer.
Detect and analyze obtained three-dimensional structure redox graphene/argent nano particle aeroge, known its has three-dimensional porous structure, and silver nano-grain size, at about 40nm, is evenly distributed on redox graphene lamella.
Embodiment 5
A preparation method for three-dimensional structure graphene/nanometer argent aeroge, comprises the following steps:
The first step, prefabricated graphene oxide water solution, step is as follows: under 10 DEG C of water bath condition, in the anhydrous concentrated sulfuric acid of 70mL, add 1.8g sodium nitrate and 3.6g crystalline flake graphite, stirs 0.5h at first 14 DEG C, 3.5h is stirred again at 51 DEG C, be cooled to room temperature, with deionized water dilution, separation of supernatant after placement sedimentation, dry after centrifugal filtration, obtain graphite products; Under 15 DEG C of water-baths, in graphite products, add the anhydrous concentrated sulfuric acid of 70mL and 8g potassium permanganate, be warming up to 39 DEG C and keep reaction 2h; Stop heating, add 56mL deionized water, stir 1h, add 13mL30% hydrogen peroxide solution again, hold over night, after the dilute nitric acid solution with 5% repeatedly washs, again with deionized water repeatedly centrifugal filtration, be diluted with water the graphene oxide water solution namely obtaining 200mg/mL;
Second step, compound concentration is the silver ammino solution of 20mg/mL, then the quality of silver-colored ammonia and graphene oxide being pressed 2:1 is than combined silver ammonia spirit and above-mentioned obtained graphene oxide water solution, and ultrasonic 10min mixes, and obtains precursor solution;
3rd step, be dissolved in the water by potassium hydroxide, the potassium hydroxide solution of preparation 180mg/mL, pipettes 4 μ L and instills in 300 μ L potassium hydroxide solutions by second described mixed liquor liquid-transfering gun, keep 5h under room temperature, obtain three-dimensional structure redox graphene/argent nano particle hydrogel.
4th step, after drying, obtains three-dimensional structure redox graphene/argent nano particle aeroge by above-mentioned three-dimensional structure redox graphene/argent nano particle hydrogel in freeze drier.
Detect and analyze obtained three-dimensional structure redox graphene/argent nano particle aeroge, known its has three-dimensional porous structure, and silver nano-grain size, at about 35nm, is evenly distributed on redox graphene lamella.
Embodiment 6
The first step, prefabricated graphene oxide water solution, step is as follows: under 10 DEG C of water bath condition, in the anhydrous concentrated sulfuric acid of 80mL, add 2.0g potassium nitrate and 4.0g crystalline flake graphite, stirs 0.5h at first 15 DEG C, 3.5h is stirred again at 60 DEG C, be cooled to room temperature, with deionized water dilution, separation of supernatant after placement sedimentation, dry after centrifugal filtration, obtain graphite products; Under 15 DEG C of water-baths, in graphite products, add the anhydrous concentrated sulfuric acid of 80mL and 9g potassium permanganate, be warming up to 40 DEG C and keep reaction 2h; Stop heating, add 60mL deionized water, stir 1h, add 15mL30% hydrogen peroxide solution again, hold over night, after the dilute nitric acid solution with 5% repeatedly washs, again with deionized water repeatedly centrifugal filtration, be diluted with water the graphene oxide water solution namely obtaining 120mg/mL;
Second step, compound concentration is the silver ammino solution of 50mg/mL, then the quality of silver-colored ammonia and graphene oxide being pressed 5:1 is than combined silver ammonia spirit and above-mentioned obtained graphene oxide water solution, and ultrasonic 20min mixes, and obtains precursor solution;
3rd step, by dissolution of ascorbic acid in water, the ascorbic acid solution of preparation 200mg/mL, pipettes 3 μ L and instills in 300 μ L ascorbic acid solutions by second described mixed liquor liquid-transfering gun, keep 6h under room temperature, obtain three-dimensional structure redox graphene/argent nano particle hydrogel.
4th step, after drying, obtains three-dimensional structure redox graphene/argent nano particle aeroge by above-mentioned three-dimensional structure redox graphene/argent nano particle hydrogel in supercritical dryer.
Detect and analyze obtained three-dimensional structure redox graphene/argent nano particle aeroge, known its has three-dimensional porous structure, and silver nano-grain size, at about 40nm, is evenly distributed on redox graphene lamella.
Above-mentioned is can understand and use invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.
