CN103172056B - Efficient separating and purifying method of graphene oxide - Google Patents
Efficient separating and purifying method of graphene oxide Download PDFInfo
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- CN103172056B CN103172056B CN201310046959.4A CN201310046959A CN103172056B CN 103172056 B CN103172056 B CN 103172056B CN 201310046959 A CN201310046959 A CN 201310046959A CN 103172056 B CN103172056 B CN 103172056B
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Abstract
The invention discloses an efficient separating and purifying method of graphene oxide. The efficient separating and purifying method comprises the following steps of: (1) filtering suspension liquid containing graphite oxide and graphene oxide to obtain graphene oxide dispersion liquid and graphite oxide paste, wherein the suspension liquid is prepared by adopting common graphite powder as the material through a wet chemical oxidation method; (2) dropping an alkaline solution to the graphene oxide dispersion liquid, so that the pH value of the dispersion fluid is 1.8-2.2, the graphene oxide is clustered and settled, the graphene oxide aggregate is obtained by filtering, and the graphene oxide solid is obtained by cleaning and drying. According to the efficient separating and purifying method of the graphene oxide disclosed by the invention, the alkaline solution is utilized as an auxiliary agent, and the graphene oxide can be separated and purified efficiently by a simple process. The efficient separating and purifying method of the graphene oxide has the advantages of being simple in process, low in cost, green and environment-friendly, easily controllable in operation conditions, pure in product, low in product loss rate and the like.
Description
Technical field
The invention belongs to carbon materials field, be specifically related to a kind of highly effective separation purification method of graphene oxide.
Background technology
Graphene oxide is a kind of Novel carbon material, is after diamond-type, graphite mould, fullerene type and carbon cast carbon material, another important new discovery in carbon material field.Research about graphene oxide can trace back to 1855, mainly concentrates on its structure and synthetic method aspect at that time.From 19th-century mid-term to mid-twentieth century, Chinese scholars mainly concentrates the preparation process of research graphene oxide.Comparatively common graphene oxide preparation method mainly contains 4 kinds: Brodie method, Staudenmaier method, Hummers method and electrochemical process etc.
Since nearest 30 years, people are while continuing to be devoted to confirmation graphene oxide structure, and the applied research also having started the upsurge to graphene oxide applied research, particularly graphene oxide and matrix material thereof is paid attention to more and more widely.Various matrix materials prepared by using graphene oxide as parent show very superior performance, become one of inorganic materials that investigator mainly pays close attention to.
At present, in employing wet chemical oxidation legal system in the research of graphene oxide, the technology separation graphite oxide ene products such as dialysis, high speed centrifugation or sedimentation are usually adopted.But dialysis also exists the technical deficiency of separation cycle long (a few weeks longer).And high speed centrifugation or sedimentation techniques are for dialysis, although separation cycle shorter (within a few hours), but due in sepn process, give up the supernatant liquid containing a large amount of graphene oxide, therefore cause the technical problem that loss of product is serious, separating-purifying productive rate is on the low side.
Summary of the invention
The present invention is directed in prior art and to be difficult to the technical problem of separating-purifying with common graphite powder through the graphene oxide that wet chemical oxidation method obtains for raw material, a kind of method of high efficiency separation purification graphene oxide is provided.
The method of high efficiency separation purification graphene oxide of the present invention comprises the steps:
1. the suspension containing graphite oxide and graphene oxide obtained through wet chemical oxidation method for raw material with common graphite powder is filtered, obtain graphene oxide dispersion and graphite oxide purees;
2. drip basic solution in graphene oxide dispersion, make pH value to 1.8 ~ 2.2 of dispersion liquid, preferable ph to 2.0, make graphene oxide reunion sedimentation, then obtain graphene oxide coacervate after filtration, cleaning, oven dry obtain graphene oxide solid.
In the present invention, described common graphite powder is crystalline graphite powder, expansible black lead powder or microlite ink powder; Described wet chemical oxidation method is Shi Taodeng mayer (Staudenmaier) method, Brodie (Brodie) method or Ha Musi (Hummers) method.
