CN106185902A - A kind of method that clean oxidation technology prepares the controlled graphene oxide of size - Google Patents
A kind of method that clean oxidation technology prepares the controlled graphene oxide of size Download PDFInfo
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- CN106185902A CN106185902A CN201610563721.2A CN201610563721A CN106185902A CN 106185902 A CN106185902 A CN 106185902A CN 201610563721 A CN201610563721 A CN 201610563721A CN 106185902 A CN106185902 A CN 106185902A
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- C01P2002/00—Crystal-structural characteristics
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- C01P2004/00—Particle morphology
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Abstract
The invention discloses a kind of method that clean oxidation technology prepares the controlled graphene oxide of size; the method comprises the following steps: employing natural flake graphite is raw material; first carry out pre-oxidation increase graphite layers away from and the oxygenated functional group at edge; the most under hydrothermal conditions, ammonia and hydrogen peroxide jointly act on not only protect that graphite flake layer is not sheared less but also utilize hydrogen peroxide to excite the hydroxyl radical free radical deep oxidation of generation to prepare graphite oxide product；By above-mentioned prepared graphite oxide after cleaning treatment, the most ultrasonic preparation graphene oxide dispersion；Dry graphene oxide dispersion obtains graphene oxide powder.Without using strong acid and heavy metal oxidation agent in preparation process of the present invention, last handling process is simple and environmentally-friendly, and cost of material is low, and preparation process is simple, is a kind of to be expected to the method that graphene oxide is prepared in scale.
Description
Technical field
The present invention relates to a kind of method that clean oxidation technology prepares the controlled graphene oxide of size.
Background technology
The concept of Graphene (GrapHene) is proposed from the seminar of the A.K. Geim leader of University of Manchester in 2004
Since, Graphene, as an other bright star of carbon family, has obtained physics, chemistry and the great attention of material scholar,
Therefore, Graphene become after CNT another yield unusually brilliant results " universal material " (Science 2004,306:
666.).Compared with CNT, there is perfect hybrid structure in Graphene, the electric transmission speed have superelevation electrical conductivity, being exceedingly fast
Degree, high rigidity, high-specific surface area and room-temperature quantum Hall effect etc. get most of the attention always (Nat. Mater. 2007,6,
183；Science 2009, 324, 1530.).Up to the present, scientific research personnel's preparation to Graphene has been carried out extensively
Research, about the preparation method of Graphene, have more literature review both at home and abroad.The magnanimity preparation method of Graphene at present
In, graphite it is considered as prepared by a kind of scale realizing high-quality graphene for preparing dilute the restoring as Graphene of graphite oxide
And the strategic starting point of application.
Graphite oxide is dilute is the derivant that graphite is dilute, and its structure is dilute with graphite to be substantially the same, and is a kind of two dimensional surface knot
Structure, relative to Graphene, it not only has good hydrophilic and the dispersibility in water, and can be made by chemical modification
It has widely purposes, the therefore dilute focus also becoming people's research of graphite oxide.Prepare the side of graphene oxide
Method mainly has chemical oxidization method.Chemical oxidization method is by using substantial amounts of inorganic strong protonic acid such as concentrated sulphuric acid, being fuming or they
Mixture process original graphite, by little for strong acid molecule insert graphite layers, be re-introduced into excess strong oxidizer such as (perchloric acid
Potassium, potassium permanganate etc.) it is carried out oxidation stripping.Main preparation method includes Brodie method, Standenmaiers method and H μ
Mmer method.Wherein H μm mer method prepares relative to additive method that degree of safety is high, the useless dusty gas of poison is few, and is widely used, also
It it is the graphene oxide preparation method of the most most application potential and development prospect.But, graphite oxide in above-mentioned preparation method
The preparation of alkene is required for introducing substantial amounts of acid solution and strong oxidizer, causes in purification phase, in order to remove substantial amounts of acid solution
And strong oxidizer, consequential to water resource and the serious waste of the energy, and all there is a huge sum of money in these strong oxidizers
Belong to ion, not recoverable, environment is caused irreversible severe contamination, thus hinders the mass of graphene oxide
Produce.Therefore, prepare to realize the mass of graphene oxide, it is necessary to a kind of method finding clean oxidation, green energy conservation
Technology of preparing, be applied to production technology prepared by scale, just can be expected to making a breakthrough property in terms of macroscopic preparation of graphene
Progress.
