CN102583358A - Method for preparing functionalized graphene based on high-energy irradiation one-step method - Google Patents
Method for preparing functionalized graphene based on high-energy irradiation one-step method Download PDFInfo
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- CN102583358A CN102583358A CN2012100958882A CN201210095888A CN102583358A CN 102583358 A CN102583358 A CN 102583358A CN 2012100958882 A CN2012100958882 A CN 2012100958882A CN 201210095888 A CN201210095888 A CN 201210095888A CN 102583358 A CN102583358 A CN 102583358A
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Abstract
The invention discloses a method for preparing functionalized graphene based on a high-energy irradiation one-step method. The method comprises the following steps of: mixing graphite oxide and polar small molecular organic solvent, and performing ultrasonic dispersion treatment on the mixed solution for 0.5 to 2 hours, wherein the polar small molecular organic solvent is one or more of epoxy chloropropane, styrene/ acetone solution, acrylic acid and lactic acid; and putting the dispersion in an irradiation source chamber of 60 Co, performing gamma ray irradiation on the mixed solution under the conditions that the irradiation dose rate is 0.6*10<3> to 6*10<3>Gy/h and the irradiation dose is 1*10<4> to 2*10<6>Gy, so that the surface of the graphite oxide is peeled, and functionalized graphene nano sheets are formed. By using the characteristics of high energy and strong penetrating power of gamma ray particles in the method, the functionalized small molecular organic substance intercalated into graphite oxide layers and the graphite oxide layers undergo grafting reaction, so that the distance between the graphite oxide layers is increased, and the graphene nano sheets are formed by peeling.
Description
Technical field
The invention belongs to inorganic carbon material structure modification technology field, particularly relate to a kind of method for preparing functionalization graphene based on one step of high-energy irradiation.
Background technology
Graphene carbon atom intensive by one deck, that be wrapped on the honeycomb crystal lattice is formed, and is the thinnest in the world two-dimensional material, and its thickness is merely 0.35nm.This special construction has contained abundant and novel physical phenomenon, makes Graphene show many excellent properties.For example: the intensity of Graphene is in the test material more than 100 times of the highest steel; Its carrier mobility is at present known twice with indium antimonide material of high mobility; Its thermal conductivity is adamantine 3 times; And it also has special propertys such as room temperature quantum hall effect and room-temperature ferromagnetic.
In recent years; Graphene and matrix material thereof occupy more and more important position with its excellent performance in field of materials, and graphene-based matrix material more is considered to and will has the major application prospect in fields such as microelectrode equipment, transmitter, biological medicine, mechanical resonator, ultracapacitors.But its shortcoming is neither hydrophilic also oleophylic not, and therefore the chemical reaction inertia has hindered it and used, thereby enlarged its range of application and promote that the effective way of its development is that this material is carried out oxidation and functionalization, so that it can be scattered in certain solution in addition.The functional method of Graphene mainly is covalent linkage functional method and non covalent bond functional method at present.The covalent linkage functional method is the functional method the most widely of research at present, and it carries out functionalization through the chemical reaction grafting to Graphene based on the carboxyl that contains in the graphene oxide, hydroxyl and epoxy bond isoreactivity group.Except that the covalent linkage functionalization, can also use non covalent bond action methods such as π-π interaction, ionic linkage and hydrogen bond to realize the functionalization of graphene nanometer sheet.The former has brought new function for graphene nanometer sheet, destroys the structure of Graphene easily, though the latter has kept the structure of graphene nanometer sheet, but in Graphene, has introduced other component.
Summary of the invention
In order to address the above problem, the object of the present invention is to provide a kind of operating process simple, with low cost prepare the method for functionalization graphene based on high-energy irradiation one step.
