CN104591173A - Method for preparing graphene by reducing graphene oxide based on camellia oleifera extract - Google Patents
Method for preparing graphene by reducing graphene oxide based on camellia oleifera extract Download PDFInfo
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- CN104591173A CN104591173A CN201510035357.8A CN201510035357A CN104591173A CN 104591173 A CN104591173 A CN 104591173A CN 201510035357 A CN201510035357 A CN 201510035357A CN 104591173 A CN104591173 A CN 104591173A
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Abstract
The invention relates to a method for preparing graphene by reducing graphene oxide based on a camellia oleifera extract and belongs to the technical field of materials. According to the method, by adopting the camellia oleifera extract procyanidine as a reductant for graphene oxide, the efficient reduction of graphene oxide can be achieved under the conditions of acidic environment and 80 DEG C water bath to prepare the graphene. Compared with the existing method for preparing the graphene, the reductant adopted in the method is derived from agricultural and forestry wastes, the system is environment friendly, safe, efficient, inexpensive, is easy to prepared on large scale and has very significant industrial application potential.
Description
Technical field
The invention belongs to field of material technology, relate to the preparation of nano-carbon material, be specifically related to a kind of method preparing Graphene based on oil tea shell extract redox graphene.
Background technology
The preparation method of Graphene mainly contains mechanically peel method, chemical Vapor deposition process, oriented growth method, electrochemical synthesis and chemical synthesis.Wherein, chemistry redox method is the most suitable method of preparation low cost and a large amount of Graphene.Chemistry redox method utilizes oxidizing reaction to be graphite oxide by graphite oxidation, then forms graphene oxide by ultrasonic stripping, then add reductive agent and reduce.Conventional reductive agent has hydrazine hydrate, ethyl hydrazine, NaBH4/ Resorcinol etc.But these reductive agents itself are poisonous or have explosivity, have larger harm.And use these reductive agents to reduce the Graphene obtained in the solution irreversible reunion easily to occur, further modification and functionalization cannot be carried out to it, this significantly limit its application to the higher field of Graphene specification of quality.Therefore, find and adopt reductive agent novel, eco-friendly, cheap and easy to get, adopting simple efficient green method of reducing significant.
Summary of the invention
For existing technology of preparing Problems existing, the present invention proposes a kind of method preparing Graphene based on oil tea shell extract redox graphene, adopt eco-friendly natural plant extract as reductive agent and stablizer, overcome that reductive agent in prior art is poisonous and Graphene that is dangerous and that generate easily produces the problem of irreversible reunion or precipitation.
Technical scheme of the present invention, a kind of method preparing Graphene based on oil tea shell extract redox graphene, is characterized in that method steps is as follows:
(1) graphene oxide is joined in the pycnogenols solution of oil tea shell extraction, add a small amount of hydrochloric acid soln, ultrasonic disperse;
(2) then by mixture Keep agitation reaction 2h under water bath condition, black dispersion stable for gained is crossed 0.22 μm of filter membrane then with milli-Q water at least three times, obtain product;
(3) by product lyophilize, redispersible reduced graphene powder is finally obtained.
Reductive agent of the present invention is the pycnogenols that oil tea shell extracts.
The amount of required pycnogenols of the present invention is the ethanol/water effluent of 50-100 mL 30%, method for preparing extractive is shown in document [Xue Kunpeng, face flowing water, Lai Wenqiang, Huang Zhimin, Guo Huiqin, ultrasonic-microwave enzymolysis is collaborative extracts oil tea shell procyanidins, chemical research and application, 2012,8:1295-1299].
In mixed solution after ultrasonic disperse of the present invention, the amount of graphene oxide is 20-50mg/L.
Solvent in pycnogenols solution of the present invention is the ethanol/water solution of 25-35%.
The amount adding hydrochloric acid of the present invention is 0.8-1mL.
Water-bath temperature of the present invention is 85 ± 5 DEG C.
Cryodesiccated temperature of the present invention is-40 ~-50 DEG C, and relative vacuum degree is lower than-0.015MPa.
