CN103496696A - Method for preparing reduction-state graphene - Google Patents
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- CN103496696A CN103496696A CN201310483115.6A CN201310483115A CN103496696A CN 103496696 A CN103496696 A CN 103496696A CN 201310483115 A CN201310483115 A CN 201310483115A CN 103496696 A CN103496696 A CN 103496696A
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Abstract
The invention discloses a method for preparing reduction-state graphene. The method includes the steps: 1), preparing graphene oxide solution and detecting a pH value of the same; 2), adjusting the pH value of the graphene oxide solution to be less than 5; 3), adopting an ultraviolet analyzer to irradiate the graphene oxide solution preformed in the step 2) till reduction reaction is complete. The method is simple in operation, short in time, high in efficiency, free of introduction of toxic and corrosive reductant, environmentally friendly, free of heating during preparation and low in cost.
Description
Technical field
The present invention relates to a kind of preparation method of reduction state graphene, relate in particular to a kind of method of utilizing UV-irradiation to prepare reduction state graphene.
Background technology
Graphene be a kind of by carbon atom with sp
2hybridized orbital forms the flat film that hexangle type is the honeycomb lattice, only has the two-dimensional material of a carbon atom thickness.It is from graphite to separate [Novoselov in 2004 by the mechanically peel method by Britain graceful Chester College Physics scholar An Deliehaimu and Constantine Nuo Woxiaoluofu at first, K.S., Geim, A.K., Morozov, S.V., et al.Electric field effect in atomically thin carbon films[J] .Science, 2004,306,666-669.].Graphene has the performance of a lot of excellences, good etc. such as high surface area, low-resistivity, high conductivity, with low cost and processability.So the research work relevant with Graphene become the current study hotspot of related discipline.
The development of Graphene technology of preparing, for the fundamental research based on Graphene and application and development provide the raw material assurance.The method for preparing at present Graphene has: [the Wu such as micromechanics is peeled off, epitaxy, graphite oxide reduction, chemical vapour deposition and organic synthesis, J., Pisula, W., M ü llen, K., Graphenes as potential material for electronics[J] .Chemical Reviews, 2007,107,718-747.].It is a kind of method that simply prepares high-quality graphene that micromechanics is peeled off, but it waste time and energy, be difficult to accurate control, repeatability is poor, and has that productive rate is low, high in cost of production is not enough, is not suitable for the requirement of industrialization and large-scale production and application.Chemical Vapor deposition process can meet the requirement that mass-producing prepares high-quality graphene, can prepare the Graphene that area is larger, but the conditional request harshness, technique is more complicated, and cost is higher.At present, the cost that the graphite oxide reduction method is cheap with it and easily realize that the advantage of mass-producing becomes the best approach for preparing Graphene, and can prepare stable graphene suspension, solve Graphene and be difficult for the problem of disperseing.
The most frequently used method of reducing of graphite oxide reduction method has chemical reduction method, hot reducing method etc. at present.In chemical reduction method, reductive agent commonly used has hydrazine hydrate, sodium borohydride etc.Its shortcoming is easily to bring waste liquor contamination, and has used in reduction process and have very malicious and chemical reagent severe corrosive.[Ding, Y.H., the Zhang such as Ding, P., Zhuo, Q., et al.A green approach to the synthesis of reduced graphene oxide nanosheets under UV irradiation[J] .Nanotechnology, 2011,22,215601.] utilize the ultraviolet lighting reduced graphene, the method is simply environment friendly and pollution-free, but the time for preparing the reduction state graphene cost is longer, reaches 48 hours.
Because the defect that above-mentioned existing reduction state graphene technology of preparing exists, the inventor is based on being engaged in this type of product design manufacture abundant practical experience and expertise for many years, and the utilization of cooperation scientific principle, positive research and innovation in addition, to founding a kind of novel method for preparing reduction state graphene, make it have more practicality.Through constantly research, design, and, after repeatedly studying sample and improving, finally create the present invention who has practical value.
Summary of the invention
Main purpose of the present invention is, overcome the defect that existing reduction state graphene technology of preparing exists, and a kind of novel method for preparing reduction state graphene is provided, shorten the preparation time of reduction state graphene, thereby more be suitable for practicality, and there is the utility value on industry.
The object of the invention to solve the technical problems realizes by the following technical solutions.The method for preparing reduction state graphene proposed according to the present invention, described preparation method comprises the steps,
1) prepare the graphite oxide aqueous solution, and test the pH value of described graphite oxide aqueous solution;
2) the pH value of adjusting graphite oxide aqueous solution<5;
3) adopt uv analyzer to irradiate described step 2) the graphite oxide aqueous solution for preparing, until reduction reaction is complete.
The aforesaid method for preparing reduction state graphene, described step 2) regulate the pH value of graphite oxide aqueous solution by adding inorganic acid.
