CN103420365A - Graphene preparation method - Google Patents
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Abstract
The invention discloses a graphene preparation method. The mixed solution of thiourea dioxide and soluable alkali or carbohydrazide and the soluable alkali is taken as a reducing agent to perform reduction-oxidation on the graphene aqueous solution, and evenly dispersed graphene powder is obtained after washing and drying. The graphene preparation method, disclosed by the invention, solves the problems that hydrazine hydrate and other existing reducing agents are high-toxic and not thorough in reduction, and the graphene is liable to gathering in the graphene preparation process. The preparation method is simple and feasible, is rapid in reaction process and moderate in reaction condition and has no special requirements to equipment, and the prepared graphene is of high quality.
Description
Technical field
The present invention relates to the preparation field of Graphene, be specifically related to a kind of mixing solutions that utilizes thiourea peroxide or carbohydrazide and solubility highly basic as reductive agent, the redox graphene aqueous solution prepares the method for Graphene.
Background technology
Graphene is by sp
2The individual layer two-dimensional material that the carbon atom arrangement of hydridization becomes cellular crystalline network to obtain, its thickness only has 0.3554 nm, has the performance of many excellences.Research shows, the tensile strength of Graphene and Young's modulus are respectively 125 GPa and 1.1 TPa, is the known the highest material of intensity at present; The conductivity of Graphene is splendid, and room temperature download stream transport factor can reach 2 * 105 cm
2/ (Vs), and do not vary with temperature with chemical doping and reduce; The room temperature thermal conductivity of Graphene is 5 * 10
3W/ (mK) is more than 10 times of thermal conductivity (401 W/mK) of copper under room temperature; It also have up to 2630 m
2The theoretical specific surface area of/g.Graphene has application prospect very widely in various fields such as photoelectron, magnetic energy, energy storage, catalysis, becomes rapidly in recent years the study hotspot in physics, chemistry and materialogy field.
Graphene is made by the mechanically peel method at first.Develop again subsequently the preparation methods such as crystal epitaxy method, chemical Vapor deposition process and chemical reduction method.At present, the reductive agent that chemical reduction method is commonly used has hydrazine hydrate, sodium borohydride and Resorcinol etc., and these reductive agents exist high toxicity, reduction not thoroughly and the easy problems such as reunion of product.
Summary of the invention
The objective of the invention is for solving in existing chemical preparation Graphene process, reductive agent used exist high toxicity, the reduction not thorough, and the easy problem such as reunion of the Graphene made, and propose a kind of employing safely and efficiently the mixing solutions of thiourea peroxide or carbohydrazide and solubility highly basic as reductive agent, prepare the method for the Graphene dispersed, that purity is high.
The method for preparing Graphene of the present invention, comprise the steps:
(1) under the condition that is 100～200r/min and ice-water bath in stir speed (S.S.), graphite and SODIUMNITRATE are joined in the sulfuric acid that mass concentration is 98% 1:0.4～0.6 in mass ratio, the volume of sulfuric acid and the mass ratio of graphite are 30～40mL:1g, continue to stir 15～30min, utilize warming-in-water that mixed solution is heated to temperature not higher than under the condition of 10 ℃, add potassium permanganate, the mass ratio of potassium permanganate and graphite is 4～6:1, continues to stir 1～2h; React 1～3h behind warming-in-water to 30～40 ℃; Then add deionized water, after continuing to stir 15～30min, add the hydrogen peroxide that the warm water of 30～35 ℃ and mass concentration are 20～30%, the volume ratio of sulfuric acid, deionized water, warm water and hydrogen peroxide is 1:0.5～1.0:2.0～2.5:0.4～0.6 again, continues to stir 10～20min; To after the ultrasonic dispersion 15～30min of above-mentioned solution, filter, then the hydrochloric acid that is 5～10% by mass concentration and deionized water wash several, by the filtration product drying, obtain graphite oxide;
(2) under Ultrasonic Conditions, the graphite oxide that step (1) is made is dissolved in deionized water, the graphite oxide aqueous solution that compound concentration is 0.1～1.0mg/mL;
(3) in stir speed (S.S.), be under 30～50r/min condition, thiourea peroxide or carbohydrazide, solubility highly basic are dissolved in deionized water, obtain reductant solution, in reductive agent, the mass ratio of the quality of the volume of deionized water and thiourea peroxide or carbohydrazide, solubility highly basic is 30～50mL:1g:2～4g;
(4) in stir speed (S.S.), be under 100～200r/min and the bath temperature condition that is 85～100 ℃, the reductive agent that step (3) is made joins in the graphite oxide aqueous solution of step (2), continue to filter after stirring reaction 5～10h, use successively ethanol and deionized water rinsing, by the filtration product drying, obtain graphene powder.
