CN107804836A

CN107804836A - It is prepared by a kind of three-dimensional grapheme and its one-step method based on biopolymer

Info

Publication number: CN107804836A
Application number: CN201711081630.6A
Authority: CN
Inventors: 向翠丽; 刘尹; 邹勇进; 孙立贤; 徐芬
Original assignee: Guilin University of Electronic Technology
Current assignee: Guilin University of Electronic Technology
Priority date: 2017-11-07
Filing date: 2017-11-07
Publication date: 2018-03-16
Anticipated expiration: 2037-11-07
Also published as: CN107804836B

Abstract

The invention discloses a kind of three-dimensional grapheme based on biopolymer, after having adsorbed Co ions by biopolymer, then after carrying out high temperature cabonization, obtained after concentrated nitric acid washs, its specific surface area is 300 400 m²/ g, the solidification persimmon tannin that described biopolymer is prepared by persimmon tannin and chitosan, prepared using Co ions as catalyst, one step carbonization.Its preparation method comprises the following steps：1）Solidify the preparation of persimmon tannin powder；2）The preparation of presoma；3）The preparation of three-dimensional grapheme.The present invention uses one step carbonization, and technique is simple, and properties of product are stable, is adapted to large batch of preparation, and aftertreatment technology is simple, is had broad application prospects in carbon field of functional materials.

Description

It is prepared by a kind of three-dimensional grapheme and its one-step method based on biopolymer

Technical field

The present invention relates to the preparing technical field of porous carbon materials, and in particular to a kind of three-dimensional based on biopolymer Graphene and preparation method thereof.

Background technology

Graphene is the two-dimensional material of the carbon to receive much concern in recent years, has many excellent specific properties, such as high conductivity, high ratio Surface area, high-termal conductivity and excellent mechanical performance, therefore have good application prospect in many fields.But due to graphite Strong attraction between alkene lamella, the graphene of solid-state is caused to lose the high ratio that single dispersing graphene has due to aggregation The excellent properties such as surface area.Three-dimensional honeycomb shape skeleton structure will be joined together to form per piece of graphite alkene, solid-state can be made Graphene shows the excellent properties similar to monolithic graphite alkene, effectively solves this problem.

Three-dimensional graphene foam is prepared by masterplate of nickel foam, and graphene sheet layer grows and connected in nickel surface For an entirety, therefore inherit the three dimensional skeletal structure that nickel foam is isotropic, porous.Three-dimensional grapheme can also use Prepared by sol-gel process, first pass through the processes such as hydro-thermal and graphene oxide is cross-linked to form into hydrogel, then by being freeze-dried or surpassing The critical dry moisture that removes generates aeroge.These three-dimensional grapheme material structures and property have differences, but they are owned by The common characteristic such as high-specific surface area and porosity, low-density, high conductivity.But these preparation methods are complicated, and time-consuming, and Cost is higher, and after first preparing graphene, could further obtain three-dimensional grapheme.

If can realize that a step prepares three-dimensional grapheme, production cost can be effectively reduced.

The content of the invention

It is an object of the invention to provide a kind of three-dimensional grapheme based on biopolymer and preparation method thereof.

It is presoma using the solidification persimmon tannins of Co ions has been adsorbed, when being carbonized at high temperature, Co presence is urged This reaction is changed, has obtained the three-dimensional grapheme material of Co doping, then washing away cobalt element using nitric acid backflow obtains three-dimensional Graphene.

Realize without under conditions of formerly preparing graphene, directly obtaining three-dimensional grapheme material.

In order to realize foregoing invention purpose, the technical solution adopted by the present invention is：

A kind of three-dimensional grapheme based on biopolymer, after having adsorbed Co ions by biopolymer, then carry out high temperature cabonization Afterwards, obtained after concentrated nitric acid washs, its specific surface area is 300-400 m²/ g, described biopolymer is by persimmon tannin and shell Solidification persimmon tannin prepared by glycan, prepared using Co ions as catalyst, one step carbonization.

The preparation method of three-dimensional grapheme based on biopolymer comprises the following steps：

Step 1）Solidify the preparation of persimmon tannin powder, be 1 by the mass ratio of persimmon tannin and chitosan:1-3, weigh persimmon list Rather it is dissolved in chitosan in water, stirs after reaction 1-2 h, product is washed, filtered, then with glutaraldehyde and persimmon list Peaceful mass ratio is 1:Glutaraldehyde solution is added dropwise in product by 1-5, after the reaction 1-2 h that stir, then adjusts pH to 6- 8, the water-bath 2-3h at 60-90 DEG C, then filter, dry, crushing, grinding, obtaining solidifying persimmon tannin powder；

Step 2）The preparation of presoma, by solidification persimmon tannin powder, Co (NO₃)₂Mass ratio with water is 1:2:50, by step 1）Solidification persimmon tannin powder add Co (NO₃)₂Mixed solution in react 1-2 h after, filtering, washing, dry, produced Thing, as the presoma for preparing three-dimensional grapheme；

Step 3）The preparation of three-dimensional grapheme, by step 2）Obtained presoma under a nitrogen atmosphere, with 5 DEG C of heating rate/ Min, 2-3h is incubated after being warming up to 600-900 DEG C of calcining, then using concentrated nitric acid under the conditions of 100-120 DEG C, washed at backflow 1-2 h are managed, filtering, dries, obtain three-dimensional grapheme after washing.

Gained three-dimensional grapheme through experimental tests of the invention are as a result as follows：

The sem test result of three-dimensional grapheme can be seen that the graphene of gained is 3 D stereo network structure.

It is peculiar to show graphene that the transmissioning electric mirror test result of three-dimensional grapheme can be seen that prepared carbon material Pleated structure.

