CN104986751A - Method for efficiently producing chlorinated graphene - Google Patents
Method for efficiently producing chlorinated graphene Download PDFInfo
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- CN104986751A CN104986751A CN201510498519.1A CN201510498519A CN104986751A CN 104986751 A CN104986751 A CN 104986751A CN 201510498519 A CN201510498519 A CN 201510498519A CN 104986751 A CN104986751 A CN 104986751A
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Abstract
The invention discloses a method for efficiently producing chlorinated graphene. The method comprises the following steps that graphene powder is heated, so that a part of moisture is removed, vacuumizing is conducted until moisture of the graphene powder is completely removed, and the graphene powder continues to be heated; the graphene powder and chlorine react at a certain temperature, and a chlorinated graphene powder material is obtained; the chlorinated graphene powder material is treated with nitrogen, free chlorine adsorbed on the surface of the chlorinated graphene powder is removed, and pure chlorinated graphene powder is obtained. Negative electricity exists among the chlorinated graphene powder prepared according to the method due to the action of a chlorine functional group, and the chlorinated graphene powder is fluffier and easier to scatter in use due to the action that like charges repel; in addition, the number of steps of the preparation method is small, the productivity is high, the technology is simple, and large-scale industrial production is easy to achieve.
Description
Technical field
The present invention relates to the technology of preparing of Graphene, be specifically related to a kind of method of High-efficient Production chlorination Graphene, be applicable to the production in enormous quantities of chlorination Graphene.
Background technology
Graphene is a kind of New Two Dimensional carbon nanomaterial by monolayer carbon atomic building, it has very high specific surface area, the advantages such as excellent conduction, thermal conductivity and mechanical property, and make it be with a wide range of applications in matrix material, functional materials, power material, the multiple field of sensor due to its special energy band structure and photoelectric property.But pure Graphene still defectiveness in many application, carrying out element doping to pure Graphene is a kind of effective means improving Graphene defect.After element doping, the energy band structure of Graphene can change, and makes its electricity, optics and magnetic performance there occurs significant change, and becomes a kind of and have brand-new composite nano material.
At present, the non-metallic element adulterated in Graphene has nitrogen, boron, phosphorus, sulphur, chlorine etc., but it is less to the research of chlorine doped graphene, Wu etc. use electron cyclotron resonace technology to prepare chlorine doped graphene, but the requirement of the method to equipment is high, complicated operation, limits it and further applies.(Justin Wu, Liming Xie, Yanguang Li, Hailiang Wang, Yijian Ouyang, Jing Guo, and Hongjie Dai. Controlled chlorine plasma reaction for noninvasive graphene doping [J]. J.Am.Chem.Soc., 2011,133:19668-19671.) Li etc. utilizes photocatalysis by the carbon atom Covalent attachment above chlorine radical and Graphene, prepare chlorine doped graphene, but the method complicated operation, can not preparation in macroscopic quantity be used for.(Bo Li, Lin Zhou, Di Wu, Hailin Peng, Kai Yan, Yu Zhou, and Zhongfan Liu. Photochemical chlorination of graphene [J]. ACS Nano, 2011, 5 (7): 5957-5961.) the magnesium rod activation methyl chloride of burning such as Jin Huile, generate dichlorocarbene, these dichlorocarbenes again self-assembly generate chlorine doped graphene, obtained chlorine doped graphene can be used as cathode catalyst material and applies in oxygen reduction electrode, but the method needs to carry out separating for several times to product, precipitation, washing, produce a large amount of tetracol phenixin and Using of Chloroform Waste Liquid, aftertreatment is comparatively complicated, if and deal with improperly, have violent in toxicity phosgene to produce.(being the Chinese invention patent application of CN 103111312 A see publication number).
Summary of the invention
The problem to be solved in the present invention is a kind of method providing High-efficient Production chlorination Graphene, and compared with prior art, method production process provided by the invention is simple, cost is low, productive rate is high, is easy to large-scale industrial production.
