CN107364856B - A method of removing sulfate radical foreign matter in graphene oxide synthetic system - Google Patents
A method of removing sulfate radical foreign matter in graphene oxide synthetic system Download PDFInfo
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- CN107364856B CN107364856B CN201710457826.4A CN201710457826A CN107364856B CN 107364856 B CN107364856 B CN 107364856B CN 201710457826 A CN201710457826 A CN 201710457826A CN 107364856 B CN107364856 B CN 107364856B
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Abstract
The embodiment of the invention provides a kind of methods of sulfate radical foreign matter in removing graphene oxide synthetic system, comprising the following steps: (1) synthesizes graphene oxide using Hummers method or improved Hummers method, obtain graphene oxide synthetic system；(2) density is greater than water, and water-immiscible organic solvent is mixed with the aqueous solution containing metal cation, obtains sulfate radical cleaning solution；The sulfate radical cleaning solution is divided into upper aqueous layer and lower layer's organic solvent layer；Wherein the metal cation can be formed with sulfate radical and be precipitated；(3) the graphene oxide synthetic system in step (1) is transported in the sulfate radical cleaning solution in the water layer of two layers of intersection, is stood, so that the graphene oxide in graphene oxide synthetic system is sunk in the organic solvent layer.The method provided by the invention for removing sulfate radical foreign matter in graphene oxide synthetic system is more succinctly more suitable for industrial production.
Description
Technical field
The present invention relates to graphene oxide synthesis technical fields, more particularly to a kind of removing graphene oxide synthetic system
The method of middle sulfate radical foreign matter.
Background technique
Graphene is single layer of carbon atom structure, by sp2The stabilization two-dimensional structure that hydridization is formed, the net of Hexagonal close arrangement
Shape crystal, unique structure impart the unique physicochemical properties of graphene.Currently, the research about graphene composite material
The numerous areas such as catalysis, luminous, energy storage and biological medicine are had been directed to, and present huge application prospect.Oxidation
Graphene (GO) is one of numerous derivatives of graphene, the characteristic with polymer, colloid, film and amphiphatic molecule.
Graphene oxide is mainly made of carbon atom and some polarity oxygen-containing functional groups (such as-OH ,-COOH, C=O ,-O-), is retained
Delocalization pi-conjugated system in graphene.Graphene oxide has good hydrophily, and high-specific surface area and pi-pi accumulation act on, this
A little advantages provide great advantage for the application of graphene oxide, become one of research emphasis of graphene composite material.
It is general in current industrial production because of the lower production costs of improved Hummers method synthesis graphene oxide
Graphene oxide is synthesized all over using improved Hummers method；But it is whole after improved Hummers method synthesis graphene oxide
It needs to remove containing a large amount of impurity sulfate ion in a synthetic system.The industrial method for removing sulfate ion at present,
It is all the mode of centrifuge washing.But centrifuge washing inefficiency and to the revolving speed of centrifuge require it is high, these are all very
It is unfavorable for industrial production, therefore needs to develop a kind of easier sulfate ion minimizing technology.
Summary of the invention
The embodiment of the present invention is designed to provide sulfate radical in a kind of easier removing graphene oxide synthetic system
The method of impurity.Specific technical solution is as follows:
A method of removing sulfate radical foreign matter in graphene oxide synthetic system, comprising the following steps: (1) use
Hummers method or improved Hummers method synthesize graphene oxide, after synthesis, obtain graphene oxide synthetic system；
(2) density is greater than water, and water-immiscible organic solvent is mixed with the aqueous solution containing metal cation, is obtained
To sulfate radical cleaning solution；The sulfate radical cleaning solution is divided into upper aqueous layer and lower layer's organic solvent layer；Wherein the metal sun from
Son can be formed with sulfate radical and be precipitated；
(3) the graphene oxide synthetic system in step (1) is transported in the sulfate radical cleaning solution close to two layers of friendship
In water layer at boundary, stand, so that the graphene oxide in graphene oxide synthetic system is sunk in the organic solvent layer.
Optionally, after step (3) further include: isolate the graphene oxide from the organic solvent layer
Come.
Optionally, the metal cation is in calcium ion, barium ions, lead ion, mercury ion, strontium ion or silver ion
One or more, preferably calcium ion.
