CN104163423A - Method for preparing spongy graphene by freeze drying - Google Patents
Method for preparing spongy graphene by freeze drying Download PDFInfo
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- CN104163423A CN104163423A CN201410397019.4A CN201410397019A CN104163423A CN 104163423 A CN104163423 A CN 104163423A CN 201410397019 A CN201410397019 A CN 201410397019A CN 104163423 A CN104163423 A CN 104163423A
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- freeze
- graphene
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- deionized water
- spongy graphene
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Abstract
The invention relates to a method for preparing spongy graphene by freeze drying, which comprises the following steps: adding natural graphite into concentrated H2SO4 in an ultrasonic ice bath within 15-60 minutes, adding NaNO3, adding potassium permanganate KMnO4 within 15-60 minutes, starting timing when all the potassium permanganate is added, and reacting for 0.5-1 hour to obtain a mixed solution; and stirring the mixed solution in the 30-35 DEG C water bath to react for 0.5-1.5 hours, adding a right amount of deionized water into the mixed solution, heating to 95-100 DEG C, continuing stirring to react for 20-30 minutes, adding deionized water and oxydol, separating out the solid-phase product, washing, carrying out freeze-drying, and carrying out low-pressure hot stripping. The method further optimizes the graphene preparation technique, has the advantages of short preparation period, high speed, high efficiency, simple technique, no environment pollution and energy saving, is easy to operate and can be popularized.
Description
Technical field
The invention belongs to the preparation field of grapheme material, particularly a kind of freeze-drying is prepared the method for spongy Graphene.
Background technology
Graphene (Graphene) is that carbon atom is with sp
2the cellular Colloidal particles sheet nano material that the tight stacking of hybrid form forms, since within 2004, being found, Graphene receives investigator's concern with excellent physical and chemical performance, become rapidly the study hotspot in the fields such as physical chemistry, the material energy, life science and information technology.The monatomic stratiform structure that Graphene is special makes it have great specific surface area, sp
2hydridization makes it have many marvellous characteristics and excellent physical and chemical performance.Aspect mechanical property, there is high strength, high-modulus; Aspect thermal property, there is high thermal conductivity; Aspect electric property, there is high conductivity.In addition, Graphene also has some special character, for example: at room temperature Graphene has quantum hall effect and ferromegnetism.
Since Graphene is found, be just devoted to attempt different methods prepares Graphene to scientific researchers always, at present, according to preparation principle difference, can be divided into physical method and chemical process.Physical method is also the method for mechanically peel, can be divided into again micromechanics stripping method and solvent stripping method etc.Chemical process mainly contains graphite oxide reduction method, thermolysis SiC method and chemical vapour deposition (CVD) method.
Nowadays, the preparation method of three-dimensional grapheme causes investigator's very big interest.Conventionally hydro-thermal---solvent-thermal method synthesizes three-dimensional grapheme in employing, in this process, need in solvent, add reductive agent, at a certain temperature graphite oxide is reduced, therefore synthetic Graphene degree of crystallinity is not high, volumetric shrinkage, easily occur the phenomenon that hardens, and productive rate is not high.Also have report Graphene lyophilize to be obtained to the method for three-dimensional grapheme, but Graphene is not easy to be dissolved in solvent, therefore there will be agglomeration.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method that freeze-drying is prepared spongy Graphene, the Graphene that the method makes is loose porous, there is large specific surface area, present three-dimensional sponge shape, density is low, there is ultralight and constitutionally stable feature, can be used as sorbing material and matrix material, widened application.
A kind of freeze-drying of the present invention is prepared the method for spongy Graphene, comprising:
(1) raw material ultrasonic blend in ice bath
Natural graphite is added to the dense H of ice-bath ultrasonic in 15-60min
2sO
4in, add afterwards NaNO
3, then in 15-60min, add potassium permanganate KMnO
4, after all adding, potassium permanganate starts timing, reaction 0.5-1h, and guarantee system temperature, higher than 10 ℃, does not obtain mixed solution;
(2) oxidizing reaction of raw material in water-bath
Above-mentioned mixed solution is reacted to 0.5-1.5h 30-35 ℃ of stirred in water bath, deionized water is added in mixed solution, be heated to 95-100 ℃, continue stirring reaction 20-30min, then add deionized water, hydrogen peroxide, until solution becomes glassy yellow, without Bubble formation (obtaining graphite oxide), then separation, washing, lyophilize, low pressure hot soarfing from, obtain spongy Graphene.Natural graphite, dense H in described step (1)
2sO
4, NaNO
3, potassium permanganate KMnO
4proportionlity be 2g:50ml:1g:7g, i.e. KMnO
4with dense H
2sO
4slightly excessive, and graphite and KMnO
4slowly join successively dense H
2sO
4in, object is to guarantee that graphite is fully oxidized intercalation in the later stage.
