CN102001651B - Method for preparing graphene based on hydroxylamine reduction - Google Patents
Method for preparing graphene based on hydroxylamine reduction Download PDFInfo
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- CN102001651B CN102001651B CN2010106132129A CN201010613212A CN102001651B CN 102001651 B CN102001651 B CN 102001651B CN 2010106132129 A CN2010106132129 A CN 2010106132129A CN 201010613212 A CN201010613212 A CN 201010613212A CN 102001651 B CN102001651 B CN 102001651B
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Abstract
The invention provides a method for preparing graphene based on hydroxylamine reduction, comprising the following steps: carrying out oxidation treatment on suspension which is prepared by blending the natural graphite powder to obtain oxidized graphite solid; preparing the oxidized graphite solid into a single-layer oxidized graphene aqueous solution; and reacting the single-layer oxidized graphene aqueous solution with ammonia water and hydroxylamine hydrochloride to obtain a graphene aqueous solution. The uniform and dispersive graphene aqueous solution is prepared by using the method of the invention.
Description
Technical field
That the present invention relates to is a kind of preparation method of Graphene technical field, specifically is a kind of based on azanol reductive graphene preparation method.
Background technology
Graphene, carbon atom is through sp
2The individual layer two dimensional crystal that the mutual bonding of hydridization is formed has excellent performances such as electricity, calorifics and mechanics, since 2004 find, has obtained investigator's extensive concern.It is with a wide range of applications in fields such as matrix material, energy storage material, solar cell, transmitters, and is expected to replace silicon materials at semiconductor applications, therefore demands seeking a kind of a large amount of method for preparing Graphene urgently.
Prior art comprises physical method and chemical process to preparation method of graphene.To prepare single crystal graphite alkene film lattice imperfection few for the physical method of graphite to utilize micromechanics to come off, excellent performance.But this method yields poorly and is only limited to the laboratory fundamental research.The template epitaxy is under high temperature and uht conditions; Prepare Graphene in monocrystalline silicon carbide surface epitaxy; This preparation method can obtain large-area Graphene, but the promotion and application that its cost is higher, product is difficult for greatly having limited from factors such as substrate separate this method.Based on the limitation of physical method, chemical process is high because of its productive rate, and cost is low, also can cause investigator's concern to the advantage that Graphene carries out chemically modified.This method is under strong acid and strong oxidizer effect, Graphite Powder 99 to be carried out the oxidation intercalation to generate graphite oxide, and ultrasonic again peeling off is separated into individual layer and is prepared into the graphene oxide water-sol, at last its deoxidation and reduction become Graphene.Wherein, selecting appropriate reductant is the problem that the investigator very pays close attention to.
Retrieval through to prior art is found; Stankovich etc. are at " Carbon " (2007; 45; Delivered " Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide " (through the chemical reduction through the graphite oxide that peels off is prepared graphene nano lamella structure) 1558-1565), this article author is that reductive agent is reduced to Graphene with graphene oxide with the Hydrazine Hydrate 80, and this method can prepare Graphene in a large number; But Hydrazine Hydrate 80 is hypertoxic, and is harmful to human body and environment.In addition; Zhang etc. are at " Chemical Communication " (chemical communication) (2010; 4; Delivered " Reduction of graphene oxide via L-ascorbic acid " (utilizing the xitix redox graphene) 1112-1114), the author replaces Hydrazine Hydrate 80 as reductive agent with xitix.Xitix is a kind of environmentally friendly reductive agent, however its cost an arm and a leg, be unfavorable for large-scale industrialization production.
Summary of the invention
The present invention is directed to the above-mentioned deficiency that prior art exists; Provide a kind of based on azanol reductive graphene preparation method; Utilize azanol as reductive agent, selecting natural graphite for use is raw material, prepares homogeneous dispersive graphene aqueous solution through ammoniacal liquor conditioned reaction system pH.
The present invention realizes through following technical scheme; The present invention is through obtaining oxidation graphite solid with natural graphite powder through the intercalation oxide treatment; And oxidation graphite solid processed behind the mono-layer graphite oxide aqueous solution and ammoniacal liquor and oxammonium hydrochloride reaction, obtain Graphene solution.
Described natural graphite powder is meant: 500 purpose particulate state natural graphite powders;
Describedly natural graphite powder obtained oxidation graphite solid through the intercalation oxide treatment be meant: with natural graphite powder with adopt the vitriol oil and potassium permanganate to carry out oxidation successively after SODIUMNITRATE mixes; Fully obtain brown graphite oxide suspension-s after the reaction, the suction filtration whiz obtains oxidation graphite solid after ydrogen peroxide 50 and deionized water dilution again.
The described employing vitriol oil and potassium permanganate carry out oxidation and is meant: the dropping mass percent is 98% the vitriol oil and fully stirs in natural graphite powder and SODIUMNITRATE in environment below 0 ℃; The dropping time is controlled to be 15min, and stirs 30min at environment below 10 ℃; In 1h, potassium permanganate is added system when keeping stirring environment then, the potassium permanganate that adds each time is 2～3g, and the timed interval is 20min, keeps system temperature to be lower than 20 ℃, finishes continued for the third time and stirs 30min.