The aforesaid method for preparing reduction state graphene, described step 3) medium ultraviolet analyser irradiates and adopts the UV-light of 254nm or 365nm long.
The aforesaid method for preparing reduction state graphene, described step 3) is 3～6cm apart from the graphite oxide aqueous solution while adopting uv analyzer to irradiate.
The aforesaid method for preparing reduction state graphene, described step 2) pH of graphite oxide aqueous solution is preferably 2～3.
The aforesaid method for preparing reduction state graphene, described inorganic acid is H
2sO
4, HCl or H
3pO
4.
By technique scheme, the method that the present invention prepares reduction state graphene at least has following advantages: present method is to utilize UV-irradiation graphite oxide aqueous solution to produce the very strong hydrated electron of reductibility, thus reduced graphene.Adopt method of the present invention to prepare reduction state graphene, the preparation method is simple to operate, time is short, efficiency is high, compared with prior art, and time shorten 1/3rd left and right, can not introduce poisonous and mordant reductive agent in preparation process, environmental friendliness, and preparation process do not need the heating, cost is lower.
Above-mentioned explanation is only the general introduction of technical solution of the present invention, in order to better understand technique means of the present invention, and can be implemented according to the content of specification sheets, below with preferred embodiment of the present invention, is described in detail as follows.
The accompanying drawing explanation
Fig. 1 is the Method And Principle schematic diagram that the present invention prepares reduction state graphene;
(230nm is the π-π of aromatic C=C key to the uv-visible absorption spectra that Fig. 2 is the graphite oxide aqueous solution
*absorb, 300nm is the n-π of C=O key
*absorption);
The uv-visible absorption spectra that Fig. 3 is reduction state graphene (peak of 230nm moves to 260nm, and the peak of 300nm disappears simultaneously).
Embodiment
Reach for further setting forth the present invention technique means and the effect that predetermined goal of the invention is taked, its embodiment of the method for preparing reduction state graphene, feature and effect thereof that foundation the present invention is proposed, be described in detail as follows.
Embodiment 1
1) adopt the hummers method to prepare the graphite oxide aqueous solution, concrete technical process is: assemble the reaction flask of 250mL in ice-water bath, add 46mL H
2sO
4, the solid mixture that adds 2g Graphite Powder 99 and 1g SODIUMNITRATE under stirring, gradation adds 6g potassium permanganate again, control temperature of reaction and be no more than 20 ℃, stirring reaction for some time, then be warmed up to 35 ℃ of left and right, continue to stir 30min, slowly add again the deionized water of 92mL, after continuing to stir 20min, add the hydrogen peroxide of 80mL3% to reduce residual oxygenant, make solution become glassy yellow, then above-mentioned solution centrifuge washing repeatedly, first centrifugal with 8000 rotating speeds that turn, take off a layer residue, then with the 3000 rotating speed centrifuging and taking supernatant liquids that turn, obtain the graphite oxide aqueous solution.And to measure the graphene oxide pH value of water solution be 5.7, concentration is 1mg/mL, and the uv-visible absorption spectra of graphite oxide aqueous solution as shown in Figure 2;
2) by adding H
2sO
4, the pH that regulates the graphite oxide aqueous solution is 0;
3) pipette the graphite oxide aqueous solution of 3mL in the vial of 5mL, adopt ZF-20D dark box type uv analyzer, regulate the long 254nm of UV-light, during irradiation, the distance of vial and ultraviolet lamp is about 5cm, until reduction reaction completes, whole reduction process needs to complete in 40 hours, and the uv-visible absorption spectra of reduction state graphene as shown in Figure 3.
Embodiment 2
1) adopt the hummers method to prepare the graphite oxide aqueous solution, concrete technical process is: assemble the reaction flask of 250mL in ice-water bath, add 46mL H
2sO
4the solid mixture that adds 2g Graphite Powder 99 and 1g SODIUMNITRATE under stirring, gradation adds 6g potassium permanganate again, controls temperature of reaction and is no more than 20 ℃, stirring reaction for some time, then be warmed up to 35 ℃ of left and right, continue to stir 30min, more slowly add the deionized water of 92mL, after continuing to stir 20min, add the hydrogen peroxide of 80mL3% to reduce residual oxygenant, make solution become glassy yellow.Then above-mentioned solution centrifuge washing repeatedly, first centrifugal with 8000 rotating speeds that turn, take off a layer residue, then with the 3000 rotating speed centrifuging and taking supernatant liquids that turn, obtain the graphite oxide aqueous solution.And to measure the graphene oxide pH value of water solution be 5.7, concentration is 1mg/mL;
2), by adding HCl, the pH that regulates the graphite oxide aqueous solution is 1;
3) pipette the graphite oxide aqueous solution of 3mL in the vial of 5mL, adopt ZF-20D dark box type uv analyzer, regulate the long 254nm of UV-light, during irradiation, the distance of vial and ultraviolet lamp is about 5cm, until reduction reaction completes, whole reduction process needs to complete in 37 hours.
