CN105645398A - Method for stripping preparation of large-scale fluorinated graphene by supercritical carbon dioxide - Google Patents

Method for stripping preparation of large-scale fluorinated graphene by supercritical carbon dioxide Download PDF

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Publication number
CN105645398A
CN105645398A CN201610134195.8A CN201610134195A CN105645398A CN 105645398 A CN105645398 A CN 105645398A CN 201610134195 A CN201610134195 A CN 201610134195A CN 105645398 A CN105645398 A CN 105645398A
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fluorinated graphene
carbon dioxide
autoclave
large scale
supercritical carbon
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戴扬
鄢浩
吴凯
郭尊民
许家伟
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00Structure or properties of graphene
    • C01B2204/04Specific amount of layers or specific thickness
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00Structure or properties of graphene
    • C01B2204/20Graphene characterized by its properties
    • C01B2204/32Size or surface area
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/03Particle morphology depicted by an image obtained by SEM
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/54Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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Abstract

The invention discloses a method for stripping preparation of large-scale fluorinated graphene by supercritical carbon dioxide. The method includes: taking supercritical carbon dioxide as a stripping agent, taking various alcohols and surfactants as dispersing agents, putting graphite powder and the dispersing agents into an autoclave, feeding the carbon dioxide, circularly flowing under a supercritical state, quickly lowering to a normal pressure, repeating the steps to enable the materials to undergo pressure increasing and reducing processes for multiple times, and controlling pressure increasing and reducing times to control fluorinated graphene layer numbers so as to obtain the large-scale fluorinated graphene. Compared with the prior art, the method has the advantages that high-quality of graphene can be prepared; due to physical stripping under mild treatment conditions, quality of the fluorinated graphene cannot be damaged; in addition, the carbon dioxide is nontoxic, cheap and easily acquirable, and technical simplicity and low cost are achieved. Therefore, the method is an environment-friendly large-scale fluorinated graphene production process which has a practical application prospect.