High-level oxidation technology also known as advanced oxidation processes, the hydroxyl radical free radical (OH) with generation with Strong oxdiative ability is
Feature, under the reaction conditions such as High Temperature High Pressure, electricity, sound, photoirradiation, catalyst, makes macromole hardly degraded organic substance be oxidized to low
Malicious or nontoxic small-molecule substance, extensively applies in sewage disposal.Research shows, OH oxidizing potential is up to+2.8V, the most secondary
In F2, and itself be electron deficiency group, there is the highest electronegativity, electrophilicity is strong, electron affinity energy 569.13KJ.mol-1, have the strongest additive reaction feature [Liu Yongdi, Xu Shouchang, Shanghai environmental science, 1994,13:26. Xie Yinde, Chen Feng,
What is for army building, Zhao Jincai, photographic science and light science, and 2000,18:357].Additionally, Li Wei etc. also utilize hydroxyl radical free radical Strong oxdiative
The delocalizedπelectron pair of sexual assault carbon nano tube surface, introduces hydroxyl and carboxyl [Li Wei, hydroxyl radical free radical pair at carbon tube-surface
The chemical modification of CNT, East China Normal University, 2005.].Additionally, the work graphene quantum dot before us forms machine
System research and dimensional effect can control graphene oxide to the addition having been proven that ammonia in the impact of its chemical property
The size of lamella, prevents the structure [Y.H. of oxidation that hydroxyl radical free radical the is stronger disruptive oxidation Graphene serious with shear ability
Liu, R.T. Wang, J.W. Lang, X.B. Yan*, Insight into the formation mechanism of
grapHene quantμm dots and size effect on their electrochemical behaviors.
PHysical Chemistry Chemical PHysics 17, 2015, 14028-14035.】。
Summary of the invention
It is an object of the invention to provide a kind of energy-saving and environment friendly type mass and prepare the controlled graphene oxide of size
Method.
In order to use free of contamination green reagent to realize the preparation of graphene oxide, and realize the chi to graphene oxide
Very little controlled, the advanced oxidation processes of present invention application hydroxyl radical free radical and the protective effect of ammonia obtain the edge that size is controlled
The graphite product of oxidation, afterwards through simple ultrasonic agitation, it is achieved the preparation of graphene oxide, this process does not use excess
Strong acid and strong base, it is pollution-free that the oxidation product decomposition of hydroxyl radical free radical obtains water by-product, it is achieved size controllable oxidization Graphene
Green technology of preparing, and form key technology.It is simple, safely controllable and in subsequent treatment mistake that the present invention has low cost, flow process
Journey does not consume the advantages such as too much resource and energy consumption, the ideal of graphene oxide can be prepared does as a kind of green that is applicable to
Method.
The technical scheme is that the natural flake graphite using different meshes is raw material, expansible graphiteization is located in advance
Reason, the edge oxidation and the graphite layers that carry out early stage process away from increasingization；Then hydro-thermal is utilized to excite hydrogen peroxide to produce hydroxyl
Free-radical oxidation graphite edge also utilizes ammonia that graphite flake layer is carried out size protection, while realizing deep oxidation graphite,
And obtain, by the protection of ammonia, the graphite oxide product that size is controlled, thus obtain the graphite oxide of controlled dimensions, then lead to
Cross simple ultrasonic disperse and dry technology, obtain the graphene oxide powder material that size is controlled.
A kind of method that clean oxidation technology prepares the controlled graphene oxide of size, it is characterised in that concrete steps are such as
Under:
The preparation of A graphite oxide: natural flake graphite is that expansible graphite product prepared by raw material, adds expansible graphite product
The mixed liquor of ammonia and hydrogen peroxide carries out hydro-thermal reaction and i.e. obtains graphite oxide product, then clean graphite oxide with deionized water
Product is until the pH=7 of aqueous phase, and this process is without danger, and safely controllable and preparation process does not introduce strong acid and heavy metal oxidation
Thing, environmental protection low cost, safely controllable；
The preparation of B graphene oxide dispersion: the graphite oxide obtained is added ultrasonic disperse in solvent and i.e. obtains graphene oxide
Dispersion liquid；
The preparation of C graphene oxide powder: the graphene oxide dispersion dried obtained is prepared graphene oxide powder.
