CN110902674B - Preparation method of high-quality graphene oxide - Google Patents
Preparation method of high-quality graphene oxide Download PDFInfo
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- CN110902674B CN110902674B CN201911301331.8A CN201911301331A CN110902674B CN 110902674 B CN110902674 B CN 110902674B CN 201911301331 A CN201911301331 A CN 201911301331A CN 110902674 B CN110902674 B CN 110902674B
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Abstract
The invention discloses a preparation method of high-quality graphene oxide, relates to the technical field of graphene oxide preparation, and aims to provide a preparation method of graphene with high oxidation degree and low defect density. The method mainly comprises the following steps: A. the mixture of the first intercalating agent concentrated sulfuric acid, the second intercalating agent sulfate, the third intercalating agent and the phosphate is diffused and expanded in the squamous graphite at room temperature to form a graphite interlayer compound; B. fully oxidizing the graphite interlayer compound by potassium permanganate at medium temperature, and further adding hydrogen peroxide to obtain a graphene oxide original sample; C. and (3) removing hydrogen peroxide under the condition of heat preservation, and further centrifugally washing to obtain a pure graphene oxide sample. The method disclosed by the invention is simple and easy to operate, low in cost and capable of preparing in a large scale, and the prepared graphene oxide has the advantages of high oxidation degree, low defect density and large and thin sheet layers, so that a reliable source is provided for the large-scale preparation of the reduced graphene.
Description
Technical Field
The invention belongs to the technical field of graphene oxide preparation, and particularly relates to high-quality graphene oxide preparation.
Background
The development of graphene oxide has been greatly improved since the first synthesis of Brodie in 1859, and particularly in 2004, the reduced graphene is obtained by taking graphene oxide as a precursor through a reduction method, so that the development and application of the graphene oxide are promoted again. Meanwhile, the graphene oxide has the characteristics of excellent dispersibility, permeability and swelling property, insulativity, near infrared absorption, functional modification and the like, and is widely applied to the fields of coating, biological medicine, organic solar cells, detectors and the like.
The Hummers method is the most commonly used method for preparing graphene oxide at present, namely, concentrated sulfuric acid and sodium nitrate are mixed with graphite, and potassium permanganate is used as an oxidant. Compared with the previous Brodie method and Saudenmailer method, the Hummers method uses potassium permanganate and sodium nitrate to replace potassium perchlorate and fuming nitric acid, so that the experimental danger and toxic gas emission are reduced, but sodium nitrate still generates a small amount of toxic gas nitrogen dioxide in the oxidation process. In 2010, marcano et al replaced the intercalating agent sodium nitrate with phosphoric acid based on the Hummers method to prepare graphene oxide, so that no toxic gas was generated during the reaction process, and the hydrophilicity of the graphene oxide was improved. However, preparing graphene oxide with higher oxidation degree and lower defect density is still a problem to be solved urgently by scientific researchers.
Disclosure of Invention
The invention provides a preparation method of high-quality graphene oxide, which is simple and easy to operate, does not need special reaction equipment, and has the characteristics of high oxidation degree and low defect density.
In order to achieve the above object, the detailed process for preparing graphene oxide according to the present invention is as follows:
(1) Graphite intercalation compound: mixing concentrated sulfuric acid, a second intercalating agent and ground third intercalating agent fine powder to obtain an intercalating agent, wherein the molar ratio of sulfate radical to phosphate radical is 1:1-25:1, adding squamous graphite powder under stirring condition, expanding and foaming for 12-48h to obtain a mixed solution A, and the total mass ratio of graphite powder to intercalating agent is 1:1-1:550;
the second intercalating agent sulfate is one or more of lithium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, barium sulfate, aluminum sulfate, ferric sulfate, sodium bisulfate and potassium bisulfate; the third intercalating agent is one or more of lithium phosphate, sodium phosphate, potassium phosphate, magnesium phosphate, zinc phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, lithium dihydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, and dilithium hydrogen phosphate.
(2) Oxidizing: slowly adding oxidant potassium permanganate into the mixed solution A within 15-45min, wherein the mass ratio of the graphite powder to the potassium permanganate is 1:1-1:10, and stirring and reacting for 4-10h at the medium temperature of 25-50 ℃; slowly dripping hydrogen peroxide with the mass concentration of 10-30% until no bubbles are generated, heating to 50 ℃, and preserving heat for 1-6h to obtain a mixed solution B;
(3) And (3) centrifugal washing: and (3) centrifugally washing the mixed solution B by using 0.1-2M hydrochloric acid aqueous solution and deionized water in sequence until the pH value is=5-7.4, and freeze-drying the precipitate to obtain the brown yellow graphene oxide.