In the present invention, the particle diameter of described graphite is less than 30 μ m.
In the present invention, described solubility highly basic is one or more in sodium hydroxide, potassium hydroxide and hydrated barta.
Described thiourea peroxide has following structural formula:
Described carbohydrazide has following structural formula:
The present invention has following advantage:
1. the method for preparing Graphene of the present invention, adopt the mixing solutions of thiourea peroxide that safety performance is good or carbohydrazide and solubility highly basic as reductive agent, overcome the reductive agent such as hydrazine hydrate and had highly toxic problem.
2. the inventive method prepares graphene uniform disperses, and has avoided easily the reunite phenomenon of caking of Graphene that existing preparation method obtains.
3. the method for preparing Graphene of the present invention, more abundant to the reduction of graphite oxide aqueous solution, and the Graphene impurity and the defect that obtain are less, and purity is higher.
The accompanying drawing explanation
Fig. 1 is X ray diffracting spectrum: in figure, (a) is the X ray diffracting spectrum of graphite oxide, is (b) X ray diffracting spectrum of the Graphene that obtains through the reduction of the mixing solutions of thiourea peroxide and solubility highly basic sodium hydroxide;
Fig. 2 is the Raman spectrum of the Graphene of embodiment 1 gained.
Fig. 3 is X ray diffracting spectrum: in figure, (a) is the X ray diffracting spectrum of graphite oxide, is (b) X ray diffracting spectrum of the Graphene that obtains through the reduction of the mixing solutions of carbohydrazide and solubility highly basic sodium hydroxide and hydrated barta;
Fig. 4 is the Raman spectrum of the Graphene of embodiment 2 gained.
Fig. 5 is X ray diffracting spectrum: in figure, (a) is the X ray diffracting spectrum of graphite oxide, is (b) X ray diffracting spectrum of the Graphene that obtains through the reduction of the mixing solutions of thiourea peroxide and solubility highly basic potassium hydroxide.
Embodiment
Below provide the specific embodiment of the present invention and be further described, yet technical solution of the present invention but is not limited to following cited embodiment.
Embodiment 1
(1) under the condition that is 200r/min and ice-water bath in stir speed (S.S.), add 3g graphite and 1.8g SODIUMNITRATE in the sulfuric acid that is 98% in the 120mL mass concentration, continue to stir 30min, utilize warming-in-water that mixed solution is heated to not higher than under the condition of 10 ℃, add 18g potassium permanganate, continue to stir 2h; React 3h after warming-in-water to 40 ℃; Then add the 120mL deionized water, continue to stir 30min, then add the hydrogen peroxide that 300mL, the warm water of 35 ℃ and 72mL mass concentration are 30%, continue to stir 20min; To after the ultrasonic dispersion of above-mentioned solution 30min, filter, then the hydrochloric acid that is 10% by mass concentration and deionized water wash 5 times, filtration product is dry under 70 ℃, make the 4.9g graphite oxide.
(2) take the 500mg graphite oxide and be dissolved in the 500mL deionized water, through ul-trasonic irradiation 2h, the graphite oxide aqueous solution that to obtain concentration be 1.0mg/mL.
