CN103420365B - A kind of method preparing Graphene - Google Patents
A kind of method preparing Graphene Download PDFInfo
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- CN103420365B CN103420365B CN201310313253.XA CN201310313253A CN103420365B CN 103420365 B CN103420365 B CN 103420365B CN 201310313253 A CN201310313253 A CN 201310313253A CN 103420365 B CN103420365 B CN 103420365B
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Abstract
The method preparing Graphene disclosed by the invention, using the mixing solutions of thiourea peroxide or carbohydrazide and solubility highly basic as reductive agent, the redox graphene aqueous solution, obtains homodisperse graphene powder after washing drying.The invention solves the existing reductive agents such as hydrazine hydrate prepare exist in Graphene process high toxicity, reduction thoroughly and Graphene the problem such as easily to reunite.This preparation method is simple, and reaction process is rapid, and reaction conditions is gentle, and to equipment without particular requirement, obtained quality of graphene is high.
Description
Technical field
The present invention relates to the preparation field of Graphene, be specifically related to a kind of mixing solutions of thiourea peroxide or carbohydrazide and solubility highly basic that utilizes 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 0.3554nm, has the performance of many excellences.Research shows, tensile strength and the Young's modulus of Graphene are respectively 125GPa and 1.1TPa, is the material that intensity known is at present the highest; The conductivity of Graphene is splendid, and room temperature download stream transport factor can reach 2 × 105cm
2/ (Vs), and do not vary with temperature and reduce with chemical doping; The room temperature thermal conductivity of Graphene is 5 × 10
3w/ (mK) is more than 10 times of thermal conductivity (401W/mK) of copper under room temperature; It also have up to 2630m
2the theoretical specific surface area of/g.Graphene has application prospect widely in various fields such as photoelectron, magnetic energy, energy storage, catalysis, becomes rapidly the study hotspot in physics, chemistry and materialogy field in recent years.
Graphene is obtained by mechanically peel method at first.Develop again the preparation methods such as crystal epitaxy method, chemical Vapor deposition process and chemical reduction method subsequently.At present, the reductive agent that chemical reduction method is conventional has hydrazine hydrate, sodium borohydride and Resorcinol etc., these reductive agents also exist high toxicity, reduction thoroughly and product the problem such as easily to reunite.
Summary of the invention
The object of the invention is for solving in existing chemical preparation Graphene process, there is high toxicity in reductive agent used, reduction is not thorough, and obtained Graphene such as easily to be reunited at the problem, and a kind of mixing solutions of thiourea peroxide or carbohydrazide and solubility highly basic safely and efficiently that adopts is proposed as reductive agent, prepare the method for dispersed, that purity is high Graphene.
The method preparing Graphene of the present invention, comprises the steps:
(1) in stir speed (S.S.) be 100 ~ 200r/min and ice-water bath condition under, by graphite and SODIUMNITRATE, 1:0.4 ~ 0.6 joins mass concentration is in mass ratio in the sulfuric acid of 98%, the volume of sulfuric acid and the mass ratio of graphite are 30 ~ 40mL:1g, continue stirring 15 ~ 30min, warming-in-water is utilized mixed solution to be heated to temperature not higher than under the condition of 10 DEG C, add potassium permanganate, the mass ratio of potassium permanganate and graphite is 4 ~ 6:1, continues stirring 1 ~ 2h; Reaction 1 ~ 3h behind warming-in-water to 30 ~ 40 DEG C; Then deionized water is added, after continuing stirring 15 ~ 30min, the warm water and the mass concentration that add 30 ~ 35 DEG C are again the hydrogen peroxide of 20 ~ 30%, and 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, continue stirring 10 ~ 20min; Filter after above-mentioned solution ultrasonic disperse 15 ~ 30min, then be hydrochloric acid and the deionized water wash several of 5 ~ 10% by mass concentration, filtration product is dry, obtain graphite oxide;
(2), under Ultrasonic Conditions, the graphite oxide that step (1) is obtained is dissolved in deionized water, and compound concentration is the graphene oxide water solution of 0.1 ~ 1.0mg/mL;
(3) under stir speed (S.S.) is 30 ~ 50r/min condition, thiourea peroxide or carbohydrazide, solubility highly basic are dissolved in deionized water, obtain reductant solution, in reductant solution, the volume of deionized water and the quality of thiourea peroxide or carbohydrazide, the mass ratio of solubility highly basic are 30 ~ 50mL:1g:2 ~ 4g;
(4) under be 100 ~ 200r/min and bath temperature being the condition of 85 ~ 100 DEG C in stir speed (S.S.), the reductant solution that step (3) is obtained joins in the graphene oxide water solution of step (2), filter after continuing stirring reaction 5 ~ 10h, use ethanol and deionized water rinsing successively, filtration product is dry, obtain graphene powder.