Optionally, the aqueous solution containing metal cation is calcium hydroxide aqueous solution or suspension.
Optionally, the metal cation synthesizes graphite oxide relative to using Hummers method or improved Hummers method
The stoichiometric excess for the sulfate radical being added when alkene.
Optionally, the organic solvent and the density ratio of water at the same temperature are greater than 1.3.
Optionally, the organic solvent is selected from least one of chloroform, carbon tetrachloride, methylene chloride, dichloroethanes.
Optionally, in step (3): the graphene oxide synthetic system in step (1) is transported to two layers of distance boundary
The height at place is less than the position of water layer height 1/15, preferably smaller than water layer height 1/20.
Optionally, the sulfate radical cleaning solution upper aqueous layer and the volume ratio of lower layer's organic solvent layer are (0.5-1.5): 1.
Optionally, the volume ratio for stating sulfate radical cleaning solution upper aqueous layer and graphene oxide synthetic system is (1-5): 1.
The present invention uses water-organic solvent two-phase system, and can be floated using the precipitating that metal cation and sulfate radical are formed
In water layer, and graphene oxide sinks to organic solvent layer due to charging neutrality.Based on the above two o'clock, we can use this
Method removes the sulfate ion in graphene oxide synthetic system.Moreover, the present invention provides compared with the mode of centrifuge washing
Removing graphene oxide synthetic system in the method for sulfate radical foreign matter be more succinctly more suitable for industrial production.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is XRD (X-Ray Diffraction, X-ray diffraction) figure of the white flock precipitate in 2 water layer of embodiment.
Fig. 2 is the XRD diagram of the yellow substance in 2 dichloromethane layer of embodiment.
Specific embodiment
The present invention provides a kind of methods of sulfate radical foreign matter in removing graphene oxide synthetic system, including following step
It is rapid:
(1) graphene oxide is synthesized using Hummers method or improved Hummers method, after synthesis, obtains oxidation stone
Black alkene synthetic system；
(2) density is greater than water, and water-immiscible organic solvent is mixed with the aqueous solution containing metal cation, is obtained
To sulfate radical cleaning solution；The sulfate radical cleaning solution is divided into upper aqueous layer and lower layer's organic solvent layer；Wherein the metal sun from
Son can be formed with sulfate radical and be precipitated；
(3) the graphene oxide synthetic system in step (1) is transported in the sulfate radical cleaning solution close to two layers of friendship
In water layer at boundary, stand, so that the graphene oxide in graphene oxide synthetic system is sunk in the organic solvent layer.
Firstly the need of explanation, " Hummers method " mentioned herein is the classical way for synthesizing graphene oxide (GO),
Its proton acid system and strong oxidizer by the inclusion of the concentrated sulfuric acid, such as potassium permanganate oxidation graphite, to obtain graphite oxide
Alkene.For Hummers method, the present invention is not necessarily to repeat herein, and those skilled in the art, can be with according to the record of existing literature
Know its specific embodiment.
" improved Hummers method " mentioned herein is also referred to as modified Hummers method or modified Hummers
method.It is technical staff on the basis of Hummers method, by it for example, proton acid system, strong oxidizer, reaction
The adjustment of condition (such as temperature) and the method formed；Such as the works such as Zhu Hongwei, Xu Zhiping, Xie Dan " graphene --- structure,
Preparation method and performance characterization " the 2nd section of page 32 of (publishing house, Tsinghua University, the 1st printing November in 2011) just describe
To include NaNO3, dense H2SO4Proton acid system, with KMnO4For the improved Hummers method of strong oxidizer；Document
(MARCANO D C,KOSYNKIN D V,BERLIN J M,et al.Improved synthesis of graphene
Oxide.ACS Nano 4:4806-4814 [J] .Acs Nano, 2010,4 (8): 4806-14.) it also describes to include dense
H2SO4And H3PO4Proton acid system, with KMnO4For the improved Hummers method of strong oxidizer.
It should be noted that the proton acid system in improved Hummers method, still mainly includes the concentrated sulfuric acid.For changing
Into Hummers method, the prior art more have been reported that, the present invention herein without limit；As long as the proton of improved Hummers method
Acid system still includes the concentrated sulfuric acid, and the graphene oxide synthetic system after synthesizing graphene oxide can be mentioned using the present invention
The method of sulfate radical foreign matter is handled in the removing graphene oxide synthetic system of confession.