Description

Utilize the method that preparation large scale fluorinated graphene peeled off by supercritical carbon dioxide
Technical field
The present invention relates to a kind of functional material preparation method; a kind of method particularly relating to fluorinated graphene material, is applied to the scale preparation of the materials such as microelectronic material, semi-conducting material, electrode material and polymer composites and the technical field of green manufacturing.
Background technology
Fluorinated graphene especially degree of fluorination is higher, its F/C atom number ratio is more than 0.5, fluorinated graphene not only inherits the high intensity of Graphene, has the height chemically and thermally stability being similar to politef, also has Bandgap extension, luminescence, surface can the characteristic such as low and local magnetic moment simultaneously. By being further introduced into a small amount of oxy radical oxygen-containing fluorinated graphene that such as hydroxyl, epoxy radicals and carboxyl etc. obtain in fluorinated graphene structure, its fluorinated graphene electronic band structure changes, show more specifically optical, electrical and thermal property, the few Rotating fields product comprising 2��10 layers of oxygen-containing fluorinated graphene is called for short the few oxygen-containing fluorinated graphene of layer, the few oxygen-containing fluorinated graphene of layer also has certain optical, electrical and thermal property, shows wider application prospect in fields such as microelectronics, quasiconductor, electrode material and polymer composites. The oxygen-containing fluorinated graphene polarizability that particularly Oil repellent is higher is relatively low, it is filled in the macromolecular materials such as polyimides and can reduce its dielectric constant, and oxygen-containing fluorinated graphene has the two-dimensional nanostructure of uniqueness, it is expected have good potentiation when modified polymer material.
Preparation method about oxygen-containing fluorinated graphene mainly has two kinds at present, one is the method carrying out fluoride for predecessor with graphene oxide, owing to adopting that toxicity is big, the fluoride device of the fluoride of severe corrosive and danger and costliness, the more difficult acquisition practical application of the method, two is adopt the method that business-like fluorographite first carries out chemical modification ultrasonic stripping again, owing to fluorographite polarizability is low, not only hydrophobic but also hate oil, even with in hyperacoustic effect, liquid medium also is difficult to insert its interlayer, it is difficult to its direct ultrasonic stripping obtain the monolayer of higher yields or few layer fluorinated graphene, adopt strong oxidizer or melted KOH NaOH etc. that fluorographite first carries out chemical modification, prepare oxygen-containing fluorographite, again by its ultrasonic stripping in organic solvent, the monolayer being stably dispersed in organic solvent or the few oxygen-containing fluorinated graphene of layer can be obtained.Document (JournalofFluorineChemistry129 (2008) 720 724) is had to adopt melted KOH NaOH chemical modification F/C than the fluorographite being 1, the method is too strong due to alkalescence, cause that fluorine atom substantially removes in modifying process, the fracture of simultaneous C C key, the original two dimensional surface of fluorinated graphene splits and is divided into a lot of small size fragment, the form the few-layer graphene alkene fluorine of 35 layers finally obtained and oxygen content is extremely low, lateral length is only 20 to hundreds of nanometer. Document (RSCAdv., 2013,3,21869 21876) adopt strong oxidizer to F/C ratio (atom number ratio, below all with) be 0.6 commercialization fluorographite first carry out oxidation modification, ultrasonic stripping obtains the oxygen-containing fluorinated graphene of the few layer with 15 layers again, but the method for ultrasonic stripping occurs mainly in F/C ratio in low fluorographite structure owing to aoxidizing after this initial oxidation, the weak effect when process F/C is than the fluorographite more than 0.6, the oxygen-containing fluorinated graphene F/C ratio of gained widow's layer is less than 0.6.
It follows that prior art hardly results in higher yields, F/C than big few layer fluorinated Graphene.
Summary of the invention
In order to solve prior art problem, it is an object of the invention to the deficiency overcoming prior art to exist, a kind of method utilizing supercritical carbon dioxide to peel off preparation large scale fluorinated graphene is provided, the high-quality fluorinated graphene of large scale can be prepared, even preparing the large scale fluorinated graphene of hundreds of microns, and the F/C of prepared fluorinated graphene is higher, the inventive method belongs to physical process and peels off, treatment conditions are gentle, will not destroy the quality of fluorinated graphene; It addition, the CO2 that the inventive method uses is nontoxic, cheap and easily-available, technique is simple, and with low cost, therefore, the inventive method is the friendly process of the large-scale production Graphene with actual application prospect.
Create purpose for reaching foregoing invention, adopt following technical proposals:
A kind of method utilizing supercritical carbon dioxide to peel off preparation large scale fluorinated graphene, employing supercritical CO 2 is remover, also using surfactant as dispersant, comprises the steps:
A. using fluoride carbon dust and dispersant as material, add in autoclave; The weight ratio of fluoride carbon dust and dispersant is preferably 1: (0.1��100); Fluoride carbon dust preferably employs any one material or arbitrarily several composite materials in fluorographite, fluoride fiber and fluoride coke; Dispersant preferably employs sodium lauryl sulphate, dodecylbenzene sodium sulfonate, ethanol or fluorine-containing surfactant;
B. after the temperature in autoclave reaches preset value, being pumped into by carbon dioxide in autoclave, after in autoclave, gas pressure reaches preset value, CO2 starts the cycle over flowing; Temperature in preferred autoclave is 45��300 DEG C, it is preferable that the gas pressure in autoclave is 12��48MPa;
C. circulate after the time reaches predetermined value until CO2, open valve fast pressure relief, reduction of blood pressure in high-speed, make gas pressure in autoclave be down to normal pressure; It is 20��120 minutes that preferred CO2 circulates the time;
D. repeat the process of b and c, making material experience repeatedly boosting and pressure reduction in autoclave, being controlled the number of plies of prepared fluorinated graphene by control boosting and blood pressure lowering number of times, thus preparing large scale fluorinated graphene. As preferred technical scheme, the number of times making the material experience boosting in autoclave and pressure reduction is 1��100 time.
The present invention compared with prior art, has following apparent prominent substantive distinguishing features and remarkable advantage:
1. present invention utilizes the dissolving of supercritical carbon dioxide and diffusivity, make supercritical carbon dioxide and dispersant penetrate in the middle of the layer structure of perfluorocarbon, reduce fluorographite active force between layers;
2. the present invention is by unexpected blood pressure lowering, makes fluorographite layer separate with layer, becomes fluorinated graphene, and dispersant original position is adsorbed on fluorinated graphene surface simultaneously, prevents the gathering of fluorinated graphene;
3. the present invention is by increasing boosting and blood pressure lowering number of times and CO2 circulation time, the number of plies of fluorinated graphene can be reduced, improve the productivity of monolayer fluorinated graphene, can preparing the fluorinated graphene that the bulk that is of a size of several 10 microns Dao hundreds of microns, perfection, the number of plies of 4��10 layers are controlled, technical process is simple, mild condition, green non-pollution, with low cost, it is with a wide range of applications, it is expected to produce huge economic benefit.