The size of described natural flake graphite is 23 μm ~ 270 μm.
In described step A, the concentration of hydrogen peroxide used is 4wt% ~ 10wt%；The concentration of ammonia is 0.3wt% ~ 1wt%；Ammonia
It is 1:5 ~ 1:22 with the volume ratio of hydrogen peroxide.
Described expansible graphite product is 1 with the mass volume ratio of deep oxidation reaction reagent (i.e. ammonia and hydrogen peroxide):
30~1:100g/mL。
The condition of described hydro-thermal reaction is 100 DEG C ~ 200 DEG C, 6h ~ 10h.
Disperseing the solvent of graphite oxide in described step B is one or more in deionized water, DMF, acetone, ethanol
Combination.
The method being dried graphene oxide in described step C is the one in freeze-drying, spray drying method.
The present invention compared with prior art has the advantage that
1, the present invention fundamentally changes the separating-purifying difficulty of graphene oxide and the problem that involves great expense, is preparing
Journey not only avoid the use problem of the concentrated sulphuric acid of substantial amounts of strong oxidizer and excess, utilize the deep oxidation reaction examination of cleaning
Agent can be achieved with the preparation of graphite oxide, and before achieving, by application ammonia protective effect, the graphene oxide that size is controlled
The preparation of end product graphite oxide.
2, the present invention does not has the introducing of heavy metal element in preparation process, and the byproduct of reaction of hydrogen peroxide and ammonia is not
Produce environmentally harmful pollutant, be truly realized the preparation process of cleanliness without any pollution.
3, course of reaction of the present invention is gentle, and without very exothermic, it is not necessary to special protection, technological process is simple, and process safety can
Control, preparation cost is low, is the magnanimity preparation method of the controlled graphene oxide of a kind of size.
Accompanying drawing explanation
Fig. 1 is the SEM photograph of graphene oxide powder.
Fig. 2 is the infrared spectrum of graphene oxide.
Fig. 3 is the SEM photograph of various sizes of graphene oxide.
Detailed description of the invention
Embodiment 1
The method using the concentrated sulphuric acid of 98wt%, potassium permanganate to be oxidation intercalation prepares expansible graphite, first
The natural flake graphite of 10g a size of 23 μm is joined 50 mL H2SO4、2g KMnO4Mixed liquor in, stir 30 min
Rear chamber is gentle and quiet puts 1 h, prepares expansible graphite.By expansible graphite clean after take out 0.3g add 0.5mL 28% ammonia and
10mL 30% hydrogen peroxide, then dilute obtains graphite oxide product, afterwards deionization to 30mL, 180 DEG C of 6h reactions of hydro-thermal
Water cleans graphite oxide product, until the pH=7 of aqueous phase, adds 800W ultrasonic disperse in 300mL deionized water, is aoxidized
Graphene aqueous dispersions；Lyophilization prepares graphene oxide powder.
Embodiment 2
The method using the concentrated sulphuric acid of 98wt%, potassium permanganate to be oxidation intercalation prepares expansible graphite, first
The natural flake graphite of 10g a size of 80 μm is joined 50 mL H2SO4、2g KMnO4Mixed liquor in, stir 30 min
Rear chamber is gentle and quiet puts 1 h, prepares expansible graphite.Ammonia and 5mL that 1g adds 1mL 28% is taken out after being cleaned by expansible graphite
30% hydrogen peroxide, then dilute obtains graphite oxide product to 30mL, 100 DEG C of 8h reactions of hydro-thermal, and deionized water is clear afterwards
Wash graphite oxide product, until the pH=7 of aqueous phase, add 800W ultrasonic disperse in 300mLDMF, obtain graphene oxide moisture
Dissipate liquid；Spray drying prepares graphene oxide powder.