Preferably, in the step (1), the mixed system of sulfuric acid/hydrogen sulfate and dihydrogen phosphate has a better oxidation effect as an intercalating agent.
Preferably, in the step (2), the medium-temperature oxidation temperature is 40 ℃, and the oxidation effect is better.
Compared with the prior art, concentrated sulfuric acid is adopted as a first intercalation agent, sulfate is adopted as a second intercalation agent and phosphate is adopted as a third intercalation agent for mixing, and the method replaces the prior art that only sulfuric acid/phosphoric acid is used for forming a graphite interlayer compound for oxidation treatment, so that the treatment is more beneficial to the diffusion of the intercalation agent among graphite layers, the graphite expansion interval is increased to form the graphite-sulfuric acid interlayer compound, and the method is simple and feasible to operate and improves the safety; furthermore, in the oxidation process of potassium permanganate, the oxidant diffuses from the edge to the center of graphite, and carbon adjacent to the surface of graphite forms cyclic manganate, so that the manganate is unstable, carbonyl carbon and holes are easily formed on the surface of a carbon ring during hydrolysis, and the addition of the third intercalating agent releases phosphate radical due to slow hydrolysis so as to protect C-O bond formed during hydrolysis of the manganate, so that the defect that the C-O bond is excessively oxidized to form carbonyl carbon is avoided, the integrity of the carbon ring on the surface of graphene oxide is maintained as much as possible, and the degree of oxidation stripping is not influenced. In a word, the method provided by the invention is simple and easy to operate, low in cost and capable of preparing large quantities, and the prepared graphene oxide is high in oxidation degree, low in defect density and large and thin in graphite sheet.
Drawings
FIG. 1 is an XRD characterization picture of graphene oxide prepared with different dihydrogen phosphate salts in the present invention;
FIG. 2 is a graph of Raman spectrum characterization of graphene oxide preparation with different dihydrogen phosphate participation in the present invention;
fig. 3 is a TEM photograph of high quality graphene oxide prepared according to a preferred embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the particular embodiments described herein are illustrative only and are not intended to limit the invention, i.e., the embodiments described are merely some, but not all, of the embodiments of the invention. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to be within the scope of the present invention.
It is noted that relational terms such as "first" and "second", and the like, are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
(1) Graphite intercalation compound: 45ml of concentrated sulfuric acid/potassium hydrogen sulfate and 11g of ground potassium dihydrogen phosphate fine powder are mixed to be used as an intercalation agent, and 0.375g of squamous graphite powder is added under the stirring condition to be expanded and foamed for 24 hours to obtain a mixed solution A;
(2) Oxidizing: slowly adding 2.25g of oxidant potassium permanganate into the mixed solution A within 30min, and stirring to react for 6h at the medium temperature of 40 ℃; slowly dripping hydrogen peroxide with the mass concentration of 30% until no bubbles are generated, heating to 50 ℃ and preserving heat for 3 hours to obtain a mixed solution B;
(3) And (3) centrifugal washing: and (3) centrifugally washing the mixed solution B with a 1M hydrochloric acid aqueous solution and deionized water in sequence until the pH value is=5-6, and freeze-drying the precipitate to obtain the brown yellow graphene oxide.
Example 2
(1) Graphite intercalation compound: 45ml of concentrated sulfuric acid/potassium hydrogen sulfate and 9.75g of ground sodium dihydrogen phosphate fine powder are mixed to be used as an intercalation agent, and 0.375g of squamous graphite powder is added under the stirring condition to be expanded and foamed for 24 hours to obtain a mixed solution A;
(2) Oxidizing: slowly adding 2.25g of oxidant potassium permanganate into the mixed solution A within 30min, and stirring to react for 6h at the medium temperature of 40 ℃; slowly dripping hydrogen peroxide with the mass concentration of 30% until no bubbles are generated, heating to 50 ℃ and preserving heat for 3 hours to obtain mustard green mixed solution B;
(3) And (3) centrifugal washing: and (3) centrifugally washing the mixed solution B with a 1M hydrochloric acid aqueous solution and deionized water in sequence until the pH value is=5-6, and freeze-drying the precipitate to obtain the brown yellow graphene oxide.