Advantage of the present invention is: successfully oil-tea camellia husks being extracted pycnogenols should in redox graphene, pycnogenols had not only played reductive agent but also had played the effect of stablizer, on the one hand graphene oxide is reduced, solve the easy agglomeration traits of Graphene prepared by current reductive agent on the other hand, extend the Application Areas dispersibling Graphene.Simple efficient, the environmental protection of this method, prepared graphene dispersion is good, has expanded its Application Areas.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) spectrogram of the Graphite Powder 99 (a) graphene oxide (b) reduced graphene (c) in embodiment.
As seen from the figure, graphite a curve is that the i.e. diffraction peak in graphite carbon (002) face appears very strong diffraction peak, in 26.7 ° of places at 2 θ, and corresponding spacing of lattice is 0.338nm.With graphite-phase ratio, the peak that graphite oxide b curve is 26.7 ° at 2 θ disappears substantially, occurs diffraction peak at 9.5 ° of places, i.e. graphite oxide (001) face diffraction peak, and corresponding spacing of lattice is 0.827nm, and spacing of lattice obviously increases, and illustrates that stripping is more abundant.Further, compared with graphene oxide, the diffraction peak that Graphene curve c is 9.5 ° at 2 θ disappears, and is about the wider weak diffraction peak of 18 ° of appearance one at 2 θ, show that the oxygen-containing functional group in graphene oxide is reduced removal substantially, obtain reduction state graphene.
Fig. 2 is the infrared spectrogram of graphene oxide (a) and reduced graphene (b).
In figure, at wave number 1730cm after reduction
-1(C=O), 1380 cm
-1(O-H), 1060 cm
-1(C=O) absorption peak at place obviously lowers, 1624 cm
-1(C=C) place's absorption peak improves greatly, shows that the oxygen-containing functional group of graphene oxide greatly reduces, and sp
2the carbon atom knot of hydridization accesses and greatly recovers.
Fig. 3 is the high-resolution-ration transmission electric-lens figure under the different enlargement ratios of reduced graphene.
Insertion figure in Fig. 2 b is the selected area electron diffraction figure of reduced graphene.
As seen from the figure, after reduction, Graphene is full plies structure, and is rendered as fabulous crystalline structure.
Fig. 4 is graphene oxide and the Graphene dispersion effect figure in aqueous after reducing.
In figure, graphene oxide dispersion is tawny transparent mixed solution in aqueous, is reduced rear solution and presents black, and favorable dispersity, show that it is reduced, obtain the Graphene of good dispersity.
Embodiment
Now the invention will be further described with accompanying drawing in conjunction with the embodiments:
Concrete pharmaceutical chemicals involved in the present invention: natural crystalline flake graphite powder, from Chemical Reagent Co., Ltd., Sinopharm Group; Tea seed shell is provided by Jiangxi Lv Hai grease company limited; Sherwood oil (boiling range is 60-90 DEG C), cellulase, methyl alcohol, ethanol, hydrochloric acid, sulfuric acid, potassium permanganate, SODIUMNITRATE, bariumchloride, hydrogen peroxide are domestic analytical reagent.
The product of preparation uses XRD-AXS D8-Advanced type X-ray diffractometer (XRD) of German Shimadzu Bruker company to test its X ray diffracting spectrum; Cu K α radiation, λ=1.5418, sweep limit 5-60 °, scanning speed 5 °/min.
The product of preparation uses the functional group of Paragon 1000 type Fourier transform infrared (FT-IR) spectrometer to product of Perkin-Elmer company of the U.S. to analyze, wavelength region 4000-400cm
-1.
The product of preparation uses the pattern of JEM-2010 type high-resolution-ration transmission electric-lens to Graphene of Jeol Ltd. to observe.