Claims (10)
1. three-dimensional structure redox graphene/nanometer metallic silver aeroge, is characterized in that, this aeroge is the three-dimensional porous structure that the polycrystalline Nano argent on redox graphene lamella forms by redox graphene lamella and uniform load.
2. a kind of three-dimensional structure redox graphene/nanometer metallic silver aeroge according to claim 1, is characterized in that, the particle diameter of described nanometer metallic silver is 25 ~ 40nm.
3. a preparation method for three-dimensional structure redox graphene/nanometer metallic silver aeroge as claimed in claim 1 or 2, is characterized in that, comprise the following steps:
(1) silver soluble saline solution is mixed with graphene oxide water solution, obtain precursor solution;
(2) precursor solution is instilled in reductant solution, react under room temperature, obtain three-dimensional structure redox graphene/argent nano particle hydrogel;
(3) object product is obtained after three-dimensional structure redox graphene/argent nano particle hydrogel being taken out cleaning, drying.
4. the preparation method of a kind of three-dimensional structure redox graphene/nanometer metallic silver aeroge according to claim 3, it is characterized in that, in step (1), in precursor solution, the mass ratio of soluble silver salt and graphene oxide is (1 ~ 5): 1, the concentration of described soluble silver salt is (10 ~ 50) mg/mL, and the concentration of graphene oxide water solution is (1 ~ 4) mg/mL.
5. the preparation method of a kind of three-dimensional structure redox graphene/nanometer metallic silver aeroge according to claim 4, it is characterized in that, described graphene oxide water solution is prepared from by following steps:
(A) under 10 DEG C of water bath condition, in the anhydrous concentrated sulfuric acid, add nitrate and crystalline flake graphite, heating stirring reaction, after having reacted, is cooled to room temperature, after being diluted with water, being separated dry, obtaining the first product;
(B) under 15 DEG C of water-baths, add the anhydrous concentrated sulfuric acid and potassium permanganate in the first product obtained in step (A), heating is reacted;
(C) after reaction terminates, stop heating, add deionized water and stir, then add hydrogen peroxide solution, hold over night, after washing and filtering, be diluted with water and namely obtain required graphene oxide water solution.
6. the preparation method of a kind of three-dimensional structure redox graphene/nanometer metallic silver aeroge according to claim 5, it is characterized in that, in step (A): described nitrate is potassium nitrate or sodium nitrate, the ratio of the addition of the anhydrous concentrated sulfuric acid, nitrate and crystalline flake graphite is (40 ~ 80) mL:(1 ~ 2) g:(2 ~ 4) g, the process conditions of heating stirring reaction are: at 10 ~ 15 DEG C, stir 0.5h, then stir 3.5h at 15 ~ 60 DEG C;
In step (B): in the anhydrous concentrated sulfuric acid, potassium permanganate and step (A), the ratio of the addition of crystalline flake graphite is (40 ~ 80) mL:(3 ~ 9) g:(2 ~ 4) g, the process conditions of heating stirring reaction are: be warming up to 35-40 DEG C and keep reaction 2h;
In step (C): in deionized water, hydrogen peroxide solution and step (A), the ratio of the addition of crystalline flake graphite is (40 ~ 60) mL:(5 ~ 15) mL:(2 ~ 4) g, mixing time is 1h, hydrogen peroxide solution is 30% hydrogen peroxide solution, the process conditions of washing are: repeatedly wash with the dilute nitric acid solution of 5%, the process conditions of filtration are: with deionized water repeatedly centrifugal filtration.
7. the preparation method of a kind of three-dimensional structure redox graphene/nanometer metallic silver aeroge according to claim 3, it is characterized in that, in step (2), the volume ratio of the addition of reductant solution and precursor solution is (5 ~ 100): 1, and the reaction time is 1 ~ 6h.
8. the preparation method of a kind of three-dimensional structure redox graphene/nanometer metallic silver aeroge according to claim 7, it is characterized in that, described reductant solution is sodium hydroxide solution, potassium hydroxide solution or ascorbic acid solution.
9. the preparation method of a kind of three-dimensional structure redox graphene/nanometer metallic silver aeroge according to claim 8, it is characterized in that, the ascorbic acid solution of described reducing agent to be concentration the be sodium hydroxide solution of 50 ~ 200mg/mL, the potassium hydroxide solution of 50 ~ 200mg/mL or 50 ~ 200mg/mL.
10. the preparation method of a kind of three-dimensional structure redox graphene/nanometer metallic silver aeroge according to claim 3, it is characterized in that, in step (3), the drying of three-dimensional structure redox graphene/argent nano particle hydrogel is freeze drying or supercritical drying.
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