CN103539108A - Method for preparing graphene oxide - Google Patents
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- CN103539108A CN103539108A CN201310525092.0A CN201310525092A CN103539108A CN 103539108 A CN103539108 A CN 103539108A CN 201310525092 A CN201310525092 A CN 201310525092A CN 103539108 A CN103539108 A CN 103539108A
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Abstract
The invention relates to a method for preparing graphene oxide, belonging to the technical field of preparation of graphene oxide. The method comprises the following steps: firstly, preparing graphite oxide by adopting a chemical treatment method for natural crystalline flake graphite; then, separating and purifying the graphite oxide; and finally, mixing the purified graphite oxide with water, carrying out ultrasonic dispersion to obtain stable dispersion liquid, and spraying and drying the dispersion liquid to obtain graphene oxide powder. According to the method for preparing graphene oxide, effective separation of graphite oxide solid and aqueous liquor is realized by room-temperature natural settling of graphite oxide suspension, most of inorganic ion impurities generated in a preparation process are removed with supernatant liquid, so that a washing step is simplified. Moreover, a centrifugal washing method of absolute ethyl alcohol is adopted, solid-liquid separation in a centrifugal process is very easy to implement, a problem that solid-liquid separation is difficult in a water-washing process is overcome, time is greatly saved, and efficiency is improved.
Description
Technical field
The present invention relates to a kind of method of preparing graphene oxide, belong to graphene oxide preparing technical field.
Background technology
Graphene is just found a kind of New Two Dimensional plane carbon nanomaterial in 2004, and special monoatomic layer structure is given the performances such as its excellent mechanics, electricity and calorifics.Graphene all shows stem-winding performance and application prospect in fields such as microelectronics, quantum physics, material, chemistry, has become the international forward position and the focus that get most of the attention.The preparation method of Graphene has mechanical stripping method, chemical Vapor deposition process, epitaxial growth method, electrochemical process, chemistry redox method at present.Aforesaid method except chemistry redox method, mostly exist that productive rate is low, cost is high, difficult quality is controlled and cannot mass-producing etc. problem.Chemistry redox method becomes current most popular method with its low-cost advantage, is also one of approach most possibly realizing Graphene mass production.First the method obtains graphite intercalation oxidation graphite oxide, graphite oxide is washed after purifying and further peels off and obtain graphene oxide, more graphene oxide reduction is obtained to Graphene.Graphene oxide is the presoma of chemical synthesis of graphene and matrix material thereof, and its efficient preparation is the prerequisite that realizes Graphene large-scale production and application.
The preparation of graphene oxide is based upon on the basis that first obtains a large amount of graphite oxides, and the separating-purifying of existing graphite oxide (separating from the aqueous solution that contains residual impurity) method be first adopt suction filtration method by the thick product separation of graphite oxide out, then adopt suction filtration or centrifugal method with rare HCl solution and deionized water, the thick product of graphite oxide repeatedly to be washed.In the separating-purifying process of above-mentioned graphite oxide, every step suction filtration or centrifugal treating be unusual difficulty all, particularly, in to the process of graphite oxide washing, adopts common suction filtration or centrifugal method to be all difficult to oxidation graphite solid to separate from the aqueous solution.So the separating-purifying of graphite oxide is that an efficiency is low, the process of length consuming time.The high efficiency separation purification that how to realize graphite oxide is that graphene oxide urgent problem is prepared in efficient mass-producing.
Summary of the invention
The object of the invention is to the difficult problem existing in graphene oxide preparation process, from the high efficiency separation of graphite oxide, purify and start with, a kind of method of efficiently preparing graphene oxide is provided.
To achieve these goals, technical scheme of the present invention is as follows.
A method of preparing graphene oxide, comprises the following steps:
(1) prepare graphite oxide:
(1a) take raw material natural flake graphite as standard, every 1g natural flake graphite is 1 part.1 part of natural flake graphite, 1 part of Potassium Persulphate and 1 part of Vanadium Pentoxide in FLAKES are joined in 10ml/ part vitriol oil, ultrasonic dispersion 5min, 80 ℃ of oil bath lower magnetic forces stir 6h, after decompress filter washing by filter cake vacuum-drying, grinding.
(1b) dried composition is put into beaker, add 50ml/ part vitriol oil ultrasonic being uniformly dispersed, slowly add 6 parts of potassium permanganate and electric stirring 4h under ice-water bath protection; After adding 100ml/ part deionized water, mixed solution is moved in water-bath and keeps 40 ℃ to continue to stir 2h.
(1c) stop stirring and adding the deionized water of 300～1000ml/ part, then add 8ml/ part hydrogen peroxide, obtain glassy yellow graphite oxide suspension.
(2) separating-purifying graphite oxide:
(2a) by after the graphite oxide suspension room temperature electric stirring 10min obtaining in step (1), room temperature sedimentation 1～2h, removes supernatant liquid, gets lower sediment and pours centrifugal settling in centrifuge tube or Centrifuge Cup into, removes upper water.