In order to solve above technical problem, the preparation method of chlorination grapheme material of the present invention, comprises the following steps:
(1) graphene powder is carried out heating remove portion moisture, the moisture being evacuated to graphene powder is drained completely, continues heating;
(2) above-mentioned graphene powder and chlorine are reacted at a certain temperature, obtain chlorination graphene powder material;
(3) above-mentioned chlorination graphene powder material nitrogen is processed, to remove the free chlorine of chlorination graphene powder surface adsorption, obtain pure chlorination graphene powder.
Described step (1) graphene powder is Graphene, graphene microchip, the purity 95 ~ 99.5% of graphene powder.
Described step is heated to 40 ~ 60 DEG C to graphene powder in (1), then vacuumizes, vacuum pressure 0.8 ~ 0.1MPa, pumpdown time 10 ~ 30min, after being drained completely to graphene powder moisture, stop vacuumizing, the heating that heats up is continued to graphene powder.
The temperature of reaction of described step (2) graphene powder and chlorine is 300 ~ 600 DEG C, and the flow velocity of logical chlorine is 450 ~ 950 ml/min, and the reaction times is 0.5 ~ 8h.
Described step (3) nitrogen gas purity is 98 ~ 99.999%, and chlorination Graphene productive rate reaches 93 ~ 98%.
Feature of the present invention and beneficial effect: the present invention utilizes the high temperature high oxidative capacity of chlorine to make edge or the surface doping grafting Shang Lv functional group of Graphene, and chlorine uniform doping in prepared chlorination Graphene, assay reproducibility is good.The productive rate of prepared chlorination Graphene is high, reaches 93 ~ 98%.This preparation method's step is few, productive rate is high, technique is simple, is easy to large-scale industrial production.
Embodiment
For a better understanding of the present invention, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to following specific embodiment.
Embodiment 1: take 100g graphene powder and put into chlorinating container, by after reactor lock sealing, graphene powder is heated, Heating temperature is arranged on 60 DEG C, open whipping appts to stir graphene powder, graphene powder is flown upward and is full of whole reactor, off-response still drain tap (valve connection chlorine recovery device), open vacuum-pumping valve, reactor is vacuumized, vacuum pressure 0.1MPa, heating pumpdown time 30min, after treating that the moisture of graphene powder is extracted out completely, close vacuum valve, stopping vacuumizes, again intensification heating is carried out to graphene powder, when temperature reaches 300 DEG C, open drain tap, open and enter chlorine into chlorine valve gate open, flow velocity 450 ~ 550 mL/min of chlorine, reaction times 4 ~ 8h, close into chlorine valve after reaction terminates, close and reclaim chlorine valve, nitrogen is passed in reactor, open vent gas treatment valve, tail gas is processed.Until in tail gas without the existence of chlorine after take out chlorination modified graphene powder.
Embodiment 2: take 100g graphene powder and put into chlorinating container, by after reactor lock sealing, graphene powder is heated, Heating temperature is arranged on 60 DEG C, open whipping appts to stir graphene powder, graphene powder is flown upward and is full of whole reactor, off-response still drain tap (valve connection chlorine recovery device), open vacuum-pumping valve, reactor is vacuumized, vacuum pressure 0.1MPa, heating pumpdown time 30min, after treating that the moisture of graphene powder is extracted out completely, close vacuum valve, stopping vacuumizes, again intensification heating is carried out to graphene powder, when temperature reaches 450 DEG C, open drain tap, open and enter chlorine into chlorine valve gate open, flow velocity 450 ~ 550 mL/min of chlorine, reaction times 3 ~ 5h, close into chlorine valve after reaction terminates, close and reclaim chlorine valve, nitrogen is passed in reactor, open vent gas treatment valve, tail gas is processed.Until in tail gas without the existence of chlorine after take out chlorination modified graphene powder.