Embodiment 3
1) adopt the hummers method to prepare the graphite oxide aqueous solution, concrete technical process is: assemble the reaction flask of 250mL in ice-water bath, add 46mL H
2sO
4the solid mixture that adds 2g Graphite Powder 99 and 1g SODIUMNITRATE under stirring, gradation adds 6g potassium permanganate again, controls temperature of reaction and is no more than 20 ℃, stirring reaction for some time, then be warmed up to 35 ℃ of left and right, continue to stir 30min, more slowly add the deionized water of 92mL, after continuing to stir 20min, add the hydrogen peroxide of 80mL3% to reduce residual oxygenant, make solution become glassy yellow.Then above-mentioned solution centrifuge washing repeatedly, first centrifugal with 8000 rotating speeds that turn, take off a layer residue, then with the 3000 rotating speed centrifuging and taking supernatant liquids that turn, obtain the graphite oxide aqueous solution.And to measure the graphene oxide pH value of water solution be 5.7, concentration is 1mg/mL;
2) by adding H
3pO
4, the pH that regulates the graphite oxide aqueous solution is 2;
3) pipette the graphite oxide aqueous solution of 3mL in the vial of 5mL, adopt ZF-20D dark box type uv analyzer, regulate the long 254nm of UV-light, during irradiation, the distance of vial and ultraviolet lamp is about 5cm, until reduction reaction completes, whole reduction process needs to complete in 30 hours.
Embodiment 4
1) adopt the hummers method to prepare the graphite oxide aqueous solution, concrete technical process is: assemble the reaction flask of 250mL in ice-water bath, add 46mL H
2sO
4the solid mixture that adds 2g Graphite Powder 99 and 1g SODIUMNITRATE under stirring, gradation adds 6g potassium permanganate again, controls temperature of reaction and is no more than 20 ℃, stirring reaction for some time, then be warmed up to 35 ℃ of left and right, continue to stir 30min, more slowly add the deionized water of 92mL, after continuing to stir 20min, add the hydrogen peroxide of 80mL3% to reduce residual oxygenant, make solution become glassy yellow.Then above-mentioned solution centrifuge washing repeatedly, first centrifugal with 8000 rotating speeds that turn, take off a layer residue, then with the 3000 rotating speed centrifuging and taking supernatant liquids that turn, obtain the graphite oxide aqueous solution.And to measure the graphene oxide pH value of water solution be 5.7, concentration is 1mg/mL;
2) by adding H
2sO
4, the pH that regulates the graphite oxide aqueous solution is 3;
3) pipette the graphite oxide aqueous solution of 3mL in the vial of 5mL, adopt ZF-20D dark box type uv analyzer, regulate the long 254nm of UV-light, during irradiation, the distance of vial and ultraviolet lamp is about 5cm, until reduction reaction completes, whole reduction process needs to complete in 33 hours.
Embodiment 5
1) adopt the hummers method to prepare the graphite oxide aqueous solution, concrete technical process is: assemble the reaction flask of 250mL in ice-water bath, add 46mL H
2sO
4the solid mixture that adds 2g Graphite Powder 99 and 1g SODIUMNITRATE under stirring, gradation adds 6g potassium permanganate again, controls temperature of reaction and is no more than 20 ℃, stirring reaction for some time, then be warmed up to 35 ℃ of left and right, continue to stir 30min, more slowly add the deionized water of 92mL, after continuing to stir 20min, add the hydrogen peroxide of 80mL3% to reduce residual oxygenant, make solution become glassy yellow.Then above-mentioned solution centrifuge washing repeatedly, first centrifugal with 8000 rotating speeds that turn, take off a layer residue, then with the 3000 rotating speed centrifuging and taking supernatant liquids that turn, obtain the graphite oxide aqueous solution.And to measure the graphene oxide pH value of water solution be 5.7, concentration is 1mg/mL;
2) by adding H
3pO
4, the pH that regulates the graphite oxide aqueous solution is 5;
3) pipette the graphite oxide aqueous solution of 3mL in the vial of 5mL, adopt ZF-20D dark box type uv analyzer, regulate the long 254nm of UV-light, during irradiation, the distance of vial and ultraviolet lamp is about 5cm, until reduction reaction completes, whole reduction process needs to complete in 48 hours.
The present invention utilizes the UV-irradiation of 254nm to regulate the graphite oxide aqueous solution of pH value, and the UV-irradiation aqueous solution produces the very strong hydrated electron of reductibility, and then reduced graphene, thereby simply environmental protection prepares reduction state graphene.