The N of three-dimensional grapheme₂Adsorption isotherm result can be seen that its specific surface area is 315 m²/g。

The three-dimensional grapheme material of the present invention has advantages below for prior art：

1. the present invention is as presoma using solidification persimmon tannin, and reaction condition is gentle, green；

2. three-dimensional grapheme one step carbonization synthesizes, intermediate steps are needed not move through；

3. a three-dimensional grapheme material, preparation method and technique are simple, and properties of product are stable, are adapted to large batch of preparation, and Aftertreatment technology is simple.

Therefore, the present invention has broad application prospects in carbon field of functional materials.

Brief description of the drawings：

Fig. 1 is the scanning electron microscope (SEM) photograph of three-dimensional grapheme prepared by the embodiment of the present invention；

Fig. 2 is the transmission electron microscope picture of three-dimensional grapheme prepared by the embodiment of the present invention.

Fig. 3 is the N of three-dimensional grapheme prepared by the embodiment of the present invention₂Adsorption isotherm line chart.

Embodiment

The present invention is described in further detail, but be not pair by embodiment with reference to Figure of description to present invention The restriction of the present invention.

Embodiment

A kind of three-dimensional grapheme material preparation method based on biopolymer：

Step 1）Solidify the preparation of persimmon tannin powder, weigh 1g persimmon tannins and be dissolved in 1g chitosans in 50 ml water, instead After answering 2 h, product is washed, filtered, be added dropwise to after 1 g glutaraldehydes then are dissolved in into 50 mL water in product, stirring is equal It is even, 1 h is reacted, then pH to 6 is adjusted, the water-bath 2h at 70 DEG C, then filter, dry, crushing, grinding, obtaining solidifying persimmon Chinese tannin powder；

Step 2）The preparation of presoma, by 1 g steps 1）Solidification persimmon tannin powder be dissolved in containing 2 g Co (NO₃)₂'s In 50mL water, solution reaction is then allowed after 2 hours, filtering, washing, is dried, is obtained preparing the presoma of three-dimensional grapheme；

Step 3）The preparation of three-dimensional grapheme, by step 2）Obtained presoma is put into tube furnace, under a nitrogen atmosphere, to rise Warm speed is warming up to 800 DEG C for 5 DEG C/min and calcined, and is then incubated 2h and obtains the three-dimensional grapheme material of Co doping, then Reflow treatment 1h is carried out under the conditions of 100 DEG C to the prepared Co three-dimensional grapheme materials adulterated using concentrated nitric acid, you can To three-dimensional grapheme.

The ESEM of three-dimensional grapheme is as shown in Figure 1, it can be seen that the graphene of gained is 3 D stereo network structure.

The transmission electron microscope of three-dimensional grapheme is as shown in Figure 2, it can be seen that prepared carbon material is special to show graphene Some pleated structures.

The N of three-dimensional grapheme₂Adsorption isotherm is as shown in figure 3, its specific surface area can reach 315 m²/g。

Claims

A kind of 1. three-dimensional grapheme based on biopolymer, it is characterised in that：After Co ions having been adsorbed by biopolymer, then After carrying out high temperature cabonization, obtained after concentrated nitric acid washs, its specific surface area is 300-400 m²/g。
2. the three-dimensional grapheme according to claim 1 based on biopolymer, it is characterised in that：Described biology is high poly- The solidification persimmon tannin that thing is prepared by persimmon tannin and chitosan.
3. the three-dimensional grapheme according to claim 1 based on biopolymer, it is characterised in that：Using Co ion conducts It is prepared by catalyst, one step carbonization.
4. the preparation method of the three-dimensional grapheme based on biopolymer according to claim 1, it is characterised in that including with Lower step：

Step 1）Solidify the preparation of persimmon tannin powder, by certain mass ratio, weigh persimmon tannin and be dissolved in chitosan in water, Reaction under certain condition obtains solidifying persimmon tannin powder；

Step 2）The preparation of presoma, by certain mass ratio, by step 1）Solidification persimmon tannin powder add Co (NO₃)₂It is mixed Close after reacting 1-2 h in solution, filtering, washing, dry, product is obtained, as the presoma for preparing three-dimensional grapheme；

Step 3）The preparation of three-dimensional grapheme, by step 2）Obtained presoma is calcined under certain condition, then using dense nitre Acid elution reflow treatment, filtering, dry, obtain three-dimensional grapheme after washing.
5. preparation method according to claim 4, it is characterised in that：The step 1）The quality of persimmon tannin and chitosan Than for 1:1-3.
6. preparation method according to claim 4, it is characterised in that：The step 1）Reaction condition is persimmon tannin and shell Glycan is stirred after reaction 1-2 h, and product is washed, filtered, then using glutaraldehyde and persimmon tannin mass ratio as 1:1-5 will Glutaraldehyde solution is added dropwise in product, after the reaction 1-2 h that stir, then adjusts pH to 6-8, the water-bath at 60-90 DEG C 2-3h is reacted, then filters, dry, crushing, grinding, obtains solidifying persimmon tannin powder.
7. preparation method according to claim 4, it is characterised in that：The step 2）Solidify persimmon tannin powder, Co (NO₃)₂Mass ratio with water is 1:2:50.
8. preparation method according to claim 4, it is characterised in that：The step 3）The condition of calcining is in condition of nitrogen gas Under, with 5 DEG C/min of heating rate, 2-3h is incubated after being warming up to 600-900 DEG C of calcining.
9. preparation method according to claim 4, it is characterised in that：The step 3）Using concentrated nitric acid washing backflow at The temperature of reason is 100-120 DEG C, and the time is 1-2 h.