In step (1), the ice bath stage adopts ultrasonic blend, and object is to guarantee that raw material fully mixes.
The deionized water adding after the deionized water adding after stirring reaction 0.5-1.5h in described step (2), lasting stirring 20-30min, the volume ratio of hydrogen peroxide are 100:182:30.
In described step (2), the concentration expressed in percentage by volume of hydrogen peroxide is 30%.
Washing is for till cleaning with the hydrochloric acid soln that concentration expressed in percentage by volume is 5% and being detected to sulfate radical-free in filtrate in described step (2).
In described step (2), lyophilize is: below-60 ℃, under the condition lower than 12Pa, and vacuum lyophilization 12-24h.
The graphite oxide of step (2) is through vacuum lyophilization, and object is to keep the original pattern of sample and activity, is beneficial to the processing of later stage sample.
Described step (2) mesolow hot soarfing is from being: keep pressure lower than 60Pa, at 180-800 ℃ of lasting 2-15h.
The present invention be take graphite oxide as presoma, by the direct lyophilize of the aqueous solution of graphite oxide, thereby guarantees that sample keeps fluffy; Finally spongy graphite oxide low pressure hot soarfing is obtained to spongy Graphene from reduction, in this process, only need to regulate the parameters such as temperature, pressure, time can obtain the spongy Graphene of different-shape and performance, do not use poisonous chemical reducing agent, avoid environmental pollution, easily realized scale operation simultaneously.
beneficial effect
(1) the prepared Graphene of the present invention is loose porous, has large specific surface area, presents three-dimensional sponge shape, and density is low, has ultralight and constitutionally stable feature, can be used as sorbing material and matrix material, has widened its application prospect;
(2) the present invention when changing vacuum lyophilization and low pressure hot soarfing from the reaction parameter of reduction phase, can change macroshape, microscopic appearance and conduction and the absorption property of three-dimensional sponge shape Graphene;
(3) simple, the easy handling of preparation technology of the present invention, preparation cycle is short, quickness and high efficiency;
(4) raw materials of the present invention source is wide, with low cost.Environmentally safe and energy-conservation, can be applicable.
Accompanying drawing explanation
Fig. 1 prepares the process route chart of spongy graphite oxide in embodiment 1;
Fig. 2 is the XRD figure of preparing graphite (GT), graphite oxide (GTO) and Graphene (GNS) in the present invention;
Fig. 3 is the SEM figure on the spongy graphite oxide surface of preparing in the present invention;
Fig. 4 is the SEM figure of the spongy Graphene prepared in the present invention, and A and B are respectively the SEM figure of low power and high power.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
(1) raw material ultrasonic blend in ice bath
2g natural graphite is slowly joined to the dense H of 50mL in ice-bath ultrasonic state in 0.5h
2sO
4in, then add 1gNaNO
3.In 0.5h, slowly add on a small quantity 7g KMnO in batches
4, after all adding, potassium permanganate starts timing, reaction 1h, and guarantee system temperature is not higher than 10 ℃.
(2) oxidizing reaction of raw material in water-bath
Stirring reaction 1.5h in 35 ℃ of water-bath systems, slowly adds 100mL deionized water in mixed solution, keeps mixeding liquid temperature at 95 to 100 ℃, then continues stirring reaction 30min.In the most backward this system, slowly add 182mL deionized water, then add the hydrogen peroxide of 30mL30%, until solution becomes glassy yellow, without Bubble formation.
(3) washing of graphite oxide and lyophilize
Above-mentioned product separation is precipitated to thing, till utilizing 5% hydrochloric acid soln to clean graphite oxide to sulfate radical-free in filtrate to be detected, then by washed with de-ionized water to neutral.Finally, sample vacuum lyophilization 12h under-60 ℃, the condition of 12Pa.
(4) the low pressure hot soarfing of graphite oxide is from reduction
Yellow spongy graphite oxide, at 190 ℃ of lasting 10h, keeps pressure lower than 60Pa.
Embodiment 2
(1) raw material ultrasonic blend in ice bath
2g natural graphite is slowly joined to the dense H of 50mL in ice-bath ultrasonic state in 15min
2sO
4in, then add 1g NaNO
3.In 15min, slowly add on a small quantity 7g KMnO in batches
4, after all adding, potassium permanganate starts timing, reaction 2h, and guarantee system temperature is not higher than 10 ℃.