The preparation of graphene oxide: adopt the Hummers legal system after improving for graphene oxide powder.1) in ice bath, by the 115ml vitriol oil (H
2sO
4, 98%) and to pour 1L there-necked flask into ice-cooled to 5 DEG C (ice baths).Then 5g natural flake graphite is slowly joined in the vitriol oil under mechanical agitation, fully add 15g potassium permanganate and 2.5g SODIUMNITRATE successively after dispersion.Control temperature of reaction between 10-15 DEG C, stirring reaction 3h.2) proceeded to by there-necked flask in 35 DEG C of thermostat water baths, constant temperature water bath stirs 30min, obtains beige thick liquid.Slowly add 230ml ultrapure water, control speed makes temperature rise between 90-100 DEG C, after when system temperature is reduced to 85 DEG C, rapidly reactant proceeded to oil bath heating systems and keep mechanical stirring.Make system temperature maintain about 90 DEG C 1h, and continue to stir.3) there-necked flask is shifted out oil bath, and in system, add the dilution of 350ml warm water, now obtain yellowish brown suspension liquid.Add about 15ml hydrogen peroxide in the backward system that stirs, stir until system presents uniform glassy yellow.While hot by mixed solution vacuum filtration, with the hydrochloric acid soln of 5%, much filtrate is fully washed, until without SO in washings
4 2-detect (10% BaCl
2detect).By product graphite oxide (GO) from filter paper scrape and in 80 DEG C of baking ovens vacuum-drying 48h, for subsequent use.
Oil tea shell extracts the preparation of pycnogenols: tea seed shell cleans crushed after being dried and crosses 100 mesh sieves, then uses sherwood oil surname extraction 12h degreasing in 50 DEG C of water-baths, dry.The powder taken after 10.0g degreaser drying is placed in the ethanolic soln of 60ml 60%, add the cellulase phosphate solution that 0.5ml concentration is 0.1%, under ultrasonic frequency 40kHz, microwave power 300W condition, enzyme assisting ultrasonic-microwave cooperating extraction method is adopted to extract 60s at 50 DEG C, by after extracting liquid filtering at 50 DEG C of concentrated evaporates to dryness, obtain sorrel oil tea shell extract coarse meal.0.25g powder is dissolved in 10ml hot methanol, crosses AB-8 macroporous resin column with 3ml/min flow velocity, then carry out gradient elution with 10%, 20% and 30% aqueous ethanolic solution respectively, collect 30% elutriant.
The preparation of graphene oxide dispersion: diluted by graphite oxide deionized water, is mixed with the dispersion liquid that concentration is 50mg/L, after supersound process, obtains the finely dispersed transparent graphene oxide dispersion liquid of tawny.
The preparation of Graphene: in the pycnogenols solution that oil tea shell 10ml graphene oxide dispersion being joined 30% ethanol elution of 100mL extracts, add 1mL concentrated hydrochloric acid, ultrasonic disperse 30min.Then by mixture Keep agitation reaction 2h under 90 DEG C of water bath condition, black dispersion stable for gained is crossed washing after 0.22 μm of membrane filtration, dry, finally obtain redispersible reduced graphene powder.
Claims (8)
1. prepare a method for Graphene based on oil tea shell extract redox graphene, it is characterized in that method steps is as follows:
(1) graphene oxide is joined in the pycnogenols solution of oil tea shell extraction, add a small amount of hydrochloric acid soln, ultrasonic disperse;
(2) then by mixture Keep agitation reaction 2h under water bath condition, black dispersion stable for gained is crossed 0.22 μm of filter membrane then with milli-Q water at least three times, obtain product;
(3) by product lyophilize, redispersible reduced graphene powder is finally obtained.
2. a kind of method preparing Graphene based on oil tea shell extract redox graphene according to claim 1, is characterized in that, reductive agent used in method steps is the pycnogenols that oil tea shell extracts.
3. a kind of method preparing Graphene based on oil tea shell extract redox graphene according to claim 1 and 2, is characterized in that, the amount of required pycnogenols is the ethanol/water effluent of 50-100 mL 30%.
4. a kind of method preparing Graphene based on oil tea shell extract redox graphene according to claim 1, it is characterized in that, in the mixed solution after ultrasonic disperse, the amount of graphene oxide is 0.02-0.05g/L.