Example 3
(1) Graphite intercalation compound: 45ml of concentrated sulfuric acid/potassium hydrogen sulfate and 8.45g of ground lithium dihydrogen phosphate fine powder are mixed to be used as an intercalation agent, and 0.375g of squamous graphite powder is added under the stirring condition to be expanded and foamed for 24 hours to obtain a mixed solution A;
(2) Oxidizing: slowly adding 2.25g of oxidant potassium permanganate into the mixed solution A within 30min, and stirring to react for 6h at the medium temperature of 40 ℃; slowly dripping hydrogen peroxide with the mass concentration of 30% until no bubbles are generated, heating to 50 ℃ and preserving heat for 3 hours to obtain mustard green mixed solution B;
(3) And (3) centrifugal washing: and (3) centrifugally washing the mixed solution B with a 1M hydrochloric acid aqueous solution and deionized water in sequence until the pH value is=5-6, and freeze-drying the precipitate to obtain the brown yellow graphene oxide.
As can be seen from fig. 1, the 2 theta values of XRD of the graphene oxides prepared in example 1, example 2 and example 3 are 8.91, 9.38 and 9.43, respectively, while the 2 theta values of the graphene oxides prepared in general literature are between 10 and 11, which indicates that the graphene oxides prepared in the invention have higher oxidation degree, mainly because of high diffusion depth of the intercalating agent in graphite, so that the subsequent potassium permanganate oxidation proceeds from the edge to the center of the graphite, and the oxidation degree and stripping efficiency are deepened.
From FIG. 2, it can be seen that the Raman spectra of graphene oxide prepared in example 1, example 2, and example 3 are shown as I D /I G The values are 0.945, 0.935 and 0.914 respectively, which shows that the oxidation degree of the graphene oxide prepared by the dihydrogen phosphate salt is highHas a low defect density at the same time.
It can be seen from fig. 3 that the graphene oxide prepared in example 1 has a characteristic that the sheets are large and thin.
Those of ordinary skill in the art will recognize that the embodiments described herein are for the purpose of aiding the reader in understanding the principles of the present invention and should be understood that the scope of the invention is not limited to such specific statements and embodiments. Those of ordinary skill in the art can make various other specific modifications and combinations from the teachings of the present disclosure without departing from the spirit thereof, and such modifications and combinations remain within the scope of the present disclosure.
Claims (3)
1. The preparation method of the high-quality graphene oxide is characterized by comprising the following steps of:
step 1: graphite intercalation compound: at room temperature, concentrated sulfuric acid is used as a first intercalation agent, sulfate and phosphate are respectively added as a second intercalation agent and a third intercalation agent, the mol ratio of sulfate to phosphate is 1:1-25:1, and squamous graphite powder is added under stirring to expand and foam for 12-48 hours to obtain a mixed solution A, and the mass ratio of graphite powder to the intercalation agent is 1:1-1:550;
step 2: oxidizing: slowly adding oxidant potassium permanganate into the mixed solution A within 15-45min, wherein the mass ratio of the graphite powder to the potassium permanganate is 1:1-1:10, and stirring and reacting for 4-10h at the medium temperature of 25-50 ℃; slowly dripping hydrogen peroxide with the mass concentration of 10-30% until no bubbles are generated, heating to 50 ℃, and preserving heat for 1-6h to obtain a mixed solution B;
step 3: and (3) centrifugal washing: and (3) centrifugally washing the mixed solution B by using 0.1-2M hydrochloric acid aqueous solution and deionized water in sequence until the pH=5.0-7.4, and freeze-drying the precipitate to obtain the graphene oxide.
2. The method for preparing high-quality graphene oxide according to claim 1, wherein the method comprises the following steps: the second intercalating agent sulfate is one or more of lithium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, barium sulfate, aluminum sulfate, ferric sulfate, sodium bisulfate and potassium bisulfate.
3. The method for preparing high-quality graphene oxide according to claim 1, wherein the method comprises the following steps: the third intercalating agent is one or more of lithium phosphate, sodium phosphate, potassium phosphate, magnesium phosphate, zinc phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, lithium dihydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, and dilithium hydrogen phosphate.
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| CN104787750A (en) * | 2014-01-16 | 2015-07-22 | 中国科学院宁波材料技术与工程研究所 | Graphene and preparation method thereof |
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