Embodiment 3
The method using the concentrated sulphuric acid of 98wt%, potassium permanganate to be oxidation intercalation prepares expansible graphite, first
The natural flake graphite of 10g a size of 75 μm is joined 50 mL H2SO4、2g KMnO4Mixed liquor in, stir 30 min
Rear chamber is gentle and quiet puts 1 h, prepares expansible graphite.Ammonia and 8mL that 1g adds 1mL 28% is taken out after being cleaned by expansible graphite
30% hydrogen peroxide, then dilute is to 60mL, and now because preexpanding graphite is unprocessed, liquid environment is acid condition, water
160 DEG C of 10h reactions of heat obtain graphite oxide product, and deionized water cleans graphite oxide product afterwards, until the pH=7 of aqueous phase,
Add 800W ultrasonic disperse in the mixed liquor of 300mL second alcohol and water, obtain graphene oxide aqueous dispersions；It is spray-dried preparation
Obtain graphene oxide powder.
Embodiment 4
The method using the concentrated sulphuric acid of 98wt%, potassium permanganate to be oxidation intercalation prepares expansible graphite, first
The natural flake graphite of 10g a size of 180 μm is joined 50 mL H2SO4、2g KMnO4Mixed liquor in, stir 30 min
Rear chamber is gentle and quiet puts 1 h, prepares expansible graphite.Ammonia and 10mL that 1g adds 1mL 28% is taken out after being cleaned by expansible graphite
30% hydrogen peroxide, then dilute obtains graphite oxide product to 40mL, 200 DEG C of 6h reactions of hydro-thermal, and deionized water is clear afterwards
Wash graphite oxide product, until the pH=7 of aqueous phase, add 800W ultrasonic disperse in 300mL acetone, obtain graphene oxide water
Dispersion liquid；Spray drying prepares graphene oxide powder.
Embodiment 5
The method using the concentrated sulphuric acid of 98wt%, potassium permanganate to be oxidation intercalation prepares expansible graphite, first
The natural flake graphite of 10g a size of 270 μm is joined 50 mL H2SO4、2g KMnO4Mixed liquor in, stir 30 min
Rear chamber is gentle and quiet puts 1 h, prepares expansible graphite.Ammonia and 20mL that 1g adds 1mL 28% is taken out after being cleaned by expansible graphite
30% hydrogen peroxide, then dilute obtains graphite oxide product to 80mL, 180 DEG C of 6h reactions of hydro-thermal, and deionized water is clear afterwards
Wash graphite oxide product, until the pH=7 of aqueous phase, add 800W ultrasonic disperse in 300mL deionized water, obtain graphite oxide
Alkene aqueous dispersions；Lyophilization prepares graphene oxide powder.
Claims (7)
1. the method that a clean oxidation technology prepares the controlled graphene oxide of size, it is characterised in that specifically comprise the following steps that
The preparation of A graphite oxide: natural flake graphite is that expansible graphite product prepared by raw material, adds expansible graphite product
The mixed liquor of ammonia and hydrogen peroxide carries out hydro-thermal reaction and i.e. obtains graphite oxide product, then clean graphite oxide with deionized water
Product is until the pH=7 of aqueous phase；
The preparation of B graphene oxide dispersion: the graphite oxide product obtained is added ultrasonic disperse in solvent and i.e. obtains oxidation stone
Ink alkene dispersion liquid；
The preparation of C graphene oxide powder: the graphene oxide dispersion dried obtained is prepared graphene oxide powder.
2. the method for claim 1, it is characterised in that the size of described natural flake graphite is 23 μm ~ 270 μm.
3. the method for claim 1, it is characterised in that in described step A the concentration of hydrogen peroxide used be 4wt% ~
10wt%；The concentration of ammonia is 0.3wt% ~ 1wt%；Ammonia is 1:5 ~ 1:22 with the volume ratio of hydrogen peroxide.
4. the method for claim 1, it is characterised in that described expansible graphite product and deep oxidation reaction reagent
Mass volume ratio is 1:30 ~ 1:100g/mL.
5. the method for claim 1, it is characterised in that the condition of described hydro-thermal reaction is 100 DEG C ~ 200 DEG C, 6h ~ 10h.
6. the method for claim 1, it is characterised in that the solvent disperseing graphite oxide in described step B is deionization
One or more combinations in water, DMF, acetone, ethanol.
