CN110589819B - Graphene aerogel and preparation method thereof - Google Patents
Graphene aerogel and preparation method thereof Download PDFInfo
- Publication number
- CN110589819B CN110589819B CN201911059651.7A CN201911059651A CN110589819B CN 110589819 B CN110589819 B CN 110589819B CN 201911059651 A CN201911059651 A CN 201911059651A CN 110589819 B CN110589819 B CN 110589819B
- Authority
- CN
- China
- Prior art keywords
- graphene
- aerogel
- guar gum
- preparation
- graphene oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to application of guar gum in preparation of graphene aerogel, and further provides a preparation method of the graphene aerogel, which comprises the following steps: uniformly mixing the colloidal solution of graphene oxide with guar gum, then reacting the obtained dispersion liquid at 170-200 ℃, and obtaining the graphene aerogel after complete reaction, wherein the mass ratio of the graphene oxide in the colloidal solution of graphene oxide to the guar gum is 10:1-1: 3. According to the invention, the graphene aerogel is prepared by utilizing the guar gum, the preparation method is simple, the prepared aerogel is not easy to break, and the mechanical strength is good.
Description
Technical Field
The invention relates to the field of functional materials, in particular to graphene aerogel and a preparation method thereof.
Background
The graphene aerogel is a high-strength aerogel, is a graphene macroscopic body material formed by three-dimensionally building and assembling graphene sheet layers, has the nanometer characteristic of graphene and the macroscopic structure of aerogel, shows a three-dimensional continuous porous network structure, has the characteristics of high conductivity, high elasticity, ultralow density, high porosity, high specific surface area and strong adsorption, and has a very good application prospect in the aspects of energy storage, sensing, adsorption, catalysis and the like.
However, the conventional three-dimensional assembly of graphene aerogel mainly adopts a local building mode of 'surface-to-surface' between graphene sheets to form a three-dimensional disordered porous network. The mode of lapping is a random and random assembly mode, graphene sheet layers are easy to stack, so that a graphite-like structure is formed, graphene cannot be effectively separated to provide enough surface area and porosity, collapse and fracture are easy, and mechanical strength is limited. At present, the preparation of graphene aerogel by adopting a one-step hydrothermal method is reported early, the prepared graphene shows excellent performance in adsorption performance, but the graphene prepared by the one-step hydrothermal method is formed by three-dimensional building and assembling of graphene sheet layers, and after hydrothermal treatment, the surface functional groups are few, so that the graphene material is greatly limited in the aspects of metal ion adsorption and the like, and the subsequent functional group modification and metal ion modification can cause the collapse of the aerogel, so that the application of the graphene in the later period is greatly limited.
CN102976347A discloses a method for preparing rectorite aerogel, which uses guar gum as a cross-linking agent to connect rectorite sheets to form an aerogel composite material, wherein the rectorite does not have self-assembly function. CN105566659 discloses a graphene oxide/nano cellulose aerogel, CN107032323A discloses a preparation method of a sheet-like porous nanomaterial, and a freeze-drying method is adopted to prepare the porous material. The former adopts a staggered structure of nano-cellulose and graphene to improve the performance of the aerogel, and belongs to the mixture of two microscopic materials; the latter is only an effective method for preparing porous materials, mainly has the function of removing the solvent in the pore channels so as to ensure that the porosity is not collapsed due to solvent evaporation, and belongs to the final step for preparing aerogel materials. The aerogel and the porous material are lack of functional groups on the surfaces, so that the subsequent modification, application and the like (such as linking metal ions, bridging other small molecules and the like) of the whole material are greatly limited; meanwhile, the whole material belongs to a structure formed by physical stacking, and the integral mechanical strength needs to be improved.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide the graphene aerogel and the preparation method thereof.
The first purpose of the invention is to disclose the application of guar gum in preparing graphene aerogel.
Guar gum can coordinate various metals, such as Ti4+，B3+，Zr4+And (3) coordinating cations to obtain the composite cross-linking agent, so that the composite cross-linking agent is used for preparing the graphene aerogel.
The second purpose of the present invention is to provide a preparation method of graphene aerogel, comprising the following steps:
uniformly mixing the colloidal solution of graphene oxide with guar gum, then reacting the obtained dispersion liquid at 170-200 ℃, and obtaining the graphene aerogel after complete reaction, wherein the mass ratio of the graphene oxide in the colloidal solution of graphene oxide to the guar gum is 10:1-1: 3.
According to the method, the guar gum functionalized graphene aerogel is prepared by adding and controlling a proper proportion of guar gum and graphene oxide. Graphene oxide is reduced to graphene at the temperature of 170-200 ℃, and the graphene oxide interacts with graphene sheets through the bonding effect of guar gum, so that the problem of sheet stacking of graphene in the self-assembly process is effectively reduced. The mechanical strength of the graphene aerogel is improved while the porosity of the graphene aerogel is improved. However, excessive guar gum can inhibit the self-assembly of graphene sheets, resulting in the eventual failure to form graphene aerogels.
Further, the preparation method of the colloidal solution of graphene oxide comprises the following steps:
and mixing the graphene oxide with water, performing ultrasonic dispersion, and standing to obtain the colloidal solution of the graphene oxide.