In order to achieve the above object, the method for preparing functionalization graphene based on high-energy irradiation one step provided by the invention comprises the following step that carries out in order:
1) will mix with polarity small molecules organic solvent as the graphite oxide of raw material; Then mixing solutions is carried out ultra-sonic dispersion and handle 0.5～2 hour so that the two mixes, polarity small molecules organic solvent is selected from one or more in epoxy chloropropane, vinylbenzene/acetone soln, vinylformic acid and the lactic acid;
2) above-mentioned dispersion liquid is placed
60The irradiation source of Co is indoor, is 0.6 * 10 at radiation dose rate then
3Gy/h～6 * 10
3Gy/h, irradiation dose are 1 * 10
4Gy～2 * 10
6Under the condition of Gy mixing solutions is carried out gamma-ray irradiation, irradiation time is 1.6～3000 hours, makes the sur-face peeling of graphite oxide and forms graphene nanometer sheet.
The amount ratio of described graphite oxide and polarity small molecules organic solvent is 1mg: 0.1～100ml.
Described radiation treatment temperature is 0～80 ℃.
The method for preparing functionalization graphene based on high-energy irradiation one step provided by the invention is a kind of covalent linkage functional method; It is to utilize the characteristics that the gamma-rays particle energy is high, penetration power is strong; Make intercalation get into the functionalization small organic molecule and the graphite oxide generation graft reaction of thicker graphite oxide interlayer; Thereby cause the graphite oxide interlamellar spacing to increase, and then peel off the formation graphene nanometer sheet.Since the graphene nanometer sheet surface grafting of this functionalization a large amount of polar functional groups, soluble in water, THF equal solvent neutralization is dispersed in the macromolecule resin, can be widely used in the research fields such as preparation of nano composite material, transmitter.In addition, it is simple, with low cost that the inventive method also has operating process, advantages such as environmental protection, and can increase the ratio of single-layer graphene nanometer sheet, and obtain high-quality functionalization graphene material, realize industrialized mass production.
Description of drawings
Fig. 1 is the graphite oxide of pre-irradiation and the graphene nanometer sheet XRD spectra behind the irradiation.
Fig. 2 is the graphite oxide of pre-irradiation and the graphene nanometer sheet XPS spectrum figure behind the irradiation.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment the method for preparing functionalization graphene based on one step of high-energy irradiation provided by the invention is elaborated.
Embodiment 1:
Obtain the graphite oxide powder after will drying according to the graphite oxide that the said method of document " Improved Synthesis of Graphene Oxide " is prepared; Get the graphite oxide powder that 50mg prepares; It is joined in the vial that 50mL epoxy chloropropane reagent is housed; Mixing solutions was carried out ultra-sonic dispersion 1 hour, and the vial that above-mentioned dispersion liquid will be housed then places
60In the gamma-ray irradiation chamber of Co, be 2.0 * 10 at radiation dose rate
3Gy/h, irradiation dose are 2 * 10
5Carry out gamma-ray irradiation under the condition of Gy, irradiation time is 100 hours, and irradiation temperature is a room temperature, makes the sur-face peeling of graphite oxide and forms graphene nanometer sheet.The above-mentioned graphene nanometer sheet that obtains is carried out X-ray diffraction (XRD) and X-ray photoelectron spectroscopic analysis respectively, and with the graphite oxide of pre-irradiation as a comparison, result such as Fig. 1, shown in Figure 2.Visible by Fig. 1, the interlamellar spacing of graphene nanometer sheet obviously increases to 1.17nm by the 0.93nm of graphite oxide, and major part is peeled off; Visible by Fig. 2, epoxy chloropropane successfully is grafted to the surface (can be observed in Graphene that irradiation obtain contain the chlorine element by the XPS collection of illustrative plates) of graphite oxide, has realized step preparation functionalization graphene nanometer sheet thus.
Embodiment 2:
Obtain the graphite oxide powder after will drying according to the graphite oxide that the said method of document " Improved synthesis of graphene oxide " is prepared; Get the graphite oxide powder that 40mg prepares; It is joined in the vial that 100mL vinylbenzene/acetone soln (50wt%) is housed; Mixing solutions is carried out ultra-sonic dispersion handled 2 hours, the vial that above-mentioned dispersion liquid will be housed then places
60In the gamma-ray irradiation chamber of Co, be 1.0 * 10 at radiation dose rate
3Gy/h, irradiation dose are 5 * 10
5Carry out gamma-ray irradiation under the condition of Gy, irradiation time is 500 hours, and irradiation temperature is 50 ℃, makes the sur-face peeling of graphite oxide and forms graphene nanometer sheet.Can know that through XRD analysis and XPS ultimate analysis vinylbenzene successfully is grafted to the surface of graphite oxide, and peel off and obtained the functionalization graphene nanometer sheet.