Accompanying drawing explanation
Fig. 1 is that the embodiment of the present invention one utilizes supercritical carbon dioxide to peel off the process unit structural representation of preparation large scale fluorinated graphene.
Fig. 2 is that the embodiment of the present invention one utilizes supercritical carbon dioxide to peel off the electron scanning micrograph of preparation large scale fluorinated graphene.
Detailed description of the invention
Details are as follows for the preferred embodiments of the present invention:
Embodiment one:
In the present embodiment, referring to Fig. 1, a kind of method utilizing supercritical carbon dioxide to peel off preparation large scale fluorinated graphene, employing supercritical CO 2 is remover, also using surfactant as dispersant, the technological equipment adopted is as shown in Figure 1, supercritical carbon dioxide peels off the process unit of preparation large scale fluorinated graphene by carbon dioxide steel cylinder 1, chiller 2, carbon dioxide pump 3, autoclave 4, temperature control system 5, control pressurer system 6 and release tank 7 form, carbon dioxide steel cylinder 1 passes sequentially through chiller 2 and connects with the fluid intake of carbon dioxide pump 3 with autoclave 4, temperature control system 5 and control pressurer system 6 detect and the temperature that controls in autoclave 4 and air pressure respectively, release tank 7 is connected with autoclave 4 by relief valve. the present embodiment utilizes the method that preparation large scale fluorinated graphene peeled off by supercritical carbon dioxide to comprise the steps:
A. using fluoride carbon dust and dispersant sodium lauryl sulphate as material, adding in autoclave 4, the weight ratio of fluoride carbon dust and sodium lauryl sulphate is 1: 0.1;
B. reaching after preset value 45 DEG C until the temperature in autoclave 4, control carbon dioxide pump 3 and pumped into by carbon dioxide in autoclave 4, after in autoclave 4, gas pressure reaches preset value 18MPa, CO2 starts the cycle over flowing;
C. circulate after the time reaches predetermined value 20 minutes until CO2, open valve fast pressure relief, reduction of blood pressure in high-speed, make gas pressure in autoclave 4 be down to normal pressure;
D. repeating the process of b and c, making the material in autoclave 4 then through going through 1 boosting and pressure reduction, thus preparing large scale fluorinated graphene. The electron scanning micrograph of fluorinated graphene prepared by the present embodiment is as in figure 2 it is shown, obtain the few layer fluorinated graphene less than 10 layers.
The present embodiment adopts supercritical CO 2 to be remover, with Surfactant SDS for dispersant, fluoride carbon dust and dispersant are placed in autoclave, passing into CO2 again, circulate under postcritical state, reduction of blood pressure in high-speed is to normal pressure afterwards, repeat said process, make material experience repeatedly boosting and pressure reduction, control the fluorinated graphene number of plies by controlling boosting and blood pressure lowering number of times, namely prepare large scale Graphene.Compared with prior art, the present embodiment can prepare high-quality Graphene, and the present embodiment method belongs to physical process and peels off, and treatment conditions are gentle, will not destroy the quality of fluorinated graphene; It addition, the CO2 that the present embodiment method uses is nontoxic, cheap and easily-available, technique is simple, and with low cost, therefore, the present embodiment method is the friendly process of the large-scale production fluorinated graphene with actual application prospect.
Embodiment two:
The present embodiment is essentially identical with embodiment one, is particular in that:
In the present embodiment, the method utilizing supercritical carbon dioxide to peel off preparation large scale fluorinated graphene, comprise the steps:
A. using fluoride carbon dust and dispersant sodium lauryl sulphate as material, adding in autoclave 4, the weight ratio of fluoride carbon dust and sodium lauryl sulphate is 1: 5;
B. reaching after preset value 40 DEG C until the temperature in autoclave 4, control carbon dioxide pump 3 and pumped into by carbon dioxide in autoclave 4, after in autoclave 4, gas pressure reaches preset value 18MPa, CO2 starts the cycle over flowing;
C. circulate after the time reaches predetermined value 120 minutes until CO2, open valve fast pressure relief, reduction of blood pressure in high-speed, make gas pressure in autoclave 4 be down to normal pressure;
D. repeating the process of b and c, making the material in autoclave 4 then through going through 1 boosting and pressure reduction, thus preparing large scale fluorinated graphene. Characterizing by testing, in fluorinated graphene product prepared by the present embodiment, the Graphene less than 10 layers accounts for 42%.
Embodiment three:
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, the method utilizing supercritical carbon dioxide to peel off preparation large scale fluorinated graphene, comprise the steps:
A. using fluoride carbon dust and dodecylbenzene sodium sulfonate as material, adding in autoclave 4, the weight ratio of fluoride carbon dust and dodecylbenzene sodium sulfonate is 1: 6;
B. reaching after preset value 45 DEG C until the temperature in autoclave 4, control carbon dioxide pump 3 and pumped into by carbon dioxide in autoclave 4, after in autoclave 4, gas pressure reaches preset value 10MPa, CO2 starts the cycle over flowing;
C. circulate after the time reaches predetermined value 60 minutes until CO2, open valve fast pressure relief, reduction of blood pressure in high-speed, make gas pressure in autoclave 4 be down to normal pressure;
D. repeating the process of b and c, making the material in autoclave 4 then through going through 3 boostings and pressure reduction, thus preparing large scale fluorinated graphene. Characterizing by testing, in fluorinated graphene product prepared by the present embodiment, the Graphene less than 10 layers accounts for 53%.
Embodiment four:
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, the method utilizing supercritical carbon dioxide to peel off preparation large scale fluorinated graphene, comprise the steps:
A. using fluoride carbon dust and ethanol as material, adding in autoclave 4, the weight ratio of fluoride carbon dust and ethanol is 1: 12;
B. reaching after preset value 55 DEG C until the temperature in autoclave 4, control carbon dioxide pump 3 and pumped into by carbon dioxide in autoclave 4, after in autoclave 4, gas pressure reaches preset value 12MPa, CO2 starts the cycle over flowing;
C. circulate after the time reaches predetermined value 30 minutes until CO2, open valve fast pressure relief, reduction of blood pressure in high-speed, make gas pressure in autoclave 4 be down to normal pressure;
D. repeating the process of b and c, making the material in autoclave 4 then through going through 3 boostings and pressure reduction, thus preparing large scale fluorinated graphene. Characterizing by testing, in fluorinated graphene product prepared by the present embodiment, the Graphene less than 10 layers accounts for 61%.
Above in conjunction with accompanying drawing, the embodiment of the present invention is illustrated; but the invention is not restricted to above-described embodiment; multiple change can also be made according to the purpose of the innovation and creation of the present invention; change, modification, replacement, combination or the simplification made under all spirit according to technical solution of the present invention and principle; all should be the substitute mode of equivalence; as long as meeting the goal of the invention of the present invention; utilize supercritical carbon dioxide to peel off know-why and the inventive concept of the method preparing large scale fluorinated graphene without departing from the present invention, broadly fall into protection scope of the present invention.

