CN103910355A - Preparation method of porous three-dimensional graphene - Google Patents
Preparation method of porous three-dimensional graphene Download PDFInfo
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- CN103910355A CN103910355A CN201410173727.XA CN201410173727A CN103910355A CN 103910355 A CN103910355 A CN 103910355A CN 201410173727 A CN201410173727 A CN 201410173727A CN 103910355 A CN103910355 A CN 103910355A
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Abstract
The invention belongs to the technical field of preparation of nano materials, and particularly relates to a preparation method of porous three-dimensional graphene. The technical scheme is as follows: the preparation method comprises the following steps: introducing carbonate or bicarbonate into the raw material graphene oxide (GO) to form a GO-carbonate or bicarbonate mixture; and adding a reducer under weakly alkaline conditions, carrying out hydrothermal reaction to obtain a graphene-carbonate or bicarbonate gel, and reacting acid with carbonate or bicarbonate to release gas so as to generate abundant perforated holes, thereby obtaining the perforated porous three-dimensional graphene. The method is simple to operate and low in cost; and the prepared porous three-dimensional graphene has the advantages of high electric conductivity, large specific area, hydrophilcity/hydrophobicity and the like, and can be widely used in the fields of heat-conducting composite materials, energy storage materials, adsorbing materials and the like.
Description
Technical field
The invention belongs to the preparing technical field of nano material, be specifically related to a kind of preparation method of porous three-dimensional Graphene.
Background technology
Graphene is an emerging material, and its theoretical specific surface area can reach 2620m
2/ g, there is potential application performance, but because the laminated structure of Graphene is easily reunited, be easy to form the two-dirnentional structure material that porosity is lower, cannot obtain the vesicular structure three-dimensional grapheme of higher porosity, then make its performance and range of application be greatly limited.At present, the method for synthetic three-dimensional grapheme adopts chemical Vapor deposition process (CVD) and hydrothermal method conventionally, but adopts CVD method growth conditions harshness, is difficult to realize the production in enormous quantities of three-dimensional grapheme; Have more pore structure although hydrothermal method is prepared three-dimensional grapheme, the connectedness of pore structure is poor, for packing material provide can be composite filled space less, this has just limited the Application Areas of three-dimensional grapheme.
Summary of the invention
The object of the invention is to solve the deficiencies in the prior art and shortcoming, a kind of method of preparing the three-dimensional grapheme that porous connects take carbonate or supercarbonate as template is provided, concrete technical scheme comprises the following steps:
(1), take graphene oxide as raw material, carbonate or supercarbonate are added in graphene oxide solution to ultrasonic 10-200 min be uniformly dispersed formation graphene oxide-carbonate or supercarbonate mixed solution.
Wherein, carbonate is any one or the multiple mixture in sodium carbonate, copper carbonate, calcium carbonate, salt of wormwood, volatile salt, Quilonum Retard, nickelous carbonate, zinc carbonate, iron carbonate, the mass ratio of carbonate and graphene oxide is 1:100-100:1, preferably 1:10-20:1; Supercarbonate is any one or the multiple mixture in sodium bicarbonate, saleratus, bicarbonate of ammonia, Calcium hydrogen carbonate, and the mass ratio of supercarbonate and graphene oxide is 1:100-100:1, preferably 1:10-20:1.
(2) in step (1) mixed solution, add appropriate basic solution, regulate the pH value of mixture, add a certain amount of reductive agent simultaneously, its mixing solutions is inserted in reactor, carry out hydro-thermal reaction, form rGO-carbonate or supercarbonate jello, lyophilize obtains Graphene-carbonate or supercarbonate solid.
Wherein, alkaline solution is any one in potassium hydroxide, sodium hydroxide, ammoniacal liquor, and alkaline solution and Graphene consumption mass ratio are 1:15-10:1, and the pH of solution is adjusted into 7-10, promote follow-up reduction reaction.