Described abundant reaction is meant: slowly drip deionized water and make temperature be no more than 90 ℃ with natural graphite powder and SODIUMNITRATE heating in water bath to 35 ± 3 ℃ and after reacting 2h, obtain brown graphite oxide suspension-s.
The dilution of described ydrogen peroxide 50 and deionized water is meant: adopting volume ratio is that 7: 55 30% the ydrogen peroxide 50 and the mixed solution of deionized water dilute.
Described suction filtration whiz is meant: after obtaining filter cake with the B suction filtration, using temperature is that 45 ℃ mass percent is 3% Hydrogen chloride repetitive scrubbing 3 times.In solid filter cake dispersed with stirring water, centrifugal 20min obtains the graphite oxide gel under the 4000rpm rotating speed, and its dry 24h under 40 ℃ vacuum environment is obtained oxidation graphite solid.
Described mono-layer graphite oxide aqueous solution is meant: adopt ultrasonic power to be scattered in the deionized water graphite oxide, graphite oxide is disperseed to peel off into individual layer, process the mono-layer graphite oxide aqueous solution;
Described ultrasonic power is meant: operating frequency is 40kHz, and power is ultrasonic 1h under the 160W effect;
The described reaction with ammoniacal liquor and oxammonium hydrochloride is meant: add ammoniacal liquor and oxammonium hydrochloride successively at graphene oxide solution; Ammoniacal liquor and oxammonium hydrochloride reaction discharge the free azanol; Azanol obtains Graphene solution as reductive agent and graphite oxide alkene reaction in 90 ℃ of water-baths.
Compared with prior art, the invention has the advantages that adopting azanol is reductive agent, toxicity is little, and cheapness helps the batch process of Graphene.
Description of drawings
Fig. 1 is a step synoptic diagram of the present invention.
Fig. 2 is the Graphene synoptic diagram;
Wherein: a is a Graphene AFM picture; B is Graphene altitude distribution figure.
Fig. 3 is a Graphene sem synoptic diagram.
Embodiment
Elaborate in the face of embodiments of the invention down, present embodiment provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.
Embodiment 1
As shown in Figure 1, present embodiment is said preparation method may further comprise the steps:
Preparation 50mL, 0.25mg/mL graphite oxide aqueous solution places the 100mL Erlenmeyer flask, adds 175 μ L ammoniacal liquor, the 0.025g oxammonium hydrochloride.Erlenmeyer flask is placed the water-bath that heats in advance, and the control temperature of reaction system is at 90 ℃, and the reaction times is 30min, makes black Graphene solution.
Embodiment 2:
Preparation 50mL, 0.25mg/mL graphite oxide aqueous solution places the 100mL Erlenmeyer flask, adds 175 μ L ammoniacal liquor, the 0.025g oxammonium hydrochloride.Erlenmeyer flask is placed the water-bath that heats in advance, and the control temperature of reaction system is at 90 ℃, and the reaction times is 1h, makes black Graphene solution.
Embodiment 3:
Preparation 50mL, 0.25mg/mL graphite oxide aqueous solution places the 100mL Erlenmeyer flask, adds 175 μ L ammoniacal liquor, the 0.025g oxammonium hydrochloride.Erlenmeyer flask is placed the water-bath that heats in advance, and the control temperature of reaction system is at 90 ℃, and the reaction times is 12h, makes black Graphene solution.
Embodiment 4:
Preparation 50mL, 0.25mg/mL graphite oxide aqueous solution places the 100mL Erlenmeyer flask, adds 175 μ L ammoniacal liquor, the 0.025g oxammonium hydrochloride.Erlenmeyer flask is placed the water-bath that heats in advance, and the control temperature of reaction system is at 90 ℃, and the reaction times is 24h, makes black Graphene solution.
In the preparation process of Graphene, the reaction times surpasses 1h does not have influence to reducing degree, and is the product serious agglomeration, so the Best Times of reduction reaction is 1h.At last, utilize shown in atomic power electron microscope Fig. 2 and shown in the scanning electron microscope diagram 3, the pattern and the structure of Graphene characterized.Shown in AFM picture Fig. 2 a of Graphene, show that the single-layer graphene layer is smooth and level and smooth, shown in the thickness chart 2b, is about 0.8～1.2nm.Simultaneously, the electron scanning micrograph of Graphene is shown in Figure 3, has further confirmed the thin layer pattern of Graphene.