Claims (7)

1. one kind utilizes the method that preparation large scale fluorinated graphene peeled off by supercritical carbon dioxide, it is characterised in that employing supercritical CO 2 is remover, also using surfactant as dispersant, comprises the steps:
A. using fluoride carbon dust and dispersant as material, add in autoclave;
B. after the temperature in autoclave reaches preset value, being pumped into by carbon dioxide in autoclave, after in autoclave, gas pressure reaches preset value, CO2 starts the cycle over flowing;
C. circulate after the time reaches predetermined value until CO2, open valve fast pressure relief, reduction of blood pressure in high-speed, make gas pressure in autoclave be down to normal pressure;
D. repeat the process of described b and c, making material experience repeatedly boosting and pressure reduction in autoclave, controlling the number of plies of prepared fluorinated graphene by controlling boosting and blood pressure lowering number of times, thus preparing large scale fluorinated graphene.
2. utilize the method that preparation large scale fluorinated graphene peeled off by supercritical carbon dioxide according to claim 1, it is characterised in that: in described step a, the weight ratio of fluoride carbon dust and dispersant is 1: (0.1��100).
3. the method utilizing supercritical carbon dioxide to peel off preparation large scale fluorinated graphene according to claim 1 or claim 2, it is characterized in that: in described step a, described fluoride carbon dust is any one material or arbitrarily several composite material in fluorographite, fluoride fiber and fluoride coke.
4. the method utilizing supercritical carbon dioxide to peel off preparation large scale fluorinated graphene according to claim 1 or claim 2, it is characterized in that: in described step a, described dispersant is sodium lauryl sulphate, dodecylbenzene sodium sulfonate, ethanol or fluorine-containing surfactant.
5. the method utilizing supercritical carbon dioxide to peel off preparation large scale fluorinated graphene according to claim 1 or claim 2, it is characterized in that: in described step b, temperature in described autoclave is 45��300 DEG C, and the gas pressure in described autoclave is 12��48MPa.
6. the method utilizing supercritical carbon dioxide to peel off preparation large scale fluorinated graphene according to claim 1 or claim 2, it is characterised in that: in described step c, it is 20��120 minutes that described CO2 circulates the time.
7. the method utilizing supercritical carbon dioxide to peel off preparation large scale fluorinated graphene according to claim 1 or claim 2, it is characterised in that: in described step c, the number of times making the material experience boosting in autoclave and pressure reduction is 1��100 time.
CN201610134195.8A 2016-03-10 2016-03-10 Method for stripping preparation of large-scale fluorinated graphene by supercritical carbon dioxide Pending CN105645398A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106517168A (en) * 2016-11-10 2017-03-22 中国石油大学(北京) Device and method for preparing graphene by exfoliating graphite through quick pressure relief
CN106829938A (en) * 2017-03-09 2017-06-13 辽宁兰晶科技有限公司 The method that overcritical sulfur hexafluoride stripping prepares Graphene or graphene nanometer sheet
CN106882795A (en) * 2016-12-28 2017-06-23 成都新柯力化工科技有限公司 A kind of scale ultrasound stripping prepares the application of the method and Graphene of Graphene
CN107399734A (en) * 2017-08-09 2017-11-28 福建猛狮新能源科技有限公司 A kind of high yield fluorinated graphene preparation method
CN107487769A (en) * 2017-08-04 2017-12-19 辽宁兰晶科技有限公司 A kind of method that oil-soluble fluorinated graphene is prepared using fluoride supercritical fluid
CN107501819A (en) * 2017-09-15 2017-12-22 中国南方电网有限责任公司超高压输电公司贵阳局 A kind of modified polytetrafluoroethylresin resin
CN107814407A (en) * 2017-11-06 2018-03-20 上海纳米技术及应用国家工程研究中心有限公司 Method that supercritical carbon dioxide prepares ultra-thin two-dimension cuprous oxide and products thereof and application
CN112624098A (en) * 2021-01-20 2021-04-09 湖北卓熙氟化股份有限公司 Preparation method and application of fluorinated graphene with high fluorocarbon ratio
CN113772666A (en) * 2021-10-25 2021-12-10 大连元晶科技有限公司 Method for preparing oil-soluble fluorinated graphene by stripping with supercritical carbon dioxide
CN116083084A (en) * 2022-11-23 2023-05-09 苏州科技大学 Method for inducing zero band gap two-dimensional material fluorescence by fluorination