Described graphene oxide synthetic system refers to closing by Hummers method or improved Hummers method in step (1)
After process at graphene oxide, the summation of the obtained each substance entirely reacted；Its without any post-processing, such as
Washing, filtering, dry etc..
The present invention is to be reacted by the metal cation in water layer with the sulfate radical in graphene oxide synthetic system, is generated
Sulfate precipitation, so that the sulfate radical in graphene oxide synthetic system be removed；In order to realize precipitating generated and GO points
From, need to guarantee it is generated precipitating stay in the water layer of sulfate radical cleaning solution, sink to GO in organic solvent layer；Inventor is logical
It crosses the study found that the graphene oxide synthetic system in step (1) is transported in the sulfate radical cleaning solution close to two layers of friendship
It in water layer at boundary, stands, without stirring, precipitating generated may be implemented and stay in the water layer of sulfate radical cleaning solution.?
In a kind of specific embodiment of the invention, the metal cation be selected from calcium ion, barium ions, lead ion, mercury ion, strontium from
One of son or silver ion are a variety of, preferably calcium ion.More specifically, anion corresponding to the metal cation can
Think hydroxyl or other can make the metal cation at least partly and can be dissolved in the anion of water, such as nitrate anion, chloride ion
(when using silver ion, anion cannot be chloride ion) etc..Preferably, anion corresponding to metal cation selects hydrogen-oxygen
Root and will not introduce other because hydroxyl can also play the role of neutralizing hydrionic in graphene oxide synthetic system
Impurity.Therefore, in a kind of specific embodiment of the invention, the aqueous solution containing metal cation can be water-soluble for calcium hydroxide
Liquid or suspension.
In order to fully remove graphene oxide synthesize this be in sulfate radical, in a kind of specific implementation of the invention
In mode, the amount of the substance of metal cation synthesizes graphite oxide relative to using Hummers method or improved Hummers method
The amount of the substance for the sulfate radical being added when alkene, stoichiometric excess.For example, metal cation is Ca2+When, if using
During Hummers method or improved Hummers method synthesis graphene oxide, the sulfuric acid of 1mol is added, then metal cation
For Ca2+Amount be preferably greater than 1mol.
For the preparation method of sulfate radical cleaning solution, the aqueous solution containing metal cation can be first prepared, then by it
It is greater than water, and water-immiscible organic solvent mixing with density, is layered completely to it.In a kind of specific reality of the invention
It applies in mode, in order to the layering of good guarantee water layer and organic solvent layer, the organic solvent and water are at the same temperature
Density ratio be greater than 1.3.It is highly preferred that the organic solvent is in chloroform, carbon tetrachloride, methylene chloride, dichloroethanes
It is at least one.
Due to the sulfate radical in graphene oxide synthetic system need to contact with water layer could pass through metal cation by its
In sulfate radical removal, but graphene oxide synthetic system is contacted with water layer for a long time excessively, can make it is more, it is synthesized
Graphene oxide enter in water layer, influence last graphene oxide yield；In order to solve this contradiction, inventor passes through
Repeatedly, largely experiment discovery, by the way that the graphene oxide synthetic system in step (1) is transported to the sulfate radical cleaning solution
In close to two layers of intersection water layer in, can solve above-mentioned contradiction, in water layer, sulfate radical can be in conjunction with metal cation
It generates precipitating and stays in water layer；And since close to two layers of intersection, graphene oxide can enter within a short period of time
Solvent layer reduces the time contacted with water layer, excessive graphene oxide is prevented to be dispensed into water layer.For graphene oxide
The specific location that synthetic system is transported to, those skilled in the art can remove sulfate radical as far as possible and maximumlly retain oxygen
Under the principle of graphite alkene, slightly adjust under the teachings of the present invention.In a specific embodiment, in step (3): can
With the graphene oxide synthetic system in step (1) is transported to two layers of intersection of distance height be less than water layer height 1/15,
The preferably smaller than position of water layer height 1/20.