(2) oxidizing reaction of raw material in water-bath
Stirring reaction 1.5h in 36 ℃ of water-bath systems, slowly adds 100mL deionized water in mixed solution, keeps mixeding liquid temperature at 95 to 100 ℃, then continues stirring reaction 25min.In the most backward this system, slowly add 182mL deionized water, then add the hydrogen peroxide of 30mL30%, until solution becomes glassy yellow, without Bubble formation.
(3) washing of graphite oxide and lyophilize
Above-mentioned product separation is precipitated to thing, till utilizing 5% hydrochloric acid soln to clean graphite oxide to sulfate radical-free in filtrate to be detected, then by washed with de-ionized water to neutral.Finally, sample vacuum lyophilization 24h under-50 ℃, the condition of 10Pa.
(4) the low pressure hot soarfing of graphite oxide is from reduction
Yellow spongy graphite oxide, at 200 ℃ of lasting 5h, keeps pressure lower than 60Pa.
Embodiment 3
(1) raw material ultrasonic blend in ice bath
2g natural graphite is slowly joined to the dense H of 50mL in ice-bath ultrasonic state in 15min
2sO
4in, then add 1g NaNO
3.In 0.5h, slowly add on a small quantity 7g KMnO in batches
4, after all adding, potassium permanganate starts timing, reaction 1.5h, and guarantee system temperature is not higher than 10 ℃.
(2) oxidizing reaction of raw material in water-bath
Stirring reaction 1.5h in 37 ℃ of water-bath systems, slowly adds 100mL deionized water in mixed solution, keeps mixeding liquid temperature at 95 to 100 ℃, then continues stirring reaction 15min.In the most backward this system, slowly add 182mL deionized water, then add the hydrogen peroxide of 30mL30%, until solution becomes glassy yellow, without Bubble formation.
(3) washing of graphite oxide and lyophilize
Above-mentioned product separation is precipitated to thing, till utilizing 10% hydrochloric acid soln to clean graphite oxide to sulfate radical-free in filtrate to be detected, then by washed with de-ionized water to neutral.Finally, sample vacuum lyophilization 18h under-55 ℃, the condition of 12Pa.
(4) the low pressure hot soarfing of graphite oxide is from reduction
Yellow spongy graphite oxide, at 500 ℃ of lasting 4h, keeps pressure lower than 60Pa.
Embodiment 4
(1) raw material ultrasonic blend in ice bath
2g natural graphite is slowly joined to the dense H of 50mL in ice-bath ultrasonic state in 15minh
2sO
4in, then add 1g NaNO
3.In 0.5h, slowly add on a small quantity 7g KMn0 in batches
4, after all adding, potassium permanganate starts timing, reaction 2h, and guarantee system temperature is not higher than 10 ℃.
(2) oxidizing reaction of raw material in water-bath
Stirring reaction 1.5h in 38 ℃ of water-bath systems, slowly adds 100mL deionized water in mixed solution, keeps mixeding liquid temperature at 95 to 100 ℃, then continues stirring reaction 20min.In the most backward this system, slowly add 182mL deionized water, then add the hydrogen peroxide of 30mL30%, until solution becomes glassy yellow, without Bubble formation.
(3) washing of graphite oxide and lyophilize
Above-mentioned product separation is precipitated to thing, till utilizing 10% hydrochloric acid soln to clean graphite oxide to sulfate radical-free in filtrate to be detected, then by washed with de-ionized water to neutral.Finally, sample vacuum lyophilization 24h. under-45 ℃, the condition of 12Pa
(4) the low pressure hot soarfing of graphite oxide is from reduction
Yellow spongy graphite oxide, at 800 ℃ of lasting 2h, keeps pressure lower than 60Pa.
Claims (7)
1. freeze-drying is prepared a method for spongy Graphene, comprising:
(1) natural graphite is added to the dense H of ice-bath ultrasonic in 15-60min
2sO
4in, add afterwards NaNO
3, then in 15-60min, add potassium permanganate KMnO
4, after all adding, potassium permanganate starts timing, and reaction 0.5-1h, obtains mixed solution;
(2) above-mentioned mixed solution is reacted to 0.5-1.5h 30-35 ℃ of stirred in water bath, deionized water is added in mixed solution, be heated to 95-100 ℃, continue stirring reaction 20-30min, then add deionized water, hydrogen peroxide, then separation, washing, lyophilize, low pressure hot soarfing from, obtain spongy Graphene.
2. a kind of freeze-drying according to claim 1 is prepared the method for spongy Graphene, it is characterized in that: natural graphite, dense H in described step (1)
2sO
4, NaNO
3, potassium permanganate KMnO
4proportionlity be 2g:50ml:1g:7g.