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102515155A (en) * 2012-01-05 2012-06-27 上海交通大学 Method for preparing large-scale graphene through supercritical carbon dioxide exfoliation

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
CN102515155A (en) * 2012-01-05 2012-06-27 上海交通大学 Method for preparing large-scale graphene through supercritical carbon dioxide exfoliation

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106517168A (en) * 2016-11-10 2017-03-22 中国石油大学(北京) Device and method for preparing graphene by exfoliating graphite through quick pressure relief
CN106882795A (en) * 2016-12-28 2017-06-23 成都新柯力化工科技有限公司 A kind of scale ultrasound stripping prepares the application of the method and Graphene of Graphene
CN106882795B (en) * 2016-12-28 2018-09-28 成都新柯力化工科技有限公司 A kind of scale ultrasound stripping prepares the method for graphene and the application of graphene
CN106829938A (en) * 2017-03-09 2017-06-13 辽宁兰晶科技有限公司 The method that overcritical sulfur hexafluoride stripping prepares Graphene or graphene nanometer sheet
CN107487769A (en) * 2017-08-04 2017-12-19 辽宁兰晶科技有限公司 A kind of method that oil-soluble fluorinated graphene is prepared using fluoride supercritical fluid
CN107399734A (en) * 2017-08-09 2017-11-28 福建猛狮新能源科技有限公司 A kind of high yield fluorinated graphene preparation method
CN107501819B (en) * 2017-09-15 2020-01-07 中国南方电网有限责任公司超高压输电公司贵阳局 Modified polytetrafluoroethylene resin
CN107501819A (en) * 2017-09-15 2017-12-22 中国南方电网有限责任公司超高压输电公司贵阳局 A kind of modified polytetrafluoroethylresin resin
CN107814407A (en) * 2017-11-06 2018-03-20 上海纳米技术及应用国家工程研究中心有限公司 Method that supercritical carbon dioxide prepares ultra-thin two-dimension cuprous oxide and products thereof and application
CN112624098A (en) * 2021-01-20 2021-04-09 湖北卓熙氟化股份有限公司 Preparation method and application of fluorinated graphene with high fluorocarbon ratio
CN113772666A (en) * 2021-10-25 2021-12-10 大连元晶科技有限公司 Method for preparing oil-soluble fluorinated graphene by stripping with supercritical carbon dioxide
CN116083084A (en) * 2022-11-23 2023-05-09 苏州科技大学 Method for inducing zero band gap two-dimensional material fluorescence by fluorination
CN116083084B (en) * 2022-11-23 2024-02-09 苏州科技大学 Method for inducing zero band gap two-dimensional material fluorescence by fluorination

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Application publication date: 20160608