In the present invention, the particle diameter of described graphite is less than 30 μm.
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:
Tool of the present invention has the following advantages:
1. the method preparing Graphene of the present invention, the mixing solutions of the thiourea peroxide that employing safety performance is good or carbohydrazide and solubility highly basic, as reductive agent, overcomes the reductive agents such as hydrazine hydrate and there is highly toxic problem.
2. the graphene uniform dispersion for preparing of the inventive method, avoids Graphene that existing preparation method obtains and easily to reunite the phenomenon of caking.
3. the method preparing Graphene of the present invention, more abundant to the reduction of graphene oxide water solution, the Graphene defect struchures obtained is less, and purity is higher.
Accompanying drawing explanation
Fig. 1 is X ray diffracting spectrum: the X ray diffracting spectrum that in figure, (a) is graphite oxide, and (b) reduces the X ray diffracting spectrum of the Graphene obtained through 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: the X ray diffracting spectrum that in figure, (a) is graphite oxide, and (b) reduces the X ray diffracting spectrum of the Graphene obtained through 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: the X ray diffracting spectrum that in figure, (a) is graphite oxide, and (b) reduces the X ray diffracting spectrum of the Graphene obtained through the mixing solutions of thiourea peroxide and solubility highly basic potassium hydroxide;
Embodiment
Below provide the specific embodiment of the present invention to be further described, but technical solution of the present invention is but not limited to following cited embodiment.
Embodiment 1
(1) in stir speed (S.S.) be 200r/min and ice-water bath condition under, be add 3g graphite and 1.8g SODIUMNITRATE in the sulfuric acid of 98% in 120mL mass concentration, continue to stir 30min, warming-in-water is utilized to be heated to by mixed solution not higher than under the condition of 10 DEG C, add 18g potassium permanganate, continue to stir 2h; 3h is reacted after warming-in-water to 40 DEG C; Then add 120mL deionized water, continue to stir 30min, then to add 300mL, the warm water of 35 DEG C and 72mL mass concentration be the hydrogen peroxide of 30%, continue to stir 20min; Filter after above-mentioned solution ultrasonic disperse 30min, then be hydrochloric acid and the deionized water wash 5 times of 10% by mass concentration, filtration product is dry at 70 DEG C, obtained 4.9g graphite oxide.
(2) taking 500mg graphite oxide is dissolved in 500mL deionized water, through ul-trasonic irradiation 2h, obtains the graphene oxide water solution that concentration is 1.0mg/mL.
(3) 4g thiourea peroxide and 16g sodium hydroxide are dissolved in 200mL deionized water, under speed is 30r/min, stirs 1h, be made into reductant solution.
(4) under be 200r/min and bath temperature being the condition of 100 DEG C in stir speed (S.S.), the reductive agent that step (3) is obtained joins in the graphene oxide water solution of step (2), filter after continuing stirring reaction 10h, after using ethanol and deionized water rinsing 5 times successively, by filtration product dry 12h at 70 DEG C, obtain the homodisperse graphene powder of 0.27g.
X-ray polycrystalline diffractometer is adopted 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 mixing solutions reduction of thiourea peroxide and sodium hydroxide, the characteristic diffraction peak at its ° place in 2 θ=9.7 disappears, the substitute is the characteristic diffraction peak of 2 θ=24.4 ° place's Graphene, illustrate that graphite oxide is reduced into Graphene by the mixing solutions of thiourea peroxide and sodium hydroxide.