Embodiment 3:
Obtain the graphite oxide powder after will drying according to the graphite oxide that the said method of document " Improved synthesis of graphene oxide " is prepared; Get the graphite oxide powder that 100mg prepares; It is joined in the vial that 100mL vinylformic acid/aqueous solution (10wt%) is housed; Mixing solutions is carried out ultra-sonic dispersion handled 2 hours, the vial that above-mentioned dispersion liquid will be housed then places
60In the gamma-ray irradiation chamber of Co, be 2.0 * 10 at radiation dose rate
3Gy/h, irradiation dose are 3 * 10
4Carry out gamma-ray irradiation under the condition of Gy, irradiation time is 15 hours, and irradiation temperature is 40 ℃, makes the sur-face peeling of graphite oxide and forms graphene nanometer sheet.Can know that through XRD analysis and XPS ultimate analysis vinylformic acid successfully is grafted to the surface of graphite oxide, and peel off and obtained the functionalization graphene nanometer sheet.
Embodiment 4:
Obtain the graphite oxide powder after will drying according to the graphite oxide that the said method of document " Improved synthesis of graphene oxide " is prepared; Get the graphite oxide powder that 100mg prepares; It is joined in the vial that 100mL lactic acid/aqueous solution (10wt%) is housed; Mixing solutions is carried out ultra-sonic dispersion handled 1.5 hours, the vial that above-mentioned dispersion liquid will be housed then places
60In the gamma-ray irradiation chamber of Co, be 2.0 * 10 at radiation dose rate
3Gy/h, irradiation dose are 3 * 10
4Carry out gamma-ray irradiation under the condition of Gy, irradiation time is 30 hours, and irradiation temperature is 60 ℃, makes the sur-face peeling of graphite oxide and forms graphene nanometer sheet.Can know that through XRD analysis and XPS ultimate analysis lactic acid successfully is grafted to the surface of graphite oxide, and peel off and obtained the functionalization graphene nanometer sheet.
Claims (3)
1. one kind prepares the method for functionalization graphene based on high-energy irradiation one step, and it is characterized in that: described method comprises the following step that carries out in order:
1) will mix with polarity small molecules organic solvent as the graphite oxide of raw material; Then mixing solutions is carried out ultra-sonic dispersion and handled 0.5～2 hour so that the two mixes, polarity small molecules organic solvent is selected from a kind of in epoxy chloropropane, vinylbenzene/acetone soln, vinylformic acid, the lactic acid;
2) above-mentioned dispersion liquid is placed
60The irradiation source of Co is indoor, is 0.6 * 10 at radiation dose rate then
3Gy/h～6 * 10
3Gy/h, irradiation dose are 1 * 10
4Gy～2 * 10
6Under the condition of Gy mixing solutions is carried out gamma-ray irradiation, irradiation time is 1.6～3000 hours, makes the sur-face peeling of graphite oxide and forms graphene nanometer sheet.
2. according to claim 1ly prepare the method for functionalization graphene based on high-energy irradiation one step, it is characterized in that: the amount ratio of described graphite oxide and polarity small molecules organic solvent is 1mg: 0.1～100ml.