(3) by 4g thiourea peroxide and 16g dissolution of sodium hydroxide in the 200mL deionized water, in speed, be under 30r/min, stir 1h, be made into reductant solution.
(4) in stir speed (S.S.), be under 200r/min and the bath temperature condition that is 100 ℃, the reductive agent that step (3) is made joins in the graphite oxide aqueous solution of step (2), continue to filter after stirring reaction 10h, after using successively ethanol and deionized water rinsing 5 times, by filtration product dry 12h under 70 ℃, obtain the homodisperse graphene powder of 0.27g.
Adopt X ray polycrystalline diffractometer to carry out material phase analysis to graphite oxide and Graphene, X ray diffracting spectrum is as shown in Figure 1: after graphite oxide is by the reduction of the mixing solutions of thiourea peroxide and sodium hydroxide, the characteristic diffraction peak that it is located in 2 θ=9.7 ° disappears, the substitute is 2 θ=24.4 ° and locate the characteristic diffraction peak of Graphene, illustrate that the mixing solutions of thiourea peroxide and sodium hydroxide is reduced into Graphene by graphite oxide.
Adopt Raman spectrometer to be analyzed Graphene, Raman spectrum as shown in Figure 2: the Graphene obtained through the mixing solutions reduction of thiourea peroxide and sodium hydroxide is at 1355cm
-1The D peak intensity at place compares 1587cm
-1The G peak intensity at place is low.Generally think, the D peak characterizes the randomness of Graphene, shows to exist oxygen-containing functional group, other defect and irregular carbon structure (sp
3Key) etc.; The G peak is carbon sp
2The characteristic peak of structure, show that carbon atom has six side's solid matter structures, and the D peak is with the G peak intensity than less, and impurity and the defect of Graphene are fewer.Graphene impurity and defect that Fig. 2 presentation of results obtains through the reduction of the mixing solutions of thiourea peroxide and sodium hydroxide are less, and quality is very high.
Embodiment 2
(1) under the condition that is 150r/min and ice-water bath in stir speed (S.S.), add 2g graphite and 1g SODIUMNITRATE in the sulfuric acid that is 98% in the 70mL mass concentration, continue to stir 20min, utilize warming-in-water that mixed solution is heated to not higher than under the condition of 10 ℃, add 10g potassium permanganate, continue to stir 1.5h; React 2h after warming-in-water to 35 ℃; Then add the 50mL deionized water, continue to stir 20min, add the hydrogen peroxide that 160mL, the warm water of 33 ℃ and 35mL mass concentration are 25%, continue to stir 15min; To after the ultrasonic dispersion of above-mentioned solution 20min, filter, then the hydrochloric acid that is 8% by mass concentration and deionized water wash 5 times, filtration product is dry under 60 ℃, make the 3.3g graphite oxide.
(2) take the 300mg graphite oxide and be dissolved in the 600mL deionized water, through ul-trasonic irradiation 1.5h, the graphite oxide aqueous solution that to obtain concentration be 0.5mg/mL.
(3) 1.8g carbohydrazide and 4g sodium hydroxide and 1.4g hydrated barta being dissolved in the 72mL deionized water, is under 50r/min in speed, stirs, and is made into reductant solution.
(4) in stir speed (S.S.), be under 150r/min and the bath temperature condition that is 95 ℃, the reductive agent that step (3) is made joins in the graphite oxide aqueous solution of step (2), continue to filter after stirring reaction 8h, after using successively ethanol and deionized water rinsing 5 times, by filtration product dry 8h under 60 ℃, obtain the homodisperse graphene powder of 0.16g.
Adopt X ray polycrystalline diffractometer to carry out material phase analysis to graphite oxide and Graphene, X ray diffracting spectrum is as shown in Figure 3: after graphite oxide is by the reduction of the mixing solutions of carbohydrazide and sodium hydroxide and hydrated barta, the characteristic diffraction peak that it is located in 2 θ=9.2 ° disappears, the substitute is 2 θ=23.9 ° and locate the characteristic diffraction peak of Graphene, illustrate that the mixing solutions of carbohydrazide and sodium hydroxide and hydrated barta is reduced into Graphene by graphite oxide.
Adopt Raman spectrometer to be analyzed Graphene, Raman spectrum as shown in Figure 4: reduce the Graphene that obtains at 1352cm through the mixing solutions of carbohydrazide and sodium hydroxide and hydrated barta
-1The D peak intensity at place compares 1594cm
-1The G peak intensity at place is low, illustrate that to reduce through the mixing solutions of carbohydrazide and sodium hydroxide and hydrated barta the Graphene impurity and the defect that obtain less, and quality is very high.
Embodiment 3
(1) under the condition that is 100r/min and ice-water bath in stir speed (S.S.), add 1g graphite and 0.4g SODIUMNITRATE in the sulfuric acid that is 98% in the 30mL mass concentration, continue to stir 15min, utilize warming-in-water that mixed solution is heated to not higher than under the condition of 10 ℃, add 4g potassium permanganate, continue to stir 1h; React 1h after warming-in-water to 30 ℃; Then add the 15mL deionized water, continue to stir 15min, add the hydrogen peroxide that 60mL, the warm water of 30 ℃ and 12mL mass concentration are 20%, continue to stir 10min; To after the ultrasonic dispersion of above-mentioned solution 15min, filter, then the hydrochloric acid that is 5% by mass concentration and deionized water wash 3 times, filtration product is dry under 50 ℃, make the 1.7g graphite oxide.
(2) take the 100mg graphite oxide and be dissolved in the 1L deionized water, through ul-trasonic irradiation 1h, the graphite oxide aqueous solution that to obtain concentration be 0.1mg/mL.
(3) 0.4g thiourea peroxide and 0.8g potassium hydroxide being dissolved in the 12mL deionized water, is under 45r/min in speed, stirs, and is made into reductant solution.
(4) in stir speed (S.S.), be under 100r/min and the bath temperature condition that is 85 ℃, the reductive agent that step (3) is made joins in the graphite oxide aqueous solution of step (2), continue to filter after stirring reaction 5h, after using successively ethanol and deionized water rinsing 3 times, by filtration product dry 6h under 50 ℃, obtain the homodisperse graphene powder of 0.06g.
Adopt X ray polycrystalline diffractometer to carry out material phase analysis to graphite oxide and Graphene, X ray diffracting spectrum is as shown in Figure 5: after graphite oxide is by the reduction of the mixing solutions of thiourea peroxide and potassium hydroxide, the characteristic diffraction peak that it is located in 2 θ=10.1 ° disappears, the substitute is 2 θ=24.1 ° and locate the characteristic diffraction peak of Graphene, illustrate that the mixing solutions of thiourea peroxide and potassium hydroxide is reduced into Graphene by graphite oxide.