Adopt Raman spectrometer to analyze Graphene, Raman spectrum as shown in Figure 2: the mixing solutions through thiourea peroxide and sodium hydroxide reduces the Graphene that obtains at 1355cm
-1the D peak intensity at place compares 1587cm
-1the G peak intensity at place is low.Generally think, D peak characterizes the randomness of Graphene, shows to there is oxygen-containing functional group, other defect and irregular carbon structure (sp
3key) etc.; G peak is carbon sp
2the characteristic peak of structure, shows that carbon atom has six side's close-packed configuration, and D peak and G peak intensity are than less, and the defect struchures of Graphene is fewer.It is less that Fig. 2 result illustrates that the mixing solutions through thiourea peroxide and sodium hydroxide reduces the Graphene defect struchures that obtains, and quality is very high.
Embodiment 2
(1) in stir speed (S.S.) be 150r/min and ice-water bath condition under, be add 2g graphite and 1g SODIUMNITRATE in the sulfuric acid of 98% in 70mL mass concentration, continue to stir 20min, warming-in-water is utilized to be heated to by mixed solution not higher than under the condition of 10 DEG C, add 10g potassium permanganate, continue to stir 1.5h; 2h is reacted after warming-in-water to 35 DEG C; Then add 50mL deionized water, continue to stir 20min, adding 160mL, the warm water of 33 DEG C and 35mL mass concentration is the hydrogen peroxide of 25%, continues to stir 15min; Filter after above-mentioned solution ultrasonic disperse 20min, then be hydrochloric acid and the deionized water wash 5 times of 8% by mass concentration, filtration product is dry at 60 DEG C, obtained 3.3g graphite oxide.
(2) taking 300mg graphite oxide is dissolved in 600mL deionized water, through ul-trasonic irradiation 1.5h, obtains the graphene oxide water solution that concentration is 0.5mg/mL.
(3) 1.8g carbohydrazide and 4g sodium hydroxide and 1.4g hydrated barta are dissolved in 72mL deionized water, under speed is 50r/min, stirs, be made into reductant solution.
(4) under be 150r/min and bath temperature being the condition of 95 DEG C in stir speed (S.S.), the reductive agent that step (3) is obtained joins in the graphene oxide water solution of step (2), filter after continuing stirring reaction 8h, after using ethanol and deionized water rinsing 5 times successively, by filtration product dry 8h at 60 DEG C, obtain the homodisperse graphene powder of 0.16g.
X-ray polycrystalline diffractometer is adopted 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 reduced by the mixing solutions of carbohydrazide and sodium hydroxide and hydrated barta, the characteristic diffraction peak at its ° place in 2 θ=9.2 disappears, the substitute is the characteristic diffraction peak of 2 θ=23.9 ° place's Graphene, illustrate that graphite oxide is reduced into Graphene by the mixing solutions of carbohydrazide and sodium hydroxide and hydrated barta.
Adopt Raman spectrometer to analyze Graphene, Raman spectrum as shown in Figure 4: the mixing solutions through carbohydrazide and sodium hydroxide and hydrated barta reduces the Graphene that obtains at 1352cm
-1the D peak intensity at place compares 1594cm
-1the G peak intensity at place is low, and it is less that the mixing solutions illustrating through carbohydrazide and sodium hydroxide and hydrated barta reduces the Graphene defect struchures obtained, and quality is very high.
Embodiment 3
(1) in stir speed (S.S.) be 100r/min and ice-water bath condition under, be add 1g graphite and 0.4g SODIUMNITRATE in the sulfuric acid of 98% in 30mL mass concentration, continue to stir 15min, warming-in-water is utilized to be heated to by mixed solution not higher than under the condition of 10 DEG C, add 4g potassium permanganate, continue to stir 1h; 1h is reacted after warming-in-water to 30 DEG C; Then add 15mL deionized water, continue to stir 15min, adding 60mL, the warm water of 30 DEG C and 12mL mass concentration is the hydrogen peroxide of 20%, continues to stir 10min; Filter after above-mentioned solution ultrasonic disperse 15min, then be hydrochloric acid and the deionized water wash 3 times of 5% by mass concentration, filtration product is dry at 50 DEG C, obtained 1.7g graphite oxide.