Wherein, reductive agent is hydrazine hydrate, sodium borohydride, highly basic, glucose, urea, tea-polyphenol, vitamins C, SOCl
2in any one, the mass ratio of reductive agent and graphene oxide is 1:80-60:1, preferential 1:5-15:1; Wherein, highly basic is mainly any one in sodium hydroxide, potassium hydroxide, lithium hydroxide, hydrated barta.
Wherein, hydrothermal temperature is 80 ℃-400 ℃, and the reaction times is 3-48 h; Described cryodesiccated temperature is-70-0 ℃, time is 2-72h, the object of hydro-thermal reaction is that graphene oxide is reduced to Graphene on the one hand, the opposing party combines the Graphene of carbonate or supercarbonate and generation together, be combined into jello, be convenient to the follow-up three-dimensional grapheme that porous connects of making.
(3) add acid solution to Graphene-carbonate or supercarbonate solid, react with its carbonate or supercarbonate, discharge gas, washing, cooling drying afterwards, obtains the three-dimensional grapheme of vesicular structure.
Wherein, acid solution is one or more the mixture in hydrochloric acid, acetic acid, nitric acid, phosphoric acid, and acid is 1:1-5:1 with the mol ratio of carbonate or supercarbonate; Acid solution reacts with the carbonate or the supercarbonate that are compounded on Graphene, discharges gas, is convenient to Graphene and forms the vesicular structure connecting.
Wherein, washing soln is ethanol or deionized water; Cryodesiccated temperature is-80-0 ℃ that the time is 6-72h.
The inventive method is simple to operate, with low cost, and the three-dimensional grapheme of the porous intercommunication of preparation has the advantages such as electric conductivity is high, specific surface area is large, close and distant water, can be widely used in the fields such as heat-conductive composite material, energy storage material, sorbing material.
Accompanying drawing explanation
Fig. 1 is the schema of preparing porous three-dimensional Graphene.
Fig. 2 is prepared three-dimensional grapheme outside drawing in kind in embodiment 1.
Fig. 3 is the scanning electron microscope (SEM) photograph of prepared three-dimensional grapheme under amplification 4000 multiples in embodiment 1.
Fig. 4 is the scanning electron microscope (SEM) photograph of prepared three-dimensional grapheme under amplification 50000 multiples in embodiment 1.
the concrete mode of implementing
Below in conjunction with the drawings and specific embodiments, technical scheme of the present invention is described in detail, but the explanation of described embodiment is only a part of embodiment of the present invention, wherein major part is not limited in this.
embodiment 1
1. prepare porous three-dimensional Graphene take sodium carbonate as template
Prepare three-dimensional grapheme process flow sheet using sodium carbonate as masterplate as shown in Figure 1, concrete steps are:
(1) get the graphene oxide solution that 10mL concentration is 8mg/mL, add 100mg sodium carbonate, stir ultrasonic 30min and disperse to form Na
2cO
3-GO mixed solution;
(2) to by step (1) Na
2cO
3in-GO mixed solution, add 1ml ammoniacal liquor, and ultrasonic agitation 0.5h, regulator solution pH value is 8, aobvious weakly alkaline, then add 100mg glucose, and this mixing solutions is inserted in reactor, be at 180 ℃ in temperature, reduction reaction 12 hours, obtains Na
2cO
3-rGO jello, is placed in jello lyophilize 24h under-30 ℃ of conditions, obtains Na
2cO
3-rGO solid;
(3) to step (2) Na
2cO
3in-rGO solid, add the hydrochloric acid that 50 mL concentration are 1mol/L, make Na
2cO
3na in-rGO solid
2cO
3reaction discharges CO
2gas, forms pore structure, obtains vesicular three-dimensional grapheme, with deionized water, three-dimensional grapheme is washed 5 times afterwards, and lyophilize 12h under-20 ℃ of conditions, obtains cavernous three-dimensional grapheme.