In the present invention, step 1. with step 2. in adopt the qualitative or quantitative paper of ordinary filter paper as experiment to filter, or adopt filter membrane such as millipore filtration to filter.
In the present invention, the basic solution that described basic solution can be greater than 7 for any pH, is preferably sodium hydroxide or the potassium hydroxide solution of 0.5 ~ 5mol/L.
Step 2. in, the bake out temperature of graphene oxide coacervate can be 40 ~ 90 DEG C, and drying time can be 6 ~ 12 hours.
Be preferably, the graphite oxide purees 1. obtained step is cleaned, dry and can obtain oxidation graphite solid product further.The bake out temperature of graphite oxide purees can be 40 ~ 90 DEG C, and drying time is 6 ~ 12 hours.
Positive progressive effect of the present invention is: the present invention is directed to and adopt wet chemical oxidation legal system in graphene oxide process a few days ago, the technical problem of product separation difficulty, while preparing graphene oxide, has carried out high efficiency separation purifying to product.The method has the advantages such as technique is simple, cost is low, environmental protection, operational condition is easily controlled, products pure, loss of product rate are low.
Accompanying drawing explanation
Fig. 1 is the graphene oxide dispersion (left side) obtained in separating and purifying method process of the present invention and the photo adding basic solution rear oxidation Graphene reunion (right side); And
Fig. 2 is the XRD analysis collection of illustrative plates of the graphene oxide that separating and purifying method of the present invention obtains.
Embodiment
Embodiment 1
Take crystalline graphite powder as main raw material, adopt Hummers legal system for graphene oxide.Get graphite oxide and graphene oxide suspension that 100mL is obtained by reacting, first add 200mL deionized water and dilute, adopt middling speed quantitative paper to carry out filtering separation, obtain dark yellow graphite oxide purees and graphene oxide solution.By the dark yellow graphite oxide purees obtained, by washed with de-ionized water, to filtrate BaCl
2inspection is without SO
4 2-, dry 6 hours in the baking oven of 90 DEG C, namely obtain oxidation graphite solid.Get 10mL and filter the graphene oxide solution obtained, add 1mol/L sodium hydroxide solution 30mL, now solution is in acid (pH value is 2.2), obtains luteotestaceous suspension oxidation Graphene coacervate.Adopt middling speed quantitative paper to carry out filtering separation to it, obtain graphene oxide coacervate, with washed with de-ionized water coacervate to filtrate BaCl
2inspection is without SO
4 2-.The coacervate obtained is dried 6 hours in the baking oven of 90 DEG C, namely obtains graphene oxide solid.
Result shows, adopt this technology separation purification graphite oxide ene product, the rate of loss of graphite oxide ene product can be reduced to 0%, product purity is up to 99.9%.
As the photo in Fig. 1, left side is graphene oxide dispersion; Right side is for adding basic solution rear oxidation Graphene coacervate.The XRD analysis result of graphene oxide solid is see Fig. 2, and described XRD analysis is X-ray diffraction analysis, adopts the D8Advance type diffractometer of German Bruker company.Fig. 2 is provable, utilizes method of the present invention can obtain pure graphene oxide.
Embodiment 2
With expansible black lead powder for main raw material, adopt Staudenmaier legal system for graphene oxide.Get graphite oxide and graphene oxide suspension that 100mL is obtained by reacting, first add 200mL deionized water and dilute, adopt middling speed quantitative paper to carry out filtering separation, obtain dark yellow graphite oxide purees and graphene oxide solution.By the dark yellow graphite oxide purees obtained, by washed with de-ionized water, to filtrate BaCl
2inspection is without SO
4 2-, dry 12 hours in the baking oven of 40 DEG C, namely obtain oxidation graphite solid.Get 10mL and filter the graphene oxide solution obtained, add 1mol/L potassium hydroxide solution 30mL, now solution is in acid (pH value is 2.0), obtains luteotestaceous suspension oxidation Graphene coacervate.Adopt middling speed quantitative paper to carry out filtering separation to it, obtain graphene oxide coacervate, with washed with de-ionized water coacervate to filtrate BaCl
2inspection is without SO
4 2-.After the coacervate obtained is dried 12 hours in the baking oven of 40 DEG C, namely obtain graphene oxide solid.