The above, it is only preferred embodiment of the present invention, not the present invention is done to any pro forma restriction, although the present invention discloses as above with preferred embodiment, yet not in order to limit the present invention, any those skilled in the art, within not breaking away from the technical solution of the present invention scope, when the technology contents that can utilize above-mentioned announcement is made a little change or is modified to the equivalent embodiment of equivalent variations, in every case be the content that does not break away from technical solution of the present invention, any simple modification of above embodiment being done according to technical spirit of the present invention, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
Claims (6)
1. a method for preparing reduction state graphene is characterized in that: described preparation method comprises the steps,
1) prepare the graphite oxide aqueous solution, and test the pH value of described graphite oxide aqueous solution;
2) the pH value of adjusting graphite oxide aqueous solution<5;
3) adopt uv analyzer to irradiate described step 2) the graphite oxide aqueous solution for preparing, until reduction reaction is complete.
2. the method for preparing reduction state graphene according to claim 1, is characterized in that: described step 2) by adding inorganic acid to regulate the pH value of graphite oxide aqueous solution.
3. the method for preparing reduction state graphene according to claim 1 is characterized in that: described step 3) medium ultraviolet analyser irradiates and adopts the UV-light of 254 nm or 365 nm long.
4. the method for preparing reduction state graphene according to claim 1, is characterized in that: during described step 3) employing uv analyzer irradiation, apart from the graphite oxide aqueous solution, be 3 ~ 6 cm.
5. the method for preparing reduction state graphene according to claim 1, it is characterized in that: described step 2) pH of graphite oxide aqueous solution is preferably 2 ~ 3.
6. the method for preparing reduction state graphene according to claim 2, it is characterized in that: described inorganic acid is H
2sO
4, HCl or H
3pO
4.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104562682A (en) * | 2015-01-16 | 2015-04-29 | 浙江大学 | Wash-wear nonwoven fabric capable of selectively blocking ultraviolet rays |
| CN105833839A (en) * | 2016-06-10 | 2016-08-10 | 苏州巨联环保科研有限公司 | Preparation method of graphene-based adsorption material |
| CN106517155A (en) * | 2016-10-10 | 2017-03-22 | 福州博力达机电有限公司 | Environment friendly method of preparing graphene |
| CN106542529A (en) * | 2016-12-06 | 2017-03-29 | 江苏悦达新材料科技有限公司 | A kind of method that green prepares high-quality graphene |
| CN109761427A (en) * | 2019-03-04 | 2019-05-17 | 南京信息工程大学 | A kind of method of resource for the sewage producing the generation of graphene factory |
| CN110201556A (en) * | 2019-05-21 | 2019-09-06 | 西南石油大学 | A kind of graphene oxide nanofiltration membrane, preparation method and applications slightly restored |
| CN115536010A (en) * | 2021-12-17 | 2022-12-30 | 曲靖华金雨林科技有限责任公司 | Preparation method of graphene |
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| CN101941694A (en) * | 2010-09-07 | 2011-01-12 | 湘潭大学 | Preparation method of high-dispersivity graphene |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104562682A (en) * | 2015-01-16 | 2015-04-29 | 浙江大学 | Wash-wear nonwoven fabric capable of selectively blocking ultraviolet rays |
| CN105833839A (en) * | 2016-06-10 | 2016-08-10 | 苏州巨联环保科研有限公司 | Preparation method of graphene-based adsorption material |
| CN106517155A (en) * | 2016-10-10 | 2017-03-22 | 福州博力达机电有限公司 | Environment friendly method of preparing graphene |
| CN106517155B (en) * | 2016-10-10 | 2018-11-06 | 福州博力达机电有限公司 | A kind of environmentally friendly method for preparing graphene |
| CN106542529A (en) * | 2016-12-06 | 2017-03-29 | 江苏悦达新材料科技有限公司 | A kind of method that green prepares high-quality graphene |
| CN109761427A (en) * | 2019-03-04 | 2019-05-17 | 南京信息工程大学 | A kind of method of resource for the sewage producing the generation of graphene factory |
| CN109761427B (en) * | 2019-03-04 | 2021-07-20 | 南京信息工程大学 | Recycling method of sewage generated in graphene production factory |
| CN110201556A (en) * | 2019-05-21 | 2019-09-06 | 西南石油大学 | A kind of graphene oxide nanofiltration membrane, preparation method and applications slightly restored |
| CN110201556B (en) * | 2019-05-21 | 2022-01-21 | 西南石油大学 | Slightly-reduced graphene oxide nanofiltration membrane, and preparation method and application thereof |
| CN115536010A (en) * | 2021-12-17 | 2022-12-30 | 曲靖华金雨林科技有限责任公司 | Preparation method of graphene |
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