3. a kind of freeze-drying according to claim 1 is prepared the method for spongy Graphene, it is characterized in that: the deionized water adding after the deionized water adding after stirring reaction 0.5-1.5h in described step (2), lasting stirring 20-30min, the volume ratio of hydrogen peroxide are 100:182:30.
4. a kind of freeze-drying according to claim 1 is prepared the method for spongy Graphene, it is characterized in that: in described step (2), the concentration expressed in percentage by volume of hydrogen peroxide is 30%.
5. a kind of freeze-drying according to claim 1 is prepared the method for spongy Graphene, it is characterized in that: washing is for till cleaning with the hydrochloric acid soln that concentration expressed in percentage by volume is 5% and being detected to sulfate radical-free in filtrate in described step (2).
6. a kind of freeze-drying according to claim 1 is prepared the method for spongy Graphene, it is characterized in that: in described step (2), lyophilize is: below-60 ℃, under the condition lower than 12Pa, and vacuum lyophilization 12-24h.
7. a kind of freeze-drying according to claim 1 is prepared the method for spongy Graphene, it is characterized in that: described step (2) mesolow hot soarfing is from being: keep pressure lower than 60Pa, at 180-800 ℃ of lasting 2-15h.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105110320A (en) * | 2015-06-26 | 2015-12-02 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of graphene porous material used for flue gas adsorption |
| CN106242297A (en) * | 2016-08-29 | 2016-12-21 | 佛山市高明区明城镇新能源新材料产业技术创新中心 | A kind of antibacterial and deodouring Ceramic Tiles and preparation method thereof |
| CN106345413A (en) * | 2016-10-20 | 2017-01-25 | 碳为（北京）新材料科技有限公司 | Preparation method of porous spongy graphene |
| CN106365453A (en) * | 2016-08-29 | 2017-02-01 | 佛山市高明区明城镇新能源新材料产业技术创新中心 | Anti-radiation ceramic tile and preparing method thereof |
| CN106396384A (en) * | 2016-08-29 | 2017-02-15 | 佛山市高明区明城镇新能源新材料产业技术创新中心 | Noctilucent deodorant ceramic glaze and preparation method thereof |
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| CN106396401A (en) * | 2016-08-29 | 2017-02-15 | 佛山市高明区明城镇新能源新材料产业技术创新中心 | Antistatic health care ceramic and preparation method thereof |
| CN106396405A (en) * | 2016-08-29 | 2017-02-15 | 佛山市高明区明城镇新能源新材料产业技术创新中心 | Photochromic ceramic tile and preparation method thereof |
| CN109809396A (en) * | 2019-03-26 | 2019-05-28 | 吉林大学 | A kind of redox graphene aeroge and its vapor hydrothermal reduction preparation method |
| CN112625282A (en) * | 2020-12-29 | 2021-04-09 | 诸暨市申嘉机械科技有限公司 | Production and processing technology of pearl graphene |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105110320A (en) * | 2015-06-26 | 2015-12-02 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of graphene porous material used for flue gas adsorption |
| CN106242297A (en) * | 2016-08-29 | 2016-12-21 | 佛山市高明区明城镇新能源新材料产业技术创新中心 | A kind of antibacterial and deodouring Ceramic Tiles and preparation method thereof |
| CN106365453A (en) * | 2016-08-29 | 2017-02-01 | 佛山市高明区明城镇新能源新材料产业技术创新中心 | Anti-radiation ceramic tile and preparing method thereof |
| CN106396384A (en) * | 2016-08-29 | 2017-02-15 | 佛山市高明区明城镇新能源新材料产业技术创新中心 | Noctilucent deodorant ceramic glaze and preparation method thereof |
| CN106396400A (en) * | 2016-08-29 | 2017-02-15 | 佛山市高明区明城镇新能源新材料产业技术创新中心 | Antibacterial negative ion health care ceramic and preparation method thereof |
| CN106396401A (en) * | 2016-08-29 | 2017-02-15 | 佛山市高明区明城镇新能源新材料产业技术创新中心 | Antistatic health care ceramic and preparation method thereof |
| CN106396405A (en) * | 2016-08-29 | 2017-02-15 | 佛山市高明区明城镇新能源新材料产业技术创新中心 | Photochromic ceramic tile and preparation method thereof |
| CN106345413A (en) * | 2016-10-20 | 2017-01-25 | 碳为（北京）新材料科技有限公司 | Preparation method of porous spongy graphene |
| CN109809396A (en) * | 2019-03-26 | 2019-05-28 | 吉林大学 | A kind of redox graphene aeroge and its vapor hydrothermal reduction preparation method |
| CN112625282A (en) * | 2020-12-29 | 2021-04-09 | 诸暨市申嘉机械科技有限公司 | Production and processing technology of pearl graphene |
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Application publication date: 20141126 |
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