3. according to claim 1ly prepare the method for functionalization graphene based on high-energy irradiation one step, it is characterized in that: described radiation treatment temperature is 0～80 ℃.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863824A (en) * | 2012-08-25 | 2013-01-09 | 华南理工大学 | Method for preparing unsaturated carboxylic zinc salt functionalized graphene |
| CN103011151A (en) * | 2012-12-28 | 2013-04-03 | 黑龙江省科学院技术物理研究所 | Method for preparing graphene/nickel nanocomposite material by utilizing gamma ray |
| CN103193227A (en) * | 2013-05-02 | 2013-07-10 | 哈尔滨工业大学 | Method for preparing highly flame retardant expansible graphite |
| CN103964419A (en) * | 2014-04-17 | 2014-08-06 | 王宏晓 | Preparation method and application of high-purity high-fineness graphite powder |
| CN104098093A (en) * | 2014-08-01 | 2014-10-15 | 天津工业大学 | Method for preparing fluorinated graphene based on gama ray irradiation |
| CN104211057A (en) * | 2014-09-12 | 2014-12-17 | 天津工业大学 | Method for preparing three-dimensional graphene ultralight foams |
| CN106299310A (en) * | 2016-09-28 | 2017-01-04 | 天津工业大学 | A kind of method of efficient preparation graphene/metal oxide composite |
| CN109023453A (en) * | 2018-08-23 | 2018-12-18 | 安徽江杰实业有限公司 | A kind of processing method promoting stainless steel tube antiseptic property |
| CN110980723A (en) * | 2019-12-27 | 2020-04-10 | 洛阳森蓝化工材料科技有限公司 | Graphite puffing treatment process |
Citations (2)
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| CN101559941A (en) * | 2009-05-26 | 2009-10-21 | 上海大学 | Method for preparing graphite alkenyl nanometer materials by electron beam irradiation method |
| CN101607706A (en) * | 2009-07-10 | 2009-12-23 | 天津工业大学 | A kind of method that is used to improve degree of graphitization of graphite material |
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2012
- 2012-04-05 CN CN2012100958882A patent/CN102583358A/en active Pending
Patent Citations (2)
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| CN101559941A (en) * | 2009-05-26 | 2009-10-21 | 上海大学 | Method for preparing graphite alkenyl nanometer materials by electron beam irradiation method |
| CN101607706A (en) * | 2009-07-10 | 2009-12-23 | 天津工业大学 | A kind of method that is used to improve degree of graphitization of graphite material |
Non-Patent Citations (1)
| Title |
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| BOWU ZHANG ET AL.: "Radiation induced reduction: an effective and clean route to synthesize functionalized graphene", 《JOURNAL OF MATERIALS CHEMISTRY》, vol. 22, 9 March 2012 (2012-03-09), pages 7775 - 7781 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863824A (en) * | 2012-08-25 | 2013-01-09 | 华南理工大学 | Method for preparing unsaturated carboxylic zinc salt functionalized graphene |
| CN103011151A (en) * | 2012-12-28 | 2013-04-03 | 黑龙江省科学院技术物理研究所 | Method for preparing graphene/nickel nanocomposite material by utilizing gamma ray |
| CN103193227A (en) * | 2013-05-02 | 2013-07-10 | 哈尔滨工业大学 | Method for preparing highly flame retardant expansible graphite |
| CN103964419A (en) * | 2014-04-17 | 2014-08-06 | 王宏晓 | Preparation method and application of high-purity high-fineness graphite powder |
| CN104098093A (en) * | 2014-08-01 | 2014-10-15 | 天津工业大学 | Method for preparing fluorinated graphene based on gama ray irradiation |
| CN104211057A (en) * | 2014-09-12 | 2014-12-17 | 天津工业大学 | Method for preparing three-dimensional graphene ultralight foams |
| CN106299310A (en) * | 2016-09-28 | 2017-01-04 | 天津工业大学 | A kind of method of efficient preparation graphene/metal oxide composite |
| CN109023453A (en) * | 2018-08-23 | 2018-12-18 | 安徽江杰实业有限公司 | A kind of processing method promoting stainless steel tube antiseptic property |
| CN110980723A (en) * | 2019-12-27 | 2020-04-10 | 洛阳森蓝化工材料科技有限公司 | Graphite puffing treatment process |
| CN110980723B (en) * | 2019-12-27 | 2022-10-21 | 洛阳森蓝化工材料科技有限公司 | Graphite puffing treatment process |
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Application publication date: 20120718 |