Result shows, adopt this technology separation purification graphite oxide ene product, the rate of loss of graphite oxide ene product can be reduced to 0%, product purity is up to 99.9%.
Embodiment 3
With microlite ink powder for main raw material, adopt Brodie legal system for graphene oxide.Get graphite oxide and graphene oxide suspension that 100mL is obtained by reacting, first add 200mL deionized water and dilute, adopt middling speed quantitative paper to carry out filtering separation, obtain dark yellow graphite oxide purees and graphene oxide solution.By the dark yellow graphite oxide purees obtained, by washed with de-ionized water, to filtrate BaCl
2inspection is without SO
4 2-, dry 6 hours in the baking oven of 90 DEG C, namely obtain oxidation graphite solid.Get 10mL and filter the graphene oxide solution obtained, add 5mol/L potassium hydroxide solution 6mL, now solution is in acid (pH value is 1.8), obtains luteotestaceous suspension oxidation Graphene coacervate.Adopt middling speed quantitative paper to carry out filtering separation to it, obtain graphene oxide coacervate, with washed with de-ionized water coacervate to filtrate BaCl
2inspection is without SO
4 2-.After the coacervate obtained is dried 6 hours in the baking oven of 90 DEG C, namely obtain graphene oxide solid.
Result shows, adopt this technology separation purification graphite oxide ene product, the rate of loss of graphite oxide ene product can be reduced to 0%, product purity is up to 99.9%.
Embodiment 4
With microlite ink powder for main raw material, adopt Hummers legal system for graphene oxide.Get graphite oxide and graphene oxide suspension that 100mL is obtained by reacting, first add 200mL deionized water and dilute, adopt middling speed quantitative paper to carry out filtering separation, obtain dark yellow graphite oxide purees and graphene oxide solution.By the dark yellow graphite oxide purees obtained, by washed with de-ionized water, to filtrate BaCl
2inspection is without SO
4 2-, dry 6 hours in the baking oven of 90 DEG C, namely obtain oxidation graphite solid.Get 10mL and filter the graphene oxide solution obtained, add 0.5mol/L potassium hydroxide solution 60mL, now solution is in acid (pH value is 2.2), obtains luteotestaceous suspension oxidation Graphene coacervate.Adopt middling speed quantitative paper to carry out filtering separation to it, obtain graphene oxide coacervate, with washed with de-ionized water coacervate to filtrate BaCl
2inspection is without SO
4 2-.After the coacervate obtained is dried 6 hours in the baking oven of 90 DEG C, namely obtain graphene oxide solid.
Result shows, adopt this technology separation purification graphite oxide ene product, the rate of loss of graphite oxide ene product can be reduced to 0%, product purity is up to 99.9%.
Embodiment 5
With expansible black lead powder for main raw material, adopt Hummers legal system for graphene oxide.Get graphite oxide and graphene oxide suspension that 100mL is obtained by reacting, first add 200mL deionized water and dilute, adopt middling speed quantitative paper to carry out filtering separation, obtain dark yellow graphite oxide purees and graphene oxide solution.By the dark yellow graphite oxide purees obtained, by washed with de-ionized water, to filtrate BaCl
2inspection is without SO
4 2-, dry 12 hours in the baking oven of 40 DEG C, namely obtain oxidation graphite solid.Get 10mL and filter the graphene oxide solution obtained, add 0.5mol/L sodium hydroxide solution 60mL, now solution is in acid (pH value is 2.2), obtains luteotestaceous suspension oxidation Graphene coacervate.Adopt middling speed quantitative paper to carry out filtering separation to it, obtain graphene oxide coacervate, with washed with de-ionized water coacervate to filtrate BaCl
2inspection is without SO
4 2-.After the coacervate obtained is dried 12 hours in the baking oven of 40 DEG C, namely obtain graphene oxide solid.