(2) taking 100mg graphite oxide is dissolved in 1L deionized water, through ul-trasonic irradiation 1h, obtains the graphene oxide water solution that concentration is 0.1mg/mL.
(3) 0.4g thiourea peroxide and 0.8g potassium hydroxide are dissolved in 12mL deionized water, under speed is 45r/min, stirs, be made into reductant solution.
(4) under be 100r/min and bath temperature being the condition of 85 DEG C in stir speed (S.S.), the reductive agent that step (3) is obtained joins in the graphene oxide water solution of step (2), filter after continuing stirring reaction 5h, after using ethanol and deionized water rinsing 3 times successively, by filtration product dry 6h at 50 DEG C, obtain the homodisperse graphene powder of 0.06g.
X-ray polycrystalline diffractometer is adopted 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 mixing solutions reduction of thiourea peroxide and potassium hydroxide, the characteristic diffraction peak at its ° place in 2 θ=10.1 disappears, the substitute is the characteristic diffraction peak of 2 θ=24.1 ° place's Graphene, illustrate that graphite oxide is reduced into Graphene by the mixing solutions of thiourea peroxide and potassium hydroxide.
Claims (3)
1. prepare a method for Graphene, comprise the steps:
(1) in stir speed (S.S.) be 100 ~ 200r/min and ice-water bath condition under, by graphite and SODIUMNITRATE, 1:0.4 ~ 0.6 joins mass concentration is in mass ratio in the sulfuric acid of 98%, the volume of sulfuric acid and the mass ratio of graphite are 30 ~ 40mL:1g, continue stirring 15 ~ 30min, warming-in-water is utilized mixed solution to be heated to temperature not higher than under the condition of 10 DEG C, add potassium permanganate, the mass ratio of potassium permanganate and graphite is 4 ~ 6:1, continues stirring 1 ~ 2h; Reaction 1 ~ 3h behind warming-in-water to 30 ~ 40 DEG C; Then deionized water is added, after continuing stirring 15 ~ 30min, the warm water and the mass concentration that add 30 ~ 35 DEG C are again the hydrogen peroxide of 20 ~ 30%, and 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, continue stirring 10 ~ 20min; Filter after above-mentioned solution ultrasonic disperse 15 ~ 30min, then be hydrochloric acid and the deionized water wash several of 5 ~ 10% by mass concentration, filtration product is dry, obtain graphite oxide;
(2), under Ultrasonic Conditions, the graphite oxide that step (1) is obtained is dissolved in deionized water, and compound concentration is the graphene oxide water solution of 0.1 ~ 1.0mg/mL;
(3) under stir speed (S.S.) is 30 ~ 50r/min condition, carbohydrazide, solubility highly basic are dissolved in deionized water, obtain reductant solution, in reductant solution, the volume of deionized water and the quality of carbohydrazide, the mass ratio of solubility highly basic are 30 ~ 50mL:1g:2 ~ 4g;
(4) under be 100 ~ 200r/min and bath temperature being the condition of 85 ~ 100 DEG C in stir speed (S.S.), the reductant solution that step (3) is obtained joins in the graphene oxide water solution of step (2), filter after continuing stirring reaction 5 ~ 10h, use ethanol and deionized water rinsing successively, filtration product is dry, obtain graphene powder.
2. the method preparing Graphene according to claim 1, is characterized in that the particle diameter of described graphite is less than 30 μm.
3. the method 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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| 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 |
| 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 |
| 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 |
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| CN108046242A (en) * | 2017-12-20 | 2018-05-18 | 昆明理工大学 | A kind of preparation method of poroid graphene |
| 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 |
| CN109576983A (en) * | 2019-01-04 | 2019-04-05 | 张永奇 | A kind of graphene oxide coated polyester 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 |
| CN113275585B (en) * | 2021-05-24 | 2023-05-19 | 北京理工大学珠海学院 | Nano nickel wire and preparation method thereof |
| CN114229836A (en) * | 2022-01-14 | 2022-03-25 | 曲靖华金雨林科技有限责任公司 | Method for electrochemically preparing graphene |
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