7. the method for claim 1, it is characterised in that the method being dried graphene oxide in described step C is freezing dry
One in dry method, spray drying method.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106587045A (en) * | 2017-01-23 | 2017-04-26 | 宣城亨旺新材料有限公司 | Production process of graphene oxide |
| CN106587018A (en) * | 2016-12-08 | 2017-04-26 | 山西大同大学 | Preparation method of graphene aggregate sol |
| CN106744910A (en) * | 2017-01-16 | 2017-05-31 | 王奉瑾 | A kind of preparation method of graphene oxide |
| CN107215868A (en) * | 2017-06-14 | 2017-09-29 | 黑龙江省宝泉岭农垦帝源矿业有限公司 | The method that the graphene product of high-purity is prepared using oxidation-reduction method Fast Purification |
| CN108300424A (en) * | 2018-02-11 | 2018-07-20 | 山东建筑大学 | Potassium aluminum sulfate dodecahydrate/hydroxylating graphene thermal energy storage material and preparation method |
| CN108329892A (en) * | 2018-02-11 | 2018-07-27 | 山东建筑大学 | Ten sulfate dihydrate aluminium ammoniums/hydroxylating graphene thermal energy storage material and preparation method |
| CN108373906A (en) * | 2018-02-11 | 2018-08-07 | 山东建筑大学 | Barium hydroxide/hydroxylating graphene microchip thermal energy storage material and preparation method |
| CN108410428A (en) * | 2018-02-11 | 2018-08-17 | 仝宇浩 | Sodium acetate trihydrate/hydroxylating graphene phase-change thermal storage composite material and preparation method |
| CN108622890A (en) * | 2018-04-04 | 2018-10-09 | 北京石墨烯技术研究院有限公司 | A kind of method of graphene oxide separation |
| CN112830480A (en) * | 2021-02-25 | 2021-05-25 | 陕西汉唐森源实业发展集团有限责任公司 | Optimized preparation method of graphene |
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| CN106587018A (en) * | 2016-12-08 | 2017-04-26 | 山西大同大学 | Preparation method of graphene aggregate sol |
| CN106587018B (en) * | 2016-12-08 | 2021-12-31 | 山西大同大学 | Preparation method of graphene aggregate sol |
| CN106744910A (en) * | 2017-01-16 | 2017-05-31 | 王奉瑾 | A kind of preparation method of graphene oxide |
| CN106587045A (en) * | 2017-01-23 | 2017-04-26 | 宣城亨旺新材料有限公司 | Production process of graphene oxide |
| CN106587045B (en) * | 2017-01-23 | 2021-08-17 | 宣城亨旺新材料有限公司 | Production process of graphene oxide |
| 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 |
| CN107215868A (en) * | 2017-06-14 | 2017-09-29 | 黑龙江省宝泉岭农垦帝源矿业有限公司 | The method that the graphene product of high-purity is prepared using oxidation-reduction method Fast Purification |
| CN108373906A (en) * | 2018-02-11 | 2018-08-07 | 山东建筑大学 | Barium hydroxide/hydroxylating graphene microchip thermal energy storage material and preparation method |
| CN108410428A (en) * | 2018-02-11 | 2018-08-17 | 仝宇浩 | Sodium acetate trihydrate/hydroxylating graphene phase-change thermal storage composite material and preparation method |
| CN108329892A (en) * | 2018-02-11 | 2018-07-27 | 山东建筑大学 | Ten sulfate dihydrate aluminium ammoniums/hydroxylating graphene thermal energy storage material and preparation method |
| CN108300424A (en) * | 2018-02-11 | 2018-07-20 | 山东建筑大学 | Potassium aluminum sulfate dodecahydrate/hydroxylating graphene thermal energy storage material and preparation method |
| CN108622890A (en) * | 2018-04-04 | 2018-10-09 | 北京石墨烯技术研究院有限公司 | A kind of method of graphene oxide separation |
| CN112830480A (en) * | 2021-02-25 | 2021-05-25 | 陕西汉唐森源实业发展集团有限责任公司 | Optimized preparation method of graphene |
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Application publication date: 20161207 Assignee: Jiangsu Risingsun Tire Co., Ltd. Assignor: Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences Contract record no.: 2019320000216 Denomination of invention: Method for preparing size-controlled graphene oxide by clean oxidation technology Granted publication date: 20171222 License type: Exclusive License Record date: 20190628 |
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Assignee: Jiangsu Risingsun Tire Co., Ltd. Assignor: Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences Contract record no.: 2019320000216 Date of cancellation: 20190820 |