Further, the concentration of the colloidal solution of graphene oxide is 0.1-5 mg/mL.
Further, guar gum is added to the colloidal solution of graphene oxide under stirring.
Further, the reaction time is 12 hours to 24 hours.
Further, the reaction also comprises the steps of cooling, immersing the product in water and then freezing and drying.
Further, the temperature of freeze-drying was-40 ℃.
According to the method, guar gum which cannot cause damage to the aerogel is used for modifying the graphene, stacking among the graphene is effectively expanded, the guar gum modified functionalized graphene is promoted to be self-assembled into the functionalized graphene aerogel, and the porosity of the reduced aerogel is improved.
The third purpose of the invention is to protect the graphene aerogel prepared by the preparation method.
According to the preparation method, guar gum which cannot cause damage to the aerogel is introduced in the process of preparing the graphene aerogel, so that stacking among the graphene can be effectively propped, the porosity of the reduced aerogel is improved, and meanwhile, effective space and contact area can be provided for subsequent loading of metal ions.
By the scheme, the invention at least has the following advantages:
1. the invention discloses a preparation method of guar gum in graphene aerogel preparationThe application and the specific preparation method of the graphene aerogel use guar gum as a connecting body to construct a functionalized graphene aerogel material. Since guar gum can coordinate with various metals, such as Ti4+，B3+，Zr4+And coordinating with cation to obtain the composite crosslinking agent.
2. The graphene aerogel disclosed by the invention is simple in preparation steps, easy to operate in a synthesis method, easy to obtain required raw materials and convenient to control conditions.
3. According to the invention, by means of the rich hydroxyl groups of the guar gum, the guar gum can interact with graphene, and hydrolysis is carried out under appropriate conditions by adjusting factors such as temperature and addition amount, so that the guar gum modified functionalized graphene is promoted to self-assemble into the functionalized graphene aerogel. By means of interaction and crosslinking of guar gum and graphene, stacking effect between graphene sheets in the graphene aerogel is reduced, porosity of the graphene aerogel is increased, corresponding mechanical strength of the graphene aerogel is increased, and collapse rate is reduced.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
Fig. 1 is an appearance picture of the graphene aerogels prepared in comparative example 1 and example 1;
fig. 2 is an infrared spectrum of the graphene aerogels prepared in comparative example 1 and example 1;
fig. 3 is a morphological photograph of the product of comparative example 2.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
(1) Preparing a 1.5mg/mL graphene oxide colloidal solution: 45mg of graphene oxide powder was dispersed in 30mL of water, sonicated for 1 hour, and allowed to stand for 12 hours. In the invention, the concentration of the graphene oxide colloidal solution is not limited to 1.5mg/mL, and the concentration can be 0.1mg/mL-5mg/L, which mainly depends on the ratio of guar gum to graphene.
(2) Weighing 50mg of guar gum, adding the guar gum into the graphene oxide colloidal solution under the stirring condition, and fully and uniformly mixing. The mass ratio of the guar gum to the graphene oxide can be adjusted within the range of 0.1-3: 1. Excessive guar gum cannot be added, so that the phenomenon that the hydroxyl functional groups in the guar gum structure act due to excessive compounding of graphene sheets and the final functionalized graphene aerogel cannot be formed is avoided.
(3) After the solution was stirred uniformly, the solution was transferred to a 50mL reaction vessel and reacted at 180 ℃ for 12 hours. And after the reaction is finished, cooling the product, and directly soaking the obtained functionalized graphene aerogel in water. After fully soaking, placing in a refrigerator for freezing.
(5) Freeze-drying the obtained graphene aerogel at-40 deg.C, continuously pumping air with vacuum pump, and maintaining pressure at 10 ℃-3pa。
Comparative example 1
A graphene aerogel was prepared according to the method of example 1, except that the step (2) was omitted. Directly heating the graphene oxide colloidal solution in a reaction kettle.
As shown in fig. 1, fig. 1a and b are the graphene aerogels prepared in comparative example 1 and example 1, respectively, and the same mass of graphene oxide raw material is added, the diameter of the aerogel of comparative example 1 is 1.0cm, the height of the aerogel is 1.5cm, and the diameter of the aerogel of example 1 is 1.15cm, and the height of the aerogel is 1.7 cm. The result shows that the addition of guar gum can effectively increase the macroscopic volume of the graphene aerogel, and the introduction of guar gum can effectively inhibit the stacking of graphene sheets. In addition, from the appearance, the graphene aerogel without guar gum is rough in surface and has numerous cracks, which indicates that the stacking action force between graphene sheet layers is relatively weak, and surface particles are easy to fall off. After the guar gum binder is added, the obtained functional aerogel is obviously finer in surface and obviously improved in mechanical strength.
Fig. 2a and b are infrared spectra of the graphene aerogels prepared in comparative example 1 and example 1, respectively, and the graphene aerogel prepared in example 1 has a signal peak of guar gum (within a dotted circle in the figure), indicating that the product contains a guar gum structure.
Comparative example 2
Graphene aerogel was prepared according to the method of example 1, except that, in the step (2), the mass ratio of the added guar gum to the graphene oxide was 5: 1.