5. a kind of method preparing Graphene based on oil tea shell extract redox graphene according to claim 1 and 2, it is characterized in that, the solvent in described pycnogenols solution is the ethanol/water solution of 25-35%.
6. a kind of method preparing Graphene based on oil tea shell extract redox graphene according to claim 1, is characterized in that, add hydrochloric acid amount be 0.8-1mL.
7. a kind of method preparing Graphene based on oil tea shell extract redox graphene according to claim 1, it is characterized in that, water-bath temperature is 85 ± 5 DEG C.
8. a kind of method preparing Graphene based on oil tea shell extract redox graphene according to claim 1, it is characterized in that, cryodesiccated temperature is-40 ~-50 DEG C, and relative vacuum degree is lower than-0.015MPa.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9688539B1 (en) | 2016-05-10 | 2017-06-27 | King Saud University | Green synthesis of reduced graphene oxide using Nigella sativa seed extract |
| CN106955738A (en) * | 2017-04-24 | 2017-07-18 | 西北师范大学 | A kind of anthocyanidin sensitization nano composite material and preparation method and application |
| CN107138160A (en) * | 2017-05-10 | 2017-09-08 | 昆明理工大学 | The preparation method and application of nano zero valence iron/titanium dioxide nano thread/graphene magnetic composite |
| CN110577757A (en) * | 2018-06-07 | 2019-12-17 | 山东欧铂新材料有限公司 | Preparation method of high-dispersion graphene |
| CN112057396A (en) * | 2020-09-11 | 2020-12-11 | 广东墨睿科技有限公司 | Graphene-containing mild cleansing facial cleanser |
| CN112522341A (en) * | 2020-12-30 | 2021-03-19 | 江西神州通油茶科技有限公司 | Co-production method for extracting xylo-oligosaccharide and procyanidine from camellia oleifera shells |
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| CN104003383A (en) * | 2014-06-17 | 2014-08-27 | 哈尔滨工业大学 | Method for preparing graphene |
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| CN104003383A (en) * | 2014-06-17 | 2014-08-27 | 哈尔滨工业大学 | Method for preparing graphene |
Non-Patent Citations (1)
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| 薛昆鹏等: "超声微波酶解协同提取油茶壳中原花青素", 《化学研究与应用》, vol. 24, no. 8, 31 August 2012 (2012-08-31), pages 1295 - 1299 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9688539B1 (en) | 2016-05-10 | 2017-06-27 | King Saud University | Green synthesis of reduced graphene oxide using Nigella sativa seed extract |
| US9850133B2 (en) | 2016-05-10 | 2017-12-26 | King Saud University | Green synthesis of reduced graphene oxide using Nigella sativa seed extract |
| US9975780B2 (en) | 2016-05-10 | 2018-05-22 | King Saud University | Green synthesis of reduced graphene oxide using Nigella sativa seed extract |
| US9988276B2 (en) | 2016-05-10 | 2018-06-05 | King Saud University | Green synthesis of reduced graphene oxide using Nigella sativa seed extract |
| CN106955738A (en) * | 2017-04-24 | 2017-07-18 | 西北师范大学 | A kind of anthocyanidin sensitization nano composite material and preparation method and application |
| CN106955738B (en) * | 2017-04-24 | 2019-10-15 | 西北师范大学 | A kind of anthocyanidin sensitization nanocomposite and the preparation method and application thereof |
| CN107138160A (en) * | 2017-05-10 | 2017-09-08 | 昆明理工大学 | The preparation method and application of nano zero valence iron/titanium dioxide nano thread/graphene magnetic composite |
| CN110577757A (en) * | 2018-06-07 | 2019-12-17 | 山东欧铂新材料有限公司 | Preparation method of high-dispersion graphene |
| CN112057396A (en) * | 2020-09-11 | 2020-12-11 | 广东墨睿科技有限公司 | Graphene-containing mild cleansing facial cleanser |
| CN112522341A (en) * | 2020-12-30 | 2021-03-19 | 江西神州通油茶科技有限公司 | Co-production method for extracting xylo-oligosaccharide and procyanidine from camellia oleifera shells |
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Application publication date: 20150506 |