Embodiment 3: take 100g graphene powder and put into chlorinating container, by after reactor lock sealing, graphene powder is heated, Heating temperature is arranged on 60 DEG C, open whipping appts to stir graphene powder, graphene powder is flown upward and is full of whole reactor, off-response still drain tap (valve connection chlorine recovery device), open vacuum-pumping valve, reactor is vacuumized, vacuum pressure 0.1MPa, heating pumpdown time 30min, after treating that the moisture of graphene powder is extracted out completely, close vacuum valve, stopping vacuumizes, again intensification heating is carried out to graphene powder, when temperature reaches 600 DEG C, open drain tap, open and enter chlorine into chlorine valve gate open, flow velocity 450 ~ 550 mL/min of chlorine, reaction times 1 ~ 3h, close into chlorine valve after reaction terminates, close and reclaim chlorine valve, nitrogen is passed in reactor, open vent gas treatment valve, tail gas is processed.Until in tail gas without the existence of chlorine after take out chlorination modified graphene powder.
Embodiment 4: take 100g graphene powder and put into chlorinating container, by after reactor lock sealing, graphene powder is heated, Heating temperature is arranged on 60 DEG C, open whipping appts to stir graphene powder, graphene powder is flown upward and is full of whole reactor, off-response still drain tap (valve connection chlorine recovery device), open vacuum-pumping valve, reactor is vacuumized, vacuum pressure 0.1MPa, heating pumpdown time 30min, after treating that the moisture of graphene powder is extracted out completely, close vacuum valve, stopping vacuumizes, again intensification heating is carried out to graphene powder, when temperature reaches 600 DEG C, open drain tap, open and enter chlorine into chlorine valve gate open, flow velocity 550 ~ 750 mL/min of chlorine, reaction times 0.5 ~ 2h, close into chlorine valve after reaction terminates, close and reclaim chlorine valve, nitrogen is passed in reactor, open vent gas treatment valve, tail gas is processed.Until in tail gas without the existence of chlorine after take out chlorination modified graphene powder.
Embodiment 5: take 100g graphene powder and put into chlorinating container, by after reactor lock sealing, graphene powder is heated, Heating temperature is arranged on 60oC, open whipping appts to stir graphene powder, graphene powder is flown upward and is full of whole reactor, off-response still drain tap (valve connection chlorine recovery device), open vacuum-pumping valve, reactor is vacuumized, vacuum pressure 0.1MPa, heating pumpdown time 30min, after treating that the moisture of graphene powder is extracted out completely, close vacuum valve, stopping vacuumizes, again intensification heating is carried out to graphene powder, when temperature reaches 600 DEG C, open drain tap, open and enter chlorine into chlorine valve gate open, flow velocity 750 ~ 950 mL/min of chlorine, reaction times 0.5 ~ 1h, close into chlorine valve after reaction terminates, close and reclaim chlorine valve, nitrogen is passed in reactor, open vent gas treatment valve, tail gas is processed.Until in tail gas without the existence of chlorine after take out chlorination modified graphene powder.
Embodiment 6: take 500g graphene powder and put into chlorinating container, by after reactor lock sealing, graphene powder is heated, Heating temperature is arranged on 60 DEG C, open whipping appts to stir graphene powder, graphene powder is flown upward and is full of whole reactor, off-response still drain tap (valve connection chlorine recovery device), open vacuum-pumping valve, reactor is vacuumized, vacuum pressure 0.1MPa, heating pumpdown time 30min, after treating that the moisture of graphene powder is extracted out completely, close vacuum valve, stopping vacuumizes, again intensification heating is carried out to graphene powder, when temperature reaches 600 DEG C, open drain tap, open and enter chlorine into chlorine valve gate open, flow velocity 750 ~ 950 mL/min of chlorine, reaction times 1 ~ 4h, close into chlorine valve after reaction terminates, close and reclaim chlorine valve, nitrogen is passed in reactor, open vent gas treatment valve, tail gas is processed.Until in tail gas without the existence of chlorine after take out chlorination modified graphene powder.
Selected embodiment is typical embodiments above, and above-mentioned explanation just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (8)
1. a preparation method for High-efficient Production chlorination Graphene, is characterized in that, comprise the steps: that graphene powder is carried out heating remove portion moisture by (1), the moisture being evacuated to graphene powder is drained completely, continues heating; (2) above-mentioned graphene powder and chlorine are reacted at a certain temperature, obtain chlorination graphene powder material; (3) above-mentioned chlorination graphene powder material nitrogen is processed, to remove the free chlorine of chlorination graphene powder surface adsorption, obtain pure chlorination graphene powder.