As shown in fig. 3, the graphene aerogel cannot be obtained by the above method, and the product of step (3) is still in a liquid state.
The prepared functionalized graphene aerogel is subjected to infrared characterization (fig. 2), and it can be found that the structure of guar gum is not damaged in the preparation process of the aerogel, which indicates that the method can be used for effectively realizing functionalized regulation and control on the graphene aerogel.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (4)
1. The preparation method of the graphene aerogel is characterized by comprising the following steps: adding guar gum into a colloidal solution of graphene oxide under the stirring condition, uniformly mixing, reacting the obtained dispersion liquid at 170-200 ℃, cooling after complete reaction, immersing the product into water, and freeze-drying to obtain the graphene aerogel, wherein the mass ratio of the graphene oxide in the colloidal solution of the graphene oxide to the guar gum is 10:1-1: 3;
the preparation method of the graphene oxide colloidal solution comprises the following steps: and mixing the graphene oxide with water, performing ultrasonic dispersion, and standing to obtain the colloidal solution of the graphene oxide.
2. The method according to claim 1, wherein the reaction time is 12 to 24 hours.
3. The method of claim 1, wherein the temperature of freeze-drying is-40 ℃.
4. A graphene aerogel prepared by the preparation method of any one of claims 1 to 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911059651.7A CN110589819B (en) | 2019-11-01 | 2019-11-01 | Graphene aerogel and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911059651.7A CN110589819B (en) | 2019-11-01 | 2019-11-01 | Graphene aerogel and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110589819A CN110589819A (en) | 2019-12-20 |
| CN110589819B true CN110589819B (en) | 2021-09-07 |
Family
ID=68852111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911059651.7A Active CN110589819B (en) | 2019-11-01 | 2019-11-01 | Graphene aerogel and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110589819B (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017217832A1 (en) * | 2016-06-17 | 2017-12-21 | 한국기계연구원 | Method for producing carbon aerogel precursor, and carbon aerogel precursor and carbon aerogel produced thereby |
| CN108465459A (en) * | 2018-05-09 | 2018-08-31 | 福建省农业科学院农业生物资源研究所 | A kind of mixing aeroge and the preparation method and application thereof |
| CN109456511B (en) * | 2018-10-30 | 2021-02-26 | 福建工程学院 | Thermosensitive, conductive and super-tensile collagen-based instant self-healing hydrogel |
-
2019
- 2019-11-01 CN CN201911059651.7A patent/CN110589819B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110589819A (en) | 2019-12-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sun et al. | Overview of cellulose-based flexible materials for supercapacitors | |
| CN104495780B (en) | Hydrophilic graphene-carbon nano-tube composite super-light elastic aerogel and preparation method thereof | |
| CN107790102B (en) | Three-dimensional folded spherical MOFs @ rGO oil absorption material and preparation method thereof | |
| CN107871617B (en) | Graphene-metal organic frame composite material and preparation method and application | |
| JP6019228B2 (en) | Method for producing high density and high hardness graphene porous carbon material | |
| CN104310389B (en) | A kind of Anti-pressure Graphene hydrogel and preparation method thereof | |
| Liu et al. | Revealing the dynamic formation process and mechanism of hollow carbon spheres: from bowl to sphere | |
| CN109399619B (en) | Preparation method of nitrogen-doped graphene aerogel | |
| CN104479174A (en) | Cellulose-based magnetic aerogel material and preparation method thereof | |
| CN100510171C (en) | Preparation method of carbon coated TiO* core-shell composite nanometer powder | |
| CN106215817B (en) | Preparation method of graphene hydrogel with adjustable internal structure | |
| CN107946086A (en) | It is a kind of using graphene as full carbon resistance rod of ultracapacitor flexible self-supporting of binding agent and preparation method thereof | |
| CN105688285B (en) | A kind of preparation method of grapheme material coating chitosan three-dimensional bracket | |
| CN103641111A (en) | Preparation method of graded porous graphene material for super-capacitor | |
| CN113526497B (en) | Preparation method of organic modified vermiculite/graphene composite aerogel | |
| CN109499497B (en) | Preparation method of graphene/carbon microsphere composite aerogel | |
| CN107583106A (en) | Poly- citrate/chitin nano whisker tissue engineering bracket and preparation method thereof | |
| CN103449427A (en) | Preparation method of porous graphene-ferric oxide composite material | |
| KR20120137111A (en) | Preparation method of core-shell silica particle with mesoporous shell | |
| CN110589819B (en) | Graphene aerogel and preparation method thereof | |
| Liu et al. | Cyclodextrin-Based Aerogels: A Review of Nanomaterials Systems and Applications | |
| CN116216720A (en) | MXene aerogel for hydrogen storage and preparation method thereof | |
| CN108190866B (en) | Method for simply controlling synthesis of echinoid graphene spheres by water-in-oil emulsion method | |
| CN103482616B (en) | Preparation method of graphene-tin dioxide nanoparticle three-dimensional foam composite material | |
| CN107827104A (en) | A kind of graphene oxide microballoon, the preparation method of graphene microballoon |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |