CN107804836B - Three-dimensional graphene based on biopolymer and one-step preparation method thereof - Google Patents
Three-dimensional graphene based on biopolymer and one-step preparation method thereof Download PDFInfo
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- CN107804836B CN107804836B CN201711081630.6A CN201711081630A CN107804836B CN 107804836 B CN107804836 B CN 107804836B CN 201711081630 A CN201711081630 A CN 201711081630A CN 107804836 B CN107804836 B CN 107804836B
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- C01B2204/00—Structure or properties of graphene
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- C01B2204/32—Size or surface area
Abstract
The invention discloses a biopolymer-based three-dimensional graphene, which is obtained by adsorbing Co ions by a biopolymer, carbonizing at high temperature, and washing with concentrated nitric acid, wherein the specific surface area of the biopolymer-based three-dimensional graphene is 400 m-2The biopolymer is prepared from solidified persimmon tannin prepared from persimmon tannin and chitosan by adopting Co ions as a catalyst and a one-step carbonization method. The preparation method comprises the following steps: 1) preparing solidified persimmon tannin powder; 2) preparing a precursor; 3) and (3) preparing three-dimensional graphene. The invention adopts a one-step carbonization method, has simple process, stable product performance, is suitable for large-batch preparation, has simple post-treatment process and has wide application prospect in the field of carbon functional materials.
Description
Technical Field
The invention relates to the technical field of preparation of porous carbon materials, in particular to a biopolymer-based three-dimensional graphene and a preparation method thereof.
Background
Graphene is a two-dimensional material of carbon which is receiving attention in recent years, and has many excellent characteristics, such as high electrical conductivity, high specific surface area, high thermal conductivity and excellent mechanical properties, so that graphene has a good application prospect in many fields. However, due to the strong attraction between graphene sheets, the solid graphene loses the excellent properties of high specific surface area and the like of the monodisperse graphene due to aggregation. Each piece of graphene is connected together to form a three-dimensional honeycomb-shaped skeleton structure, so that the solid graphene can show excellent performance similar to that of single graphene, and the problem is effectively solved.
The three-dimensional graphene foam is prepared by taking foamed nickel as a template, and graphene sheets grow on the surface of nickel and are connected into a whole, so that the isotropic and porous three-dimensional skeleton structure of the foamed nickel is inherited. The three-dimensional graphene can also be prepared by a sol-gel method, namely, firstly, graphene oxide is crosslinked to form hydrogel through hydrothermal processes and the like, and then, moisture is removed through freeze drying or supercritical drying to generate the aerogel. The three-dimensional graphene materials have different structures and properties, but all of the three-dimensional graphene materials have the common characteristics of high specific surface area and porosity, low density, high conductivity and the like. However, these preparation methods are complicated, time-consuming and costly, and the three-dimensional graphene can be further obtained only after the graphene is prepared.
If the three-dimensional graphene can be prepared in one step, the production cost can be effectively reduced.
Disclosure of Invention
The invention aims to provide a biopolymer-based three-dimensional graphene and a preparation method thereof.
The solidified persimmon tannin adsorbed with Co ions is used as a precursor, when carbonization is carried out at high temperature, Co catalyzes the reaction to obtain a Co-doped three-dimensional graphene material, and then nitric acid is adopted for refluxing and washing to remove cobalt element to obtain the three-dimensional graphene.
The three-dimensional graphene material can be directly obtained without preparing graphene in advance.
In order to achieve the purpose of the invention, the invention adopts the technical scheme that:
the three-dimensional graphene based on the biopolymer is obtained by adsorbing Co ions by the biopolymer, carbonizing at high temperature and washing with concentrated nitric acid, and the specific surface area of the three-dimensional graphene is 300-400 m-2The biopolymer is prepared from solidified persimmon tannin prepared from persimmon tannin and chitosan by adopting Co ions as a catalyst and a one-step carbonization method.
The preparation method of the three-dimensional graphene based on the biopolymer comprises the following steps:
step 1) preparing solidified persimmon tannin powder, weighing persimmon tannin and chitosan according to the mass ratio of 1:1-3, dissolving the persimmon tannin and the chitosan in water, uniformly stirring, reacting for 1-2 h, washing and filtering a product, then dropwise adding glutaraldehyde solution into the product according to the mass ratio of 1:1-5 of glutaraldehyde to persimmon tannin, uniformly stirring, reacting for 1-2 h, adjusting the pH value to 6-8, reacting for 2-3h in a water bath at 60-90 ℃, filtering, drying, crushing and grinding to obtain the solidified persimmon tannin powder;
step 2) preparation of precursor, namely solidifying persimmon tannin powder and Co (NO)3)2Mixing with water at a mass ratio of 1:2:50, adding the solidified persimmon tannin powder obtained in step 1) into Co (NO)3)2Reacting the mixed solution for 1 to 2 hours, filtering, washing and drying to obtain a product which is used as a precursor for preparing the three-dimensional graphene;
and 3) preparing the three-dimensional graphene, namely heating the precursor obtained in the step 2) to 600-plus-one-temperature 900 ℃ at a heating rate of 5 ℃/min under the condition of nitrogen, calcining, then preserving heat for 2-3h, washing and refluxing for 1-2 h by adopting concentrated nitric acid at the temperature of 100-plus-one-temperature 120 ℃, and filtering, drying and washing to obtain the three-dimensional graphene.
The three-dimensional graphene obtained by the invention is detected by experiments, and the result is as follows:
the scanning electron microscope test result of the three-dimensional graphene can show that the obtained graphene is in a three-dimensional mesh structure.
The transmission electron microscope test result of the three-dimensional graphene shows that the prepared carbon material shows a unique fold structure of the graphene.
N of three-dimensional graphene2The specific surface area of the adsorption isotherm result is 315 m2/g。
Compared with the prior art, the three-dimensional graphene material disclosed by the invention has the following advantages:
1. the invention adopts the solidified persimmon tannin as the precursor, and has mild reaction condition and environmental protection;
2. the three-dimensional graphene is synthesized by a one-step carbonization method without intermediate steps;
3. the three-dimensional graphene material is simple in preparation method and process, stable in product performance, suitable for large-batch preparation, and simple in post-treatment process.
Therefore, the invention has wide application prospect in the field of carbon functional materials.
Description of the drawings:
fig. 1 is a scanning electron microscope image of three-dimensional graphene prepared according to an embodiment of the present invention;
fig. 2 is a transmission electron microscope image of the three-dimensional graphene prepared in the embodiment of the present invention.
FIG. 3 shows N of three-dimensional graphene prepared according to an embodiment of the present invention2Adsorption isotherm plot.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings, which are given by way of examples, but are not intended to limit the present invention.
Examples
A preparation method of a three-dimensional graphene material based on a biopolymer comprises the following steps:
step 1) preparation of solidified persimmon tannin powder, weighing 1g of persimmon tannin and 1g of chitosan, dissolving the persimmon tannin and the chitosan into 50mL of water, reacting for 2 hours, washing and filtering a product, dissolving 1g of glutaraldehyde into 50mL of water, dropwise adding the glutaraldehyde into the product, stirring uniformly, reacting for 1 hour, adjusting the pH to 6, carrying out water bath reaction for 2 hours at 70 ℃, filtering, drying, crushing and grinding to obtain solidified persimmon tannin powder;
step 2) preparation of precursor, dissolving 1g of the solidified persimmon tannin powder obtained in step 1) in a solution containing 2 g of Co (NO)3)2Reacting the solution for 2 hours in 50mL of water, and filtering, washing and drying to obtain a precursor for preparing the three-dimensional graphene;
and 3) preparing the three-dimensional graphene, namely putting the precursor obtained in the step 2) into a tube furnace, heating to 800 ℃ at a heating rate of 5 ℃/min under the condition of nitrogen, calcining, then preserving heat for 2h to obtain a Co-doped three-dimensional graphene material, and then carrying out reflux treatment on the prepared Co-doped three-dimensional graphene material for 1h at 100 ℃ by adopting concentrated nitric acid to obtain the three-dimensional graphene.
A scanning electron microscope of the three-dimensional graphene is shown in fig. 1, and it can be seen that the obtained graphene is a three-dimensional network structure.
The transmission electron microscope of the three-dimensional graphene is shown in fig. 2, and it can be seen that the prepared carbon material shows a unique fold structure of graphene.
N of three-dimensional graphene2The adsorption isotherm is shown in FIG. 3, and the specific surface area thereof may beUp to 315 m2/g。
Claims (6)
1. A three-dimensional graphene based on a biopolymer, characterized in that: after absorbing Co ions by the biopolymer, carbonizing at high temperature, and washing by concentrated nitric acid to obtain the material with the specific surface area of 300-400 m2(ii)/g; the biopolymer is solidified persimmon tannin prepared from persimmon tannin and chitosan; co ions are used as a catalyst, and the catalyst is prepared by a one-step carbonization method.
2. The method for preparing biopolymer based three-dimensional graphene according to claim 1, characterized by comprising the steps of:
step 1) preparation of solidified persimmon tannin powder, weighing persimmon tannin and chitosan according to a certain mass ratio, dissolving in water, and reacting under certain conditions to obtain solidified persimmon tannin powder;
the reaction condition of the step 1) is that the persimmon tannin and chitosan are uniformly stirred and react for 1-2 hours, then the product is washed and filtered, then glutaraldehyde solution is dropwise added into the product according to the mass ratio of 1:1-5 of glutaraldehyde to persimmon tannin, after uniform stirring and reaction for 1-2 hours, the pH is adjusted to 6-8, water bath reaction is carried out for 2-3 hours at the temperature of 60-90 ℃, and then filtering, drying, crushing and grinding are carried out to obtain solidified persimmon tannin powder;
step 2) preparation of precursor, namely adding the solidified persimmon tannin powder obtained in the step 1) into Co (NO) according to a certain mass ratio3)2Reacting the mixed solution for 1 to 2 hours, filtering, washing and drying to obtain a product which is used as a precursor for preparing the three-dimensional graphene;
and 3) preparing the three-dimensional graphene, namely calcining the precursor obtained in the step 2) under a certain condition, washing and refluxing the calcined precursor by using concentrated nitric acid, and filtering, drying and washing the calcined precursor to obtain the three-dimensional graphene.
3. The method of claim 2, wherein: the mass ratio of the persimmon tannin to the chitosan in the step 1) is 1: 1-3.
4. The method of claim 2, wherein: the step 2) solidifying the persimmon tannin powder and Co (NO)3)2The mass ratio of the water to the water is 1:2: 50.
5. The method of claim 2, wherein: the calcining condition in the step 3) is that the temperature is raised to 600-900 ℃ at the heating rate of 5 ℃/min under the condition of nitrogen, and then the temperature is kept for 2-3 h.
6. The method of claim 2, wherein: the temperature of the washing reflux treatment by the concentrated nitric acid in the step 3) is 100-120 ℃, and the time is 1-2 h.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103922328A (en) * | 2014-04-18 | 2014-07-16 | 山东大学 | Method for preparing nitrogenous hierarchical pore three-dimensional graphene by using chitosan |
| CN104009242A (en) * | 2014-04-30 | 2014-08-27 | 安徽大学 | Preparation method of metal/metal oxide loaded nitrogen-doped porous carbon network-structure material |
| CN104891483A (en) * | 2015-06-03 | 2015-09-09 | 常州大学 | Preparation method of three-dimensional graphene |
| CN105152280A (en) * | 2015-09-10 | 2015-12-16 | 上海大学 | Preparation method of three-dimensional graphene-based membrane capacitive deionization electrode |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103922328A (en) * | 2014-04-18 | 2014-07-16 | 山东大学 | Method for preparing nitrogenous hierarchical pore three-dimensional graphene by using chitosan |
| CN104009242A (en) * | 2014-04-30 | 2014-08-27 | 安徽大学 | Preparation method of metal/metal oxide loaded nitrogen-doped porous carbon network-structure material |
| CN104891483A (en) * | 2015-06-03 | 2015-09-09 | 常州大学 | Preparation method of three-dimensional graphene |
| CN105152280A (en) * | 2015-09-10 | 2015-12-16 | 上海大学 | Preparation method of three-dimensional graphene-based membrane capacitive deionization electrode |
Non-Patent Citations (1)
| Title |
|---|
| Pore structure and electrochemical performances of tannin-based carbon cryogels;G. Amaral-Labat等;《BIOMASS AND BIOENERGY》;20120131;第39卷;摘要、实验部分 * |
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