(2b) in the precipitation remaining in centrifuge tube, pour dehydrated alcohol into, centrifugal after stirring or ultrasonic dispersion, remove supernatant liquid.
(2c) in step (2b), with dehydrated alcohol centrifuge washing, repeat 2～3 times, now the pH value of system is 6.0～6.5, collects lower sediment, dry, obtains the graphite oxide of purifying.
(3) prepare graphene oxide: the graphite oxide of purifying and water are mixed 1:500～1000 in mass ratio, and the ultrasonic dispersion 1～3h of 500W, obtains the stable dispersions of brown color, and this dispersion liquid spray drying treatment can be obtained to graphene oxide powder.
Further, in step (2a), centrifugal rotational speed is 4000 revs/min, and the time is 5min.
Further, in step (2b), centrifugal rotational speed is 4000～6000 revs/min; Time is 5min.
This beneficial effect of the invention is: (1) by the room temperature natural subsidence 1～2h of graphite oxide suspension, can realize the effectively separated of oxidation graphite solid and the aqueous solution.Because graphite oxide is prepared the later stage and added a large amount of water, the most mineral ion impurity that produce in preparation process can be eliminated along with supernatant liquid, have simplified washing step.(2) adopt the method for dehydrated alcohol centrifuge washing, in centrifugal process, solid-liquid separation is easy to implement, and centrifuge washing 15～30min can complete, and has overcome the problem of solid-liquid separation difficulty in water washing process, has greatly saved the time, has improved efficiency.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of graphene oxide in the embodiment of the present invention 1.
Fig. 2 is the infrared spectrogram of graphene oxide in the embodiment of the present invention 1.
Embodiment
Below in conjunction with embodiment, further set forth the embodiment of this invention.
Embodiment 1
A method of preparing graphene oxide, comprises the following steps:
(1) prepare graphite oxide:
(1a) 10g natural flake graphite, 10g Potassium Persulphate and 10g Vanadium Pentoxide in FLAKES are joined in the 100ml vitriol oil, ultrasonic dispersion 5min, 80 ℃ of oil bath lower magnetic forces stir 6h, after decompress filter washing by filter cake vacuum-drying, grinding.
(1b) dried composition is put into beaker, add the 500ml vitriol oil ultrasonic being uniformly dispersed, slowly add 60g potassium permanganate and electric stirring 4h under ice-water bath protection; After adding 1L deionized water, mixed solution is moved in water-bath and keeps 40 ℃ to continue to stir 2h.
(1c) stop stirring and adding the deionized water of 3L, then add 80ml hydrogen peroxide, obtain glassy yellow graphite oxide suspension.
(2) separating-purifying graphite oxide:
(2a) by after the graphite oxide suspension room temperature electric stirring 10min obtaining in step (1), room temperature sedimentation 1h, removes supernatant liquid, get lower sediment and pour centrifugal settling in centrifuge tube or Centrifuge Cup into, centrifugal rotational speed is 4000 revs/min, and the time is 5min, removes upper water.
(2b) in the precipitation remaining in centrifuge tube, pour dehydrated alcohol into, centrifugal after stirring or ultrasonic dispersion, centrifugal rotational speed is 4000 revs/min; Time is 5min, removes supernatant liquid.
(2c) in step (2b), with dehydrated alcohol centrifuge washing, repeat 2 times, now the pH value of system is 6.0, collects lower sediment, dry, obtains the graphite oxide of purifying.
(3) prepare graphene oxide: by the graphite oxide of purifying and water 1:500 mixing in mass ratio, the ultrasonic dispersion of 500W 3h, obtain the stable dispersions of brown color, this dispersion liquid spray drying treatment can be obtained to graphene oxide powder, transmission electron microscope photo is shown in Fig. 1, and the infrared spectrogram of graphene oxide is shown in Fig. 2.
Embodiment 2
A method of preparing graphene oxide, comprises the following steps:
(1) prepare graphite oxide:
(1a) 10g natural flake graphite, 10g Potassium Persulphate and 10g Vanadium Pentoxide in FLAKES are joined in the 100ml vitriol oil, ultrasonic dispersion 5min, 80 ℃ of oil bath lower magnetic forces stir 6h, after decompress filter washing by filter cake vacuum-drying, grinding.
(1b) dried composition is put into beaker, add the 500ml vitriol oil ultrasonic being uniformly dispersed, slowly add 60g potassium permanganate and electric stirring 4h under ice-water bath protection; After adding 1L deionized water, mixed solution is moved in water-bath and keeps 40 ℃ to continue to stir 2h.
(1c) stop stirring and adding the deionized water of 5L, then add 80ml hydrogen peroxide, obtain glassy yellow graphite oxide suspension.
(2) separating-purifying graphite oxide:
(2a) by after the graphite oxide suspension room temperature electric stirring 10min obtaining in step (1), room temperature sedimentation 2h, removes supernatant liquid, get lower sediment and pour centrifugal settling in centrifuge tube or Centrifuge Cup into, centrifugal rotational speed is 4000 revs/min, and the time is 5min, removes upper water.