Claims (6)
1. one kind based on azanol reductive graphene preparation method; It is characterized in that; Through natural graphite powder is obtained oxidation graphite solid through the intercalation oxide treatment, and oxidation graphite solid processed behind the mono-layer graphite oxide aqueous solution and ammoniacal liquor and oxammonium hydrochloride reaction, obtain Graphene solution;
Described natural graphite powder obtains oxidation graphite solid through the intercalation oxide treatment and is meant: with natural graphite powder with adopt the vitriol oil and potassium permanganate to carry out oxidation successively after SODIUMNITRATE mixes; Fully obtain brown graphite oxide suspension-s after the reaction, the suction filtration whiz obtains oxidation graphite solid after ydrogen peroxide 50 and deionized water dilution again;
Adopting the vitriol oil and potassium permanganate to carry out oxidation is meant: the dropping mass percent is 98% the vitriol oil and fully stirs that the dropping time is controlled to be 15min, and stirs 30min at environment below 10 ℃ in natural graphite powder and SODIUMNITRATE in environment below 0 ℃; In 1h, potassium permanganate is added system when keeping stirring environment then, the potassium permanganate that adds each time is 2 ~ 3g, and the timed interval is 20min, keeps system temperature to be lower than 20 ℃, finishes continued for the third time and stirs 30min;
The mono-layer graphite oxide aqueous solution is meant: adopt ultrasonic power to be scattered in the deionized water graphite oxide, graphite oxide is disperseed to peel off into individual layer, process the mono-layer graphite oxide aqueous solution;
Be meant with ammoniacal liquor and oxammonium hydrochloride reaction: add ammoniacal liquor and oxammonium hydrochloride successively at graphene oxide solution, ammoniacal liquor and oxammonium hydrochloride reaction discharge the free azanol, and azanol obtains Graphene solution as reductive agent and graphite oxide alkene reaction in 90 ℃ of water-baths.
2. according to claim 1ly it is characterized in that based on azanol reductive graphene preparation method described natural graphite powder is meant: 500 purpose particulate state natural graphite powders.
3. according to claim 1 based on azanol reductive graphene preparation method; It is characterized in that; Described abundant reaction is meant: slowly drip deionized water and make temperature be no more than 90 ℃ with natural graphite powder and SODIUMNITRATE heating in water bath to 35 ± 3 ℃ and after reacting 2h, obtain brown graphite oxide suspension-s.
4. according to claim 1ly it is characterized in that based on azanol reductive graphene preparation method that described ydrogen peroxide 50 and deionized water dilution are meant: adopting volume ratio is that 30% the ydrogen peroxide 50 of 7:55 and the mixed solution of deionized water dilute.
5. according to claim 1 based on azanol reductive graphene preparation method; It is characterized in that; Described suction filtration whiz is meant: after obtaining filter cake with the B suction filtration, using temperature is that 45 ℃ mass percent is 3% Hydrogen chloride repetitive scrubbing 3 times, in solid filter cake dispersed with stirring water; Centrifugal 20min obtains the graphite oxide gel under the 4000rpm rotating speed, and its dry 24h under 40 ℃ vacuum environment is obtained oxidation graphite solid.
6. according to claim 1ly it is characterized in that based on azanol reductive graphene preparation method described ultrasonic power is meant: operating frequency is 40kHZ, and power is ultrasonic 1h under the 160W effect.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102167314B (en) * | 2011-05-23 | 2012-12-12 | 浙江大学 | Method for preparing graphene |
| CN102557018B (en) * | 2011-12-16 | 2015-07-29 | 中国热带农业科学院农产品加工研究所 | A kind of based on green deoxidation technology graphene preparation method |
| CN103224228A (en) * | 2013-04-07 | 2013-07-31 | 怀化学院 | Selectively reduced graphene oxide and preparation method |
| CN103233296B (en) * | 2013-05-17 | 2015-09-30 | 山西大学 | A kind of preparation method of N doping Flexible graphene fiber |
| CN103723710A (en) * | 2013-11-22 | 2014-04-16 | 盐城纳新天地新材料科技有限公司 | Preparation method of single-layer graphene pyridine solution |
| CN103723709A (en) * | 2013-11-22 | 2014-04-16 | 盐城纳新天地新材料科技有限公司 | Preparation method of aqueous single-layer graphene solution |
| CN104291328B (en) * | 2014-09-25 | 2017-04-12 | 深圳粤网节能技术服务有限公司 | Method for grading and separating graphene materials |
| CN107215868B (en) * | 2017-06-14 | 2019-05-28 | 黑龙江省宝泉岭农垦帝源矿业有限公司 | Utilize the method for the graphene oxide product of oxidation-reduction method Fast Purification preparation high-purity |
| CN108310380A (en) * | 2018-05-07 | 2018-07-24 | 临沂大学 | A kind of graphene-gold nano flower composite material and its preparation method and application |
| CN108854261A (en) * | 2018-07-09 | 2018-11-23 | 山东佳星环保科技有限公司 | The preparation method of graphene high-efficiency filtering material for air purifying |
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| CN101602504A (en) * | 2009-07-16 | 2009-12-16 | 上海交通大学 | Graphene preparation method based on xitix |
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Effective date of registration: 20160617 Address after: 201702, Qingpu District, Shanghai North Green Road No. 1, 9138, 3, K District, room 316 Patentee after: Shanghai carbon Valley New Mstar Technology Ltd Address before: 200240 Dongchuan Road, Shanghai, No. 800, No. Patentee before: Shanghai Jiao Tong University |
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