CN104843677B - porous graphene and preparation method thereof - Google Patents

porous graphene and preparation method thereof Download PDF

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Publication number
CN104843677B
CN104843677B CN201510150669.3A CN201510150669A CN104843677B CN 104843677 B CN104843677 B CN 104843677B CN 201510150669 A CN201510150669 A CN 201510150669A CN 104843677 B CN104843677 B CN 104843677B
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China
Prior art keywords
shitosan
acetic acid
aqueous acetic
ultrasonically treated
porous graphene
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CN201510150669.3A
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Chinese (zh)
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CN104843677A (en
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王小英
李晓云
孙润仓
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华南理工大学
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Priority claimed from US15/563,406 external-priority patent/US10005957B2/en
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Abstract

The invention discloses a kind of porous graphene and preparation method thereof.Methods described is:By in the aqueous acetic acid of graphite raw material addition shitosan, using shitosan as remover, by ultrasonically treated, centrifugal purification, the grapheme material with loose structure is prepared for.The grapheme material not only has loose structure, and the number of plies is less, and lamella lateral dimension is larger.Compared with prior art, ultrasonically treated due to only having been used in the present invention, preparation method is simple and easy to apply;Due to using graphite as raw material, the porous graphene material degree of graphitization of preparation is high.The porous graphene material has huge application value in fields such as absorption, catalysis, gas separation and ultracapacitors.

Description

Porous graphene and preparation method thereof

Technical field

The invention belongs to grapheme material technical field, and in particular to a kind of porous graphene and preparation method thereof.

Background technology

The nanoscale graphite material that grapheme material is made up of mono-layer graphite, porous graphene is the lamella in Graphene In some are manufactured by the method for physics or chemistry there is the hole of nano-scale, loose structure cause Graphene the energy, Catalysis or sorbing material aspect have very big advantage.

The current preparation on the grapheme material with loose structure mainly has following methods:(1) by the graphite of multilayer Alkene carries out hydro-thermal reaction with surfactant in strong alkali aqueous solution, but this method is added in stone due to surfactant Many functional groups are introduced in black alkene lamella;(2) carbon materials such as Graphene and transition metal are heated simultaneously and obtains porous stone Black alkene, but this method has used expensive transition metal;(3) chemical deposition obtains graphene sheet layer, Ran Houtong Over etching formation porous graphene, but this method complex process, it is relatively costly;(4) graphite is mixed with nano-metal particle After conjunction, dissolved by acid treatment and obtain porous graphene material, because the introducing of nano metal improves the cost of reaction.

The content of the invention

It is an object of the invention to overcome deficiencies of the prior art, there is provided porous graphene and its preparation side Method.The present invention adds graphite raw material in the aqueous acetic acid of shitosan, using shitosan as remover, by ultrasonically treated, Centrifugal purification, is prepared for the grapheme material with loose structure.

The purpose of the present invention is realized at least through one of following technical scheme.

A kind of porous graphene, its graphene sheet layer thickness is 0.5~2 nanometer, 1~30 micron of lateral dimension;Graphene Surface holes are uniformly distributed, and aperture is 10 nanometers~500 nanometers.

The method for preparing a kind of above-mentioned porous graphene, step is as follows:A certain amount of shitosan is dissolved in acetic acid water-soluble In liquid, the aqueous acetic acid of shitosan is obtained;Graphite is added in the aqueous acetic acid of shitosan, stirring must be mixed to well mixed Close liquid;Mixed liquor is put into ultrasonic cleaning machine, is carried out ultrasonically treated;By the mixed liquor after above-mentioned ultrasound by centrifugal purification, Obtain the grapheme material with loose structure;The ultrasonically treated temperature is 10~75 DEG C;Ultrasonically treated power is 420 ~600W.

Further optimally, the shitosan and the mass ratio of the graphite are 1:10~10:1.

Further optimally, the weight average molecular weight of the shitosan is 5.0 × 103~1.0 × 106

Further optimally, the deacetylation of the shitosan is 40%~95%.

Further optimally, the volumetric concentration of the aqueous acetic acid is 0.5%~4%.

Further optimally, the mass concentration of the aqueous acetic acid of the shitosan is 0.1~0.5mg/mL.

Further optimally, the ultrasonically treated time is 0.5~24 hour.

Further optimally, the mixed liquor is centrifuged 5~10 minutes by 1000~2000rpm.

Further optimally, the product after centrifugation reuses the aqueous acetic acid that volumetric concentration is 0.5%~4% and carries out 15000~20000rpm eccentric cleanings, the time of eccentric cleaning is 1.5~3 hours.

Compared with prior art, the present invention has advantages below:

Preparation method of the present invention is simple and easy to apply, and raw material is easy to get.By present invention uses work that is ultrasonically treated and being limited Skill parameter, makes obtained porous graphene material degree of graphitization high, and the thickness of lamella is 0.5~2 nanometer, lamella lateral dimension compared with Greatly, 1~30 micron, a diameter of 10~500 nanometers of lamella hole.The grapheme material not only has loose structure, and the number of plies Less, lamella lateral dimension is larger.The method is simple and easy to apply, and cost is relatively low.

Brief description of the drawings

The porous stone that Fig. 1 a~Fig. 1 d are respectively by ultrasonically treated 0.5 hour, 8 hours, 16 hours and obtain for 24 hours The AFM data of black alkene;

Fig. 1 e are the AFM data and its height of the big size porous Graphene for obtaining for ultrasonically treated 8 hours Figure;

Fig. 2 a, Fig. 2 b are respectively the x-ray photoelectron power spectrum of graphite and porous graphene of the invention.

Specific embodiment

Below in conjunction with the drawings and specific embodiments, the invention will be further described, but implementation of the invention and protection are not It is limited to this, is that those skilled in the art can refer to prior art realization if having not describing part in detail especially below.

Embodiment 1:

Dose volume concentration is 0.5% aqueous acetic acid, is 5.0 × 10 by weight average molecular weight3, deacetylation is 40% Shitosan be dissolved in aqueous acetic acid, be obtained mass concentration for 0.1mg/mL chitosan solution, stir;

Graphite is added in above-mentioned chitosan solution, it is 1 with the mass ratio of graphite to control shitosan:10;

Above-mentioned mixed liquor is put into ultrasonic cleaning machine carry out it is ultrasonically treated, temperature be 75 DEG C, the time be 0.5 hour, surpass The power of sound is 600W.

Solution after above-mentioned ultrasound is carried out after 1000rpm is centrifuged centrifugation in 10 minutes using above-mentioned aqueous acetic acid 15000rpm eccentric cleanings, the time of centrifugation is 0.5 hour.

Embodiment 2:

Dose volume concentration is 2% aqueous acetic acid, is 2.0 × 10 by weight average molecular weight4, deacetylation is 53% Shitosan is dissolved in aqueous acetic acid, and it is the chitosan solution of 0.2mg/mL that mass concentration is obtained, and is stirred;

Graphite is added in above-mentioned chitosan solution, it is 1 with the mass ratio of graphite to control shitosan:5;

Above-mentioned mixed liquor is put into ultrasonic cleaning machine carry out it is ultrasonically treated, temperature be 60 DEG C, the time be 2 hours, ultrasound Power be 540W.

Solution after above-mentioned ultrasound is carried out after 2000rpm is centrifuged centrifugation in 10 minutes using above-mentioned aqueous acetic acid 20000rpm eccentric cleanings, the time of centrifugation is 1 hour.

Embodiment 3:

Dose volume concentration is 4% aqueous acetic acid, is 1.5 × 10 by weight average molecular weight5, deacetylation is 60% Shitosan is dissolved in aqueous acetic acid, and it is the chitosan solution of 0.5mg/mL that mass concentration is obtained, and is stirred;

Graphite is added in above-mentioned chitosan solution, it is 1 with the mass ratio of graphite to control shitosan:1;

Above-mentioned mixed liquor is put into ultrasonic cleaning machine carry out it is ultrasonically treated, temperature be 30 DEG C, the time be 8 hours, ultrasound Power be 480W.

Solution after above-mentioned ultrasound is carried out after 2000rpm is centrifuged centrifugation in 5 minutes using above-mentioned aqueous acetic acid 16000rpm eccentric cleanings, the time of centrifugation is 1.5 hours.

Embodiment 4:

Dose volume concentration is 0.5% aqueous acetic acid, is 4.5 × 10 by weight average molecular weight5, deacetylation is 80% Shitosan be dissolved in aqueous acetic acid, be obtained mass concentration for 0.2mg/mL chitosan solution, stir;

Graphite is added in above-mentioned chitosan solution, it is 5 with the mass ratio of graphite to control shitosan:1;

Above-mentioned mixed liquor is put into ultrasonic cleaning machine carry out it is ultrasonically treated, temperature be 10 DEG C, the time be 16 hours, ultrasound Power be 420W.

Solution after above-mentioned ultrasound is carried out after 1000rpm is centrifuged centrifugation in 10 minutes using above-mentioned aqueous acetic acid 18000rpm eccentric cleanings, the time of centrifugation is 2 hours.

Embodiment 5:

Dose volume concentration is 0.5% aqueous acetic acid, is 1.0 × 10 by weight average molecular weight6, deacetylation is 95% Shitosan be dissolved in aqueous acetic acid, be obtained mass concentration for 0.2mg/mL chitosan solution, stir;

Graphite is added in above-mentioned chitosan solution, it is 10 with the mass ratio of graphite to control shitosan:1;

Above-mentioned mixed liquor is put into ultrasonic cleaning machine carry out it is ultrasonically treated, temperature be 30 DEG C, the time be 24 hours, ultrasound Power be 600W.

Solution after above-mentioned ultrasound is carried out after 2000rpm is centrifuged centrifugation in 10 minutes using above-mentioned aqueous acetic acid 15000rpm eccentric cleanings, the time of centrifugation is 3 hours.

Fig. 1 a~Fig. 1 d give the change of the size of the pore structure with the change Graphene of ultrasonic time.Contrast hair Existing, with the extension of ultrasonic time, pore structure becomes big from small, and size is from 10 nanometers to 500 nanometers.Fig. 1 e are ultrasonically treated 8 small When the AFM data and its height map of big size porous Graphene that obtain, graphene sheet layer thickness is 0.9 nanometer, Lateral dimension has reached 30 microns.

Fig. 2 a, Fig. 2 b give the x-ray photoelectron power spectrum of porous graphene, it is recognised that prepared by the present invention from figure The grapheme material with loose structure oxygen-containing functional group it is less, degree of graphitization is high.

Claims (3)

1. the method for preparing porous graphene, the porous graphene lamellar spacing is 0.5~2 nanometer, and lateral dimension 1~30 is micro- Rice;Graphenic surface hole is uniformly distributed, and aperture is 10 nanometers~500 nanometers;It is characterized in that preparation process is as follows:Will be a certain amount of Shitosan be dissolved in aqueous acetic acid, obtain the aqueous acetic acid of shitosan;Added in the aqueous acetic acid of shitosan Graphite, stirs to well mixed to obtain mixed liquor;Mixed liquor is put into ultrasonic cleaning machine, is carried out ultrasonically treated;By above-mentioned ultrasound Mixed liquor afterwards obtains the grapheme material with loose structure by centrifugal purification;The ultrasonically treated temperature is 10 ~ 75 ℃;Ultrasonically treated power is 420 ~ 600W;The shitosan is 1 with the mass ratio of the graphite:10~10:1;The shell gathers The weight average molecular weight of sugar is 5.0 × 103~1.0×106;The deacetylation of the shitosan is 40% ~ 95%;The aqueous acetic acid Volumetric concentration be 0.5% ~ 4%;The mass concentration of the aqueous acetic acid of the shitosan is 0.1 ~ 0.5mg/mL;Ultrasonically treated Time is 0.5 ~ 24 hour.
2. preparation method according to claim 1, it is characterised in that the mixed liquor is centrifuged 5 by 1000 ~ 2000 rpm ~ 10 minutes.
3. preparation method according to claim 1, it is characterised in that it is 0.5% that the product after centrifugation reuses volumetric concentration ~ 4% aqueous acetic acid carries out 15000 ~ 20000 rpm eccentric cleanings, and the time of eccentric cleaning is 1.5 ~ 3 hours.
CN201510150669.3A 2015-03-31 2015-03-31 porous graphene and preparation method thereof CN104843677B (en)

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US15/563,406 US10005957B2 (en) 2015-03-31 2015-12-31 Porous graphene, graphene quantum dot and green preparation method for porous graphene and graphene quantum dot
PCT/CN2015/100021 WO2016155396A1 (en) 2015-03-31 2015-12-31 Porous graphene, graphene quantum dot, and green manufacturing method therefor

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US10005957B2 (en) 2015-03-31 2018-06-26 South China University Of Technology Porous graphene, graphene quantum dot and green preparation method for porous graphene and graphene quantum dot
CN105502352A (en) * 2015-12-11 2016-04-20 华南理工大学 Porous graphene, graphene quantum dot and green preparation method of porous graphene and graphene quantum dot
CN105523549B (en) * 2016-01-28 2017-10-27 成都新柯力化工科技有限公司 A kind of remover and application that graphene is prepared for mechanical stripping method
US10160653B2 (en) 2016-05-31 2018-12-25 City University Of Hong Kong Method of producing graphene-based materials, obtainable materials and their use

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CN103738957A (en) * 2014-01-17 2014-04-23 上海交通大学 Graphene surface pore-forming method
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WO2014154911A1 (en) * 2012-11-21 2014-10-02 Abengoa Solar New Technologies, S.A. Method for obtaining solid graphene samples or suspensions
CN103738957A (en) * 2014-01-17 2014-04-23 上海交通大学 Graphene surface pore-forming method

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