(2b) in the precipitation remaining in centrifuge tube, pour dehydrated alcohol into, centrifugal after stirring or ultrasonic dispersion, centrifugal rotational speed is 6000 revs/min; Time is 5min, removes supernatant liquid.
(2c) in step (2b), with dehydrated alcohol centrifuge washing, repeat 3 times, now the pH value of system is 6.5, collects lower sediment, dry, obtains the graphite oxide of purifying.
(3) prepare graphene oxide: by the graphite oxide of purifying and water in mass ratio 1:1000 mix, the ultrasonic dispersion of 500W 1h, obtains the stable dispersions of brown color, and this dispersion liquid spray drying treatment can be obtained to graphene oxide powder.
The above is the preferred embodiment of the present invention; 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 make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (3)
1. a method of preparing graphene oxide, is characterized in that: comprise the following steps:
(1) prepare graphite oxide:
(1a) take raw material natural flake graphite as standard, every 1g natural flake graphite is 1 part; 1 part of natural flake graphite, 1 part of Potassium Persulphate and 1 part of Vanadium Pentoxide in FLAKES are joined in 10ml/ part vitriol oil, ultrasonic dispersion 5min, 80 ℃ of oil bath lower magnetic forces stir 6h, after decompress filter washing by filter cake vacuum-drying, grinding;
(1b) dried composition is put into beaker, add 50ml/ part vitriol oil ultrasonic being uniformly dispersed, slowly add 6 parts of potassium permanganate and electric stirring 4h under ice-water bath protection; After adding 100ml/ part deionized water, mixed solution is moved in water-bath and keeps 40 ℃ to continue to stir 2h;
(1c) stop stirring and adding the deionized water of 300～1000ml/ part, then add 8ml/ part hydrogen peroxide, obtain glassy yellow graphite oxide suspension;
(2) separating-purifying graphite oxide:
(2a) by after the graphite oxide suspension room temperature electric stirring 10min obtaining in step (1), room temperature sedimentation 1～2h, removes supernatant liquid, gets lower sediment and pours centrifugal settling in centrifuge tube or Centrifuge Cup into, removes upper water;
(2b) in the precipitation remaining in centrifuge tube, pour dehydrated alcohol into, centrifugal after stirring or ultrasonic dispersion, remove supernatant liquid;
(2c) in step (2b), with dehydrated alcohol centrifuge washing, repeat 2～3 times, now the pH value of system is 6.0～6.5, collects lower sediment, dry, obtains the graphite oxide of purifying;
(3) prepare graphene oxide: the graphite oxide of purifying and water are mixed 1:500～1000 in mass ratio, and the ultrasonic dispersion 1～3h of 500W, obtains the stable dispersions of brown color, by this, dispersion liquid spraying is dry can obtain graphene oxide powder.
2. a kind of method of preparing graphene oxide described in 1 as requested, is characterized in that: in described step (2a), centrifugal rotational speed is 4000 revs/min, and the time is 5min.
3. a kind of method of preparing graphene oxide described in 1 as requested, is characterized in that: in described step (2b), centrifugal rotational speed is 4000～6000 revs/min; Time is 5min.
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| CN103950921A (en) * | 2014-04-23 | 2014-07-30 | 中国科学院山西煤炭化学研究所 | Method for efficient separation and purification of graphite oxide |
| CN103964429A (en) * | 2014-05-26 | 2014-08-06 | 苏州斯迪克新材料科技股份有限公司 | Preparation method of graphene |
| CN104332321A (en) * | 2014-10-23 | 2015-02-04 | 齐鲁工业大学 | Rutile type TiO2 nanorod oxidized grapheme composite material and preparation method thereof |
| CN104445168A (en) * | 2014-11-28 | 2015-03-25 | 张明 | Preparation method of graphene oxide |
| CN104759269A (en) * | 2015-03-31 | 2015-07-08 | 苏州佰锐生物科技有限公司 | Preparation method of graphene microsphere biological separation medium with controllable particle size |
| CN104891567A (en) * | 2015-06-24 | 2015-09-09 | 齐鲁工业大学 | Preparing method of tubular TiO2/reduced graphene oxide composite |
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| CN106915741A (en) * | 2017-04-11 | 2017-07-04 | 深圳市佩成科技有限责任公司 | The preparation method of improved graphene oxide |
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| CN103950921A (en) * | 2014-04-23 | 2014-07-30 | 中国科学院山西煤炭化学研究所 | Method for efficient separation and purification of graphite oxide |
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| CN105399088B (en) * | 2015-12-11 | 2017-06-27 | 中国电子科技集团公司第十八研究所 | A kind of washing separating method of Graphene graphite oxide |
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| CN112374493A (en) * | 2020-12-28 | 2021-02-19 | 中国科学技术大学先进技术研究院 | Method for preparing monolayer graphene oxide with controllable sheet diameter size |
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