It, can be according to different applications as the mode being transported to graphene oxide synthetic system close to two layers of intersection
Scene selects different modes, and the present invention is herein without limiting；Such as when the synthesis graphene oxide of laboratory, stone is aoxidized at this time
The amount of black alkene synthetic system is smaller, can be conveyed using machinery such as peristaltic pumps.And work as the amount of graphene oxide synthetic system
It, then can be by being provided with the spreading channel of dispersion hole, under the action of pressure pump, by oxygen such as when industrial production when larger
Graphite alkene synthetic system is transported in spreading channel, and is transported to leaning on for sulfate radical cleaning solution by the dispersion hole of spreading channel
In the water layer of nearly two layers of intersection.
For the volume of sulfate radical cleaning solution upper aqueous layer and lower layer's organic solvent layer, can be synthesized according to graphene oxide
The concrete condition of the total volume of sulfuric acid dosage and synthetic system in system determines, in a kind of specific embodiment party of the invention
In formula, the volume ratio of sulfate radical cleaning solution upper aqueous layer and lower layer's organic solvent layer is (0.5-1.5): 1.
It, equally can be according to oxidation stone for the volume of sulfate radical cleaning solution upper aqueous layer and graphene oxide synthetic system
The concrete condition of the total volume of sulfuric acid dosage and synthetic system in black alkene synthetic system determines, in a kind of tool of the invention
In body embodiment, the volume ratio of sulfate radical cleaning solution upper aqueous layer and graphene oxide synthetic system is (1-5): 1.
In a kind of specific embodiment of the invention, after step (3) further include: by the graphene oxide from institute
It states in organic solvent layer and separates, and carry out subsequent processing according to the actual conditions of graphene oxide；Including but not limited to
It decides whether or not to wash according to dry aftereffect fruit.If conventional drying processing can make product dry, it was demonstrated that sulfate ion
It removes more then without washing, if product cannot be made dry, it was demonstrated that there is a small amount of sulfate ion to retain then with distillation washing
It washs 1-2 times, re-dry.
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
The improved Hummers method of embodiment 1 synthesizes graphene oxide
3g crystalline flake graphite is weighed on pan paper with assay balance in the large beaker of 2L, weighs 360ml respectively with graduated cylinder
It is added in graphite together with the 40ml concentrated sulfuric acid and phosphoric acid.It weighs 18g potassium permanganate with small beaker to be ground into a powder with mortar, 0 DEG C
Under the conditions of be slowly added into mixture while stirring.Mixture is allowed to stir 12 hours under conditions of 50 DEG C later.It takes
400ml mixture of ice and water is added after being cooled to room temperature after out, quickly stirs and be gradually added into the hydrogen peroxide of 3ml 30%.It stands
3 days, obtain graphene oxide synthetic system.
Embodiment 2 removes sulfate ion using calcium hydroxide solution-methylene chloride two-phase system sulfate radical cleaning solution
It takes the methylene chloride of 150ml to be added in the beaker of 500ml, 32g calcium hydroxide is added to the water and 200ml is made hangs
Turbid is poured on methylene chloride, it can be seen that solution is obviously divided into upper layer and lower layer, and upper layer is calcium hydroxide suspension, lower layer two
Chloromethanes.It crosses peristaltic pump and the graphene oxide synthetic system 50ml that embodiment 1 obtains is added to two layers of intersection, be not added and stir
It mixes.It was found that there is yellow substance to sink to methylene chloride bottom, and there is white flock precipitate generation in water layer.
3 XRD of embodiment detection
The yellow substance in the white flock precipitate and methylene chloride bottom in 2 water layer of Example, drying are gone forward side by side respectively
Row XRD test.As a result as shown in Figures 1 and 2 respectively.
As can be seen from Figure 1 white flock precipitate is calcium sulfate, it was demonstrated that can be removed using method provided by the invention
Sulfate radical foreign matter in graphene oxide synthetic system.
From in Fig. 2 it is observed that graphene oxide is at 2 θ=12.839 one very strong diffraction maximum, and interlamellar spacing
ForIt can be seen that graphite layers after being oxidized increase away from obvious, be after being oxidized due to graphite between layers
There is the oxygen-containing functional groups such as a large amount of hydrone and hydroxyl, carboxyl, epoxy group.There is a diffraction in 2 θ=43.198
Peak, it is graphene planes diffraction maximum, it is possible to find out that yellow substance is exactly graphene oxide.
It is absolutely proved by testing above, method provided by the invention can remove sulfuric acid in graphene oxide synthetic system
Root impurity；And this method is easy, is very suitable to industrial production.
Above to a kind of method progress for removing sulfate radical foreign matter in graphene oxide synthetic system provided by the present invention
It is discussed in detail.Principle and implementation of the present invention are described for specific embodiment used herein, the above implementation
The explanation of example is merely used to help understand method and its central idea of the invention.It should be pointed out that for the common skill of this field
, without departing from the principle of the present invention, can be with several improvements and modifications are made to the present invention for art personnel, these change
Into the protection for also falling into the claims in the present invention with modification.
Claims (12)
1. a kind of method for removing sulfate radical foreign matter in graphene oxide synthetic system, which comprises the following steps:
(1) graphene oxide is synthesized using Hummers method or improved Hummers method, after synthesis, obtains graphene oxide
Synthetic system；
(2) density is greater than water, and water-immiscible organic solvent is mixed with the aqueous solution containing metal cation, obtains sulphur
Acid group cleaning solution；The sulfate radical cleaning solution is divided into upper aqueous layer and lower layer's organic solvent layer；The wherein metal cation energy
Enough and sulfate radical, which is formed, to be precipitated；
(3) the graphene oxide synthetic system in step (1) is transported in the sulfate radical cleaning solution close to two layers of intersection
Water layer in, stand so that the graphene oxide in graphene oxide synthetic system is sunk in the organic solvent layer.
2. the method as described in claim 1, which is characterized in that after step (3) further include: by the graphene oxide from
It is separated in the organic solvent layer.
3. the method as described in claim 1, which is characterized in that the metal cation be selected from calcium ion, barium ions, lead from
One of son, mercury ion, strontium ion or silver ion are a variety of.
4. method as claimed in claim 3, which is characterized in that the metal cation is calcium ion.
5. method as claimed in claim 4, which is characterized in that the aqueous solution containing metal cation is calcium hydroxide aqueous solution
Or suspension.
6. the method as described in claim 1, which is characterized in that the metal cation is relative to use Hummers method or changes
Into Hummers method synthesize graphene oxide when the stoichiometric excess of sulfate radical that is added.
7. the method as described in claim 1, which is characterized in that the organic solvent and the density ratio of water at the same temperature are big
In 1.3.
8. the method for claim 7, which is characterized in that the organic solvent is selected from chloroform, carbon tetrachloride, dichloromethane
At least one of alkane, dichloroethanes.
9. the method as described in claim 1, which is characterized in that in step (3): the graphene oxide in step (1) is closed
The height that architectonical is transported to two layers of intersection of distance is less than the position of water layer height 1/15.
10. method as claimed in claim 9, which is characterized in that in step (3): the graphene oxide in step (1) is closed
The height that architectonical is transported to two layers of intersection of distance is less than the position of water layer height 1/20.
11. the method as described in claim 1, which is characterized in that the sulfate radical cleaning solution upper aqueous layer and lower layer are organic molten
The volume ratio of oxidant layer is (0.5-1.5): 1.
12. the method as described in claim 1, which is characterized in that the sulfate radical cleaning solution upper aqueous layer and graphene oxide
The volume ratio of synthetic system is (1-5): 1.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103708442A (en) * | 2013-11-08 | 2014-04-09 | 江苏科技大学 | Method using ionic liquid to prepare high dispersion graphene |
| CN105314623A (en) * | 2014-07-30 | 2016-02-10 | 郭琳 | Graphene synthesis method |
| CN105565299A (en) * | 2015-11-26 | 2016-05-11 | 陕西高华知本化工科技有限公司 | Method for preparing oxidized graphene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103708442A (en) * | 2013-11-08 | 2014-04-09 | 江苏科技大学 | Method using ionic liquid to prepare high dispersion graphene |
| CN105314623A (en) * | 2014-07-30 | 2016-02-10 | 郭琳 | Graphene synthesis method |
| CN105565299A (en) * | 2015-11-26 | 2016-05-11 | 陕西高华知本化工科技有限公司 | Method for preparing oxidized graphene |
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