Claims (3)
1. a method for preparing Graphene, comprise the steps:
(1) under the condition that is 100～200r/min and ice-water bath in stir speed (S.S.), graphite and SODIUMNITRATE are joined in the sulfuric acid that mass concentration is 98% 1:0.4～0.6 in mass ratio, the volume of sulfuric acid and the mass ratio of graphite are 30～40mL:1g, continue to stir 15～30min, utilize warming-in-water that mixed solution is heated to temperature not higher than under the condition of 10 ℃, add potassium permanganate, the mass ratio of potassium permanganate and graphite is 4～6:1, continues to stir 1～2h; React 1～3h behind warming-in-water to 30～40 ℃; Then add deionized water, after continuing to stir 15～30min, add the hydrogen peroxide that the warm water of 30～35 ℃ and mass concentration are 20～30%, the volume ratio of sulfuric acid, deionized water, warm water and hydrogen peroxide is 1:0.5～1.0:2.0～2.5:0.4～0.6 again, continues to stir 10～20min; To after the ultrasonic dispersion 15～30min of above-mentioned solution, filter, then the hydrochloric acid that is 5～10% by mass concentration and deionized water wash several, by the filtration product drying, obtain graphite oxide;
(2) under Ultrasonic Conditions, the graphite oxide that step (1) is made is dissolved in deionized water, the graphite oxide aqueous solution that compound concentration is 0.1～1.0mg/mL;
(3) in stir speed (S.S.), be under 30～50r/min condition, thiourea peroxide or carbohydrazide, solubility highly basic are dissolved in deionized water, obtain reductant solution, in reductive agent, the mass ratio of the quality of the volume of deionized water and thiourea peroxide or carbohydrazide, solubility highly basic is 30～50mL:1g:2～4g;
(4) in stir speed (S.S.), be under 100～200r/min and the bath temperature condition that is 85～100 ℃, the reductive agent that step (3) is made joins in the graphite oxide aqueous solution of step (2), continue to filter after stirring reaction 5～10h, use successively ethanol and deionized water rinsing, by the filtration product drying, obtain graphene powder.
2. the method for preparing Graphene according to claim 1, is characterized in that the particle diameter of described graphite is less than 30 μ m.
3. the method for preparing Graphene according to claim 1, is characterized in that described solubility highly basic is one or more in sodium hydroxide, potassium hydroxide and hydrated barta.
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| 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 |
| CN106824142A (en) * | 2016-12-19 | 2017-06-13 | 华南农业大学 | A kind of thiourea dioxide reduces magnetic oxygenated Graphene and preparation method and application |
| CN106966844A (en) * | 2017-02-24 | 2017-07-21 | 西北工业大学 | Graphene-based carbohydrazide metal complex crystal energetic material and preparation method thereof |
| CN107335320A (en) * | 2017-09-04 | 2017-11-10 | 北京金逸科技有限公司 | The net taste of environment-friendly type is except formaldehyde composition and preparation method thereof |
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| 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 |
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| CN106824142A (en) * | 2016-12-19 | 2017-06-13 | 华南农业大学 | A kind of thiourea dioxide reduces magnetic oxygenated Graphene and preparation method and application |
| CN106966844A (en) * | 2017-02-24 | 2017-07-21 | 西北工业大学 | Graphene-based carbohydrazide metal complex crystal energetic material and preparation method thereof |
| CN106966844B (en) * | 2017-02-24 | 2018-11-20 | 西北工业大学 | Graphene-based carbohydrazide metal complex crystal energetic material and preparation method thereof |
| CN107352535A (en) * | 2017-08-18 | 2017-11-17 | 复旦大学 | A kind of high efficiency preparation method of graphene oxide |
| CN107335320A (en) * | 2017-09-04 | 2017-11-10 | 北京金逸科技有限公司 | The net taste of environment-friendly type is except formaldehyde composition and preparation method thereof |
| CN107335320B (en) * | 2017-09-04 | 2020-02-07 | 北京金逸科技有限公司 | Environment-friendly odor-removing and formaldehyde-removing composition and preparation method thereof |
| CN108046242A (en) * | 2017-12-20 | 2018-05-18 | 昆明理工大学 | A kind of preparation method of poroid graphene |
| CN109576983A (en) * | 2019-01-04 | 2019-04-05 | 张永奇 | A kind of graphene oxide coated polyester fabric and preparation method thereof |
| CN109594328A (en) * | 2019-01-04 | 2019-04-09 | 张永奇 | A kind of graphite oxide ene coatings polyester-cotton fabric and preparation method thereof |
| CN111944593A (en) * | 2020-08-28 | 2020-11-17 | 刘云顺 | Environment-friendly anti-wear lubricating oil and preparation method thereof |
| CN113275585A (en) * | 2021-05-24 | 2021-08-20 | 北京理工大学珠海学院 | Nano nickel wire and preparation method thereof |
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