The pictorial diagram of prepared three-dimensional grapheme as shown in Figure 2, and the three-dimensional grapheme of preparation is carried out to scanning electron microscope analysis under different magnifications, as shown in Figure 3 and Figure 4, as seen from the figure, the three-dimensional grapheme of preparation is the network structure that porous connects, and the size in hole is 1 micron of left and right.
embodiment 2
2. to prepare porous three-dimensional Graphene with magnesiumcarbonate as template
Using magnesiumcarbonate as the concrete steps of preparing three-dimensional grapheme in the same manner as in Example 1, just sodium carbonate is replaced with to magnesiumcarbonate, glucose replaces with hydrazine hydrate.
Claims (7)
1. a preparation method for porous three-dimensional Graphene, comprises the following steps:
(1), take graphene oxide as raw material, carbonate or supercarbonate are added in graphene oxide solution to ultrasonic formation graphene oxide-carbonate or the supercarbonate mixed solution of being uniformly dispersed;
(2) in step (1) mixed solution, add appropriate basic solution, regulate the pH value of mixture, add a certain amount of reductive agent simultaneously, its mixing solutions is inserted in reactor, carry out hydro-thermal reaction, form rGO-carbonate or supercarbonate jello, lyophilize obtains Graphene-carbonate or supercarbonate solid;
(3) add acid solution to Graphene-carbonate or supercarbonate solid, react with its carbonate or supercarbonate, discharge gas, washing, cooling drying afterwards, obtains the three-dimensional grapheme of vesicular structure.
2. according to the preparation method of a kind of porous three-dimensional Graphene described in claim 1, it is characterized in that: the described carbonate of step (1) is any one or the multiple mixture in sodium carbonate, copper carbonate, calcium carbonate, salt of wormwood, volatile salt, Quilonum Retard, nickelous carbonate, zinc carbonate, iron carbonate, the mass ratio of carbonate and graphene oxide is 1:100-100:1, preferably 1:10-20:1; Described supercarbonate is any one or the multiple mixture in sodium bicarbonate, saleratus, bicarbonate of ammonia, Calcium hydrogen carbonate, and the mass ratio of supercarbonate and graphene oxide is 1:100-100:1, preferably 1:10-20:1.
3. according to the preparation method of a kind of porous three-dimensional Graphene described in claim 1, it is characterized in that: the alkaline solution described in step (2) is any one in potassium hydroxide, sodium hydroxide, ammoniacal liquor, alkaline solution and Graphene consumption mass ratio are 1:15-10:1; Described pH is 7-10.
4. according to the preparation method of a kind of porous three-dimensional Graphene described in claim 1, it is characterized in that: the reductive agent described in step (2) is hydrazine hydrate, sodium borohydride, highly basic, glucose, urea, tea-polyphenol, vitamins C, SOCl
2in any one, the mass ratio of reductive agent and graphene oxide is 1:80-60:1, preferential 1:5-15:1; Wherein, highly basic is mainly any one in sodium hydroxide, potassium hydroxide, lithium hydroxide, hydrated barta.
5. according to the preparation method of a kind of porous three-dimensional Graphene described in claim 1, it is characterized in that: the hydrothermal temperature described in step (2) is 80 ℃-400 ℃, and the reaction times is 3-48 h; Described cryodesiccated temperature is-70-0 ℃ that the time is 2-72h.
6. according to the preparation method of a kind of porous three-dimensional Graphene described in claim 1, it is characterized in that: the acid solution described in step (3) is one or more the mixture in hydrochloric acid, acetic acid, nitric acid, phosphoric acid, acid is 1:1-5:1 with the mol ratio of carbonate or supercarbonate.
7. according to the preparation method of a kind of porous three-dimensional Graphene described in claim 1, it is characterized in that: the washing soln described in step (3) is ethanol or deionized water; Described cryodesiccated temperature is-80-0 ℃ that the time is 6-72h.