2. the preparation method of chlorination Graphene as claimed in claim 1, it is characterized in that the graphene powder described in step (1) is Graphene, graphene microchip, the purity of graphene powder is 95 ~ 99.5%.
3. the preparation method of chlorination Graphene as claimed in claim 1, it is characterized in that the Heating temperature described in step (1) is arranged on 40 ~ 60 DEG C, vacuum pressure is 0.08 ~ 0.1MPa, and the pumpdown time is 10 ~ 30min.
4. the preparation method of chlorination Graphene as claimed in claim 1, is characterized in that the purity of chlorine in step (2) is 99 ~ 99.999%.
5. the preparation method of chlorination Graphene as claimed in claim 1, it is characterized in that in step (2), temperature of reaction is 300 ~ 600 DEG C, the flow velocity of chlorine is 450 ~ 950 mL/min, and the reaction times is 0.5 ~ 8h.
6. the preparation method of chlorination Graphene as claimed in claim 1, is characterized in that the productive rate of chlorination Graphene is 93 ~ 98%.
7. the preparation method of chlorination Graphene as claimed in claim 1, is characterized in that in step (3), nitrogen gas purity is 98 ~ 99.999%.
8. a chlorination Graphene, is characterized in that, described chlorination Graphene is prepared by the method as described in claim 1 ~ 7.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105600780A (en) * | 2016-02-29 | 2016-05-25 | 昆明物理研究所 | Co-combustion preparation method of chlorine doped graphene quantum dots |
| CN107117599A (en) * | 2017-04-19 | 2017-09-01 | 东华大学 | A kind of preparation method of the miscellaneous graphene of chlorine |
| CN108314005A (en) * | 2018-03-27 | 2018-07-24 | 广西师范大学 | A kind of method and its device preparing chlorine doped graphene quantum dot |
| CN108373149A (en) * | 2018-03-15 | 2018-08-07 | 常州恒利宝纳米新材料科技有限公司 | The preparation method of industrial amination graphene |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101818059A (en) * | 2010-03-29 | 2010-09-01 | 中国科学院合肥物质科学研究院 | Method for preparing graphene oxide with high fluorescent quantum yield |
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2015
- 2015-08-14 CN CN201510498519.1A patent/CN104986751A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101818059A (en) * | 2010-03-29 | 2010-09-01 | 中国科学院合肥物质科学研究院 | Method for preparing graphene oxide with high fluorescent quantum yield |
Non-Patent Citations (2)
| Title |
|---|
| BO LI ET AL.: "Photochemical Chlorination of Graphene", 《ACS NANO》 * |
| HWEE LING POH ET AL.: "Halogenation of Graphene with Chlorine,Bromine,or Iodine by Exfoliation in a Halogen Atmosphere", 《CHEMISTRY A EUROPEAN JOURNAL》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105600780A (en) * | 2016-02-29 | 2016-05-25 | 昆明物理研究所 | Co-combustion preparation method of chlorine doped graphene quantum dots |
| CN107117599A (en) * | 2017-04-19 | 2017-09-01 | 东华大学 | A kind of preparation method of the miscellaneous graphene of chlorine |
| CN107117599B (en) * | 2017-04-19 | 2020-11-13 | 东华大学 | Preparation method of chloro-hybrid graphene |
| CN108373149A (en) * | 2018-03-15 | 2018-08-07 | 常州恒利宝纳米新材料科技有限公司 | The preparation method of industrial amination graphene |
| CN108314005A (en) * | 2018-03-27 | 2018-07-24 | 广西师范大学 | A kind of method and its device preparing chlorine doped graphene quantum dot |
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Address after: 361027, Fujian, Haicang District, Xiamen East Fu Fu Road, No. 16, No. 2881 Workshop on the south side of the 2 floor Applicant after: XIAMEN KNANO GRAPHENE TECHNOLOGY CORPORATION LIMITED Address before: 361027, Fujian, Haicang District, Xiamen East Fu Fu Road, No. 16, No. 2881 Workshop on the south side of the 2 floor Applicant before: Xiamen Knano Graphene Technology Corporation Limited |
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Application publication date: 20151021 |