Result shows, adopt this technology separation purification graphite oxide ene product, the rate of loss of graphite oxide ene product can be reduced to 0%, product purity is up to 99.9%.
Claims (7)
1. a highly effective separation purification method for graphene oxide, it comprises the steps:
1. the suspension containing graphite oxide and graphene oxide obtained through wet chemical oxidation method for raw material with common graphite powder is filtered, obtain graphene oxide dispersion and graphite oxide purees, described common graphite powder is crystalline graphite powder, expansible black lead powder or microlite ink powder; Described wet chemical oxidation method is Shi Taodeng mayer method, Brodie method or Ha Musifa;
2. drip basic solution in graphene oxide dispersion, make pH value to 1.8 ~ 2.2 of dispersion liquid, make graphene oxide reunion sedimentation, then obtain graphene oxide coacervate after filtration, cleaning, oven dry obtain graphene oxide solid.
2. the method for claim 1, is characterized in that: the step 2. middle basic solution that drips, in graphene oxide dispersion, makes the pH value to 2.0 of dispersion liquid.
3. the method for claim 1, is characterized in that: 1. 2. middle employing ordinary filter paper or filter membrane filter step with step; Described ordinary filter paper is qualitative or quantitative paper; Described filter membrane is millipore filtration.
4. the method for claim 1, is characterized in that: described basic solution is sodium hydroxide or the potassium hydroxide solution of 0.5 ~ 5mol/L.
5. the method for claim 1, is characterized in that: step 2. in, the bake out temperature of graphene oxide coacervate is 40 ~ 90 DEG C, and drying time is 6 ~ 12 hours.
6. the method for claim 1, is characterized in that: the graphite oxide purees 1. obtained step is cleaned, dry and obtain oxidation graphite solid.
7. method as claimed in claim 6, is characterized in that: step 1. in, the bake out temperature of graphite oxide purees is 40 ~ 90 DEG C, and drying time is 6 ~ 12 hours.
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| CN104118872B (en) * | 2014-08-04 | 2017-03-22 | 长沙赛维能源科技有限公司 | Method and device for purifying oxidized graphene/graphene solution |
| CN104264179B (en) * | 2014-09-17 | 2016-06-22 | 中国科学院山西煤炭化学研究所 | A kind of method being prepared Graphene by graphite raw ore electrolysis |
| CN105776189A (en) * | 2016-01-30 | 2016-07-20 | 山西大学 | Method for preparing high-purity small oxidized graphene |
| CN106006623A (en) * | 2016-06-16 | 2016-10-12 | 三达膜科技（厦门）有限公司 | Separating and impurity-removing method for graphene oxide |
| CN106587042B (en) * | 2016-12-19 | 2019-02-19 | 上海交通大学 | The method that a kind of pair of crude liquid of graphene oxide is rapidly purified |
| CN110683537A (en) * | 2019-10-21 | 2020-01-14 | 复旦大学 | Method for separating and purifying graphene oxide |
| CN113274763A (en) * | 2021-06-08 | 2021-08-20 | 清华大学深圳国际研究生院 | Method and device for concentrating graphene oxide dispersion liquid |
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| CN101591014A (en) * | 2009-06-30 | 2009-12-02 | 湖北大学 | A kind of method of realizing large-scale preparation of monolayer oxidized graphene |
| CN102145887A (en) * | 2011-05-18 | 2011-08-10 | 中国科学院长春应用化学研究所 | Method for preparing and purifying graphene oxide |
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| CN101591014A (en) * | 2009-06-30 | 2009-12-02 | 湖北大学 | A kind of method of realizing large-scale preparation of monolayer oxidized graphene |
| CN102145887A (en) * | 2011-05-18 | 2011-08-10 | 中国科学院长春应用化学研究所 | Method for preparing and purifying graphene oxide |
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