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| CN104826629A (en) * | 2015-04-17 | 2015-08-12 | 华南师范大学 | Synthetic method and applications of porous graphene composite catalyst |
| CN105217607A (en) * | 2015-08-22 | 2016-01-06 | 苏州正业昌智能科技有限公司 | A kind of graphene preparation method based on xylogen |
| CN105253880A (en) * | 2015-11-29 | 2016-01-20 | 南京新月材料科技有限公司 | Three-dimensional graphene preparing method |
| CN105321724A (en) * | 2015-11-20 | 2016-02-10 | 中国科学技术大学 | Three-dimensional porous graphene, preparation method and application therefor |
| CN105329883A (en) * | 2015-10-14 | 2016-02-17 | 南京邮电大学 | Porous graphene preparation method |
| CN106449180A (en) * | 2016-11-28 | 2017-02-22 | 北京航空航天大学 | Method for increasing specific capacitance of graphene-based supercapacitor |
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| CN107161984A (en) * | 2017-06-28 | 2017-09-15 | 华南理工大学 | The method that a kind of ascorbic acid/Tea Polyphenols synergy prepares graphene |
| CN107311155A (en) * | 2017-08-07 | 2017-11-03 | 中国科学院合肥物质科学研究院 | The preparation method of porous graphene |
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| CN109569549A (en) * | 2018-12-25 | 2019-04-05 | 咸阳师范学院 | A kind of preparation method of porous oxidation graphene/CaO/ glucose compound adsorbent |
| CN110015746A (en) * | 2019-05-13 | 2019-07-16 | 上海大学 | A kind of preparation method and application of graphene multi-element metal composite material |
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| CN104826629A (en) * | 2015-04-17 | 2015-08-12 | 华南师范大学 | Synthetic method and applications of porous graphene composite catalyst |
| CN105217607A (en) * | 2015-08-22 | 2016-01-06 | 苏州正业昌智能科技有限公司 | A kind of graphene preparation method based on xylogen |
| CN105329883A (en) * | 2015-10-14 | 2016-02-17 | 南京邮电大学 | Porous graphene preparation method |
| CN105321724A (en) * | 2015-11-20 | 2016-02-10 | 中国科学技术大学 | Three-dimensional porous graphene, preparation method and application therefor |
| CN105253880A (en) * | 2015-11-29 | 2016-01-20 | 南京新月材料科技有限公司 | Three-dimensional graphene preparing method |
| CN108445166A (en) * | 2016-10-27 | 2018-08-24 | 苏州大学 | A kind of three-dimensional porous graphene extra-thin film and preparation method thereof |
| CN106449180A (en) * | 2016-11-28 | 2017-02-22 | 北京航空航天大学 | Method for increasing specific capacitance of graphene-based supercapacitor |
| CN106449180B (en) * | 2016-11-28 | 2018-10-26 | 北京航空航天大学 | A method of improving the specific capacitance of graphene-based ultracapacitor |
| CN106587026A (en) * | 2016-12-28 | 2017-04-26 | 山东理工大学 | Preparation method of reinforced mass transfer type 3D nitrogen-doped graphene with multi-stage pores communicated |
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| CN107151010A (en) * | 2017-06-08 | 2017-09-12 | 福建师范大学 | A kind of method that graphene is prepared by reducing agent of leaf extract solution |
| CN107161984A (en) * | 2017-06-28 | 2017-09-15 | 华南理工大学 | The method that a kind of ascorbic acid/Tea Polyphenols synergy prepares graphene |
| CN107311155A (en) * | 2017-08-07 | 2017-11-03 | 中国科学院合肥物质科学研究院 | The preparation method of porous graphene |
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| CN110015746A (en) * | 2019-05-13 | 2019-07-16 | 上海大学 | A kind of preparation method and application of graphene multi-element metal composite material |
| CN112537768A (en) * | 2019-09-23 | 2021-03-23 | 中国科学院上海硅酸盐研究所苏州研究院 | High-strength three-dimensional graphene macroscopic body and preparation method thereof |
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Application publication date: 20140709 |