CN115650222A - Method for applying organic acid in graphene preparation process - Google Patents
Method for applying organic acid in graphene preparation process Download PDFInfo
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- CN115650222A CN115650222A CN202211378454.3A CN202211378454A CN115650222A CN 115650222 A CN115650222 A CN 115650222A CN 202211378454 A CN202211378454 A CN 202211378454A CN 115650222 A CN115650222 A CN 115650222A
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Abstract
The invention discloses a method for applying organic acid in a graphene preparation process, and relates to the technical field of graphene preparation. The method of the invention comprises the following steps: s1, soaking a mixed product containing a graphene crude product in deionized water to obtain a suspension; s2, adding organic acid into the suspension obtained in the S1 until the pH value of the suspension is 6-7; repeatedly washing with deionized water and absolute ethyl alcohol for many times; and after high-speed centrifugal separation, placing the precipitate in an oven and drying to obtain the graphene product. The method can completely avoid using inorganic acid such as strong acid such as hydrochloric acid in the operation of neutralization and washing, has green and environment-friendly production process, and reduces the production cost of the graphene.
Description
Technical Field
The invention relates to the technical field of graphene preparation, in particular to a method for applying organic acid in a graphene preparation process.
Background
Since the discovery of graphene in the nineties of the last century, scientists discovered and revealed the characteristics of graphene, high electron mobility at normal temperature (15000 cm) 2 ·V -1 ·s -1 ) And excellent thermal conductivity (about 5300 W.m) -1 ·K -1 Single layer), large specific surface area (2600 m) 2 ·g -1 ) And excellent mechanical strength (fracture strength 130 GPa). Therefore, how to prepare graphene becomes a research hotspot at that time, wherein the graphene preparation by the oxidation-reduction method is reported in many cases, the method takes graphite powder as a raw material, the graphite powder is oxidized by a strong oxidant potassium permanganate, the reaction is carried out under the conditions of concentrated sulfuric acid and concentrated nitric acid, and then the graphene is obtained by chemical reduction and separation. Due to the reaction under acidic conditions, the preparation method has the following problems in the specific industrial implementation: firstly, the production equipment has high requirements and must resist strong acid and strong alkali; and secondly, alkali is used for neutralization and separation in the separation and purification of the graphene, so that the production cost of the graphene is increased due to large sewage treatment amount in the production process, and the industrial production is difficult to realize due to damage to the ecological environment.
On the contrary, zhzhenping et al invented graphene (CN 103601177A) obtained by using organic acid as a precursor material for preparing graphene and graphitizing at high temperature under the catalysis of alkali metal salt, but alkali metal salt, especially alkali chloride metal, has great damage to a hearth at high temperature and great equipment loss. Onhe et al use cheap biomass carbon as raw material, various activators, in N 2 Carrying out high-temperature graphitization treatment under an atmosphere condition, washing with hydrochloric acid and neutralizing with alkali, and separating to obtain graphene (CN 111686761B). However, in the preparation method, inorganic acid is adopted to wash the product to ensure that the pH is less than 7, and then deionized water and absolute ethyl alcohol are used for repeatedly washing until the product is neutral, so that hydrochloric acid can cause pollution to water and environment, and the cost of sewage treatment can be increased when the hydrochloric acid is used in large quantity.
Disclosure of Invention
The technical problem to be solved by the invention is that the existing method for preparing graphene needs to use inorganic acid for washing, so that the production sewage treatment cost is high.
In order to solve the above problems, the present invention proposes the following technical solutions:
the invention provides a method for applying organic acid in a graphene preparation process, which comprises the following steps:
s1, soaking a mixed product containing a graphene crude product in deionized water to obtain a suspension;
s2, adding organic acid into the suspension obtained in the S1 until the pH value of the suspension is 6-7; repeatedly washing with deionized water and absolute ethyl alcohol for many times; and after high-speed centrifugal separation, putting the precipitate into an oven and drying to obtain the graphene product.
Specifically, in step S2, adding an organic acid to the suspension obtained in step S1, wherein bubbles may be generated, and adding the organic acid until the bubbles are not generated, wherein the pH of the suspension is adjusted to 6-7 by the organic acid; and repeatedly washing the precipitate with deionized water and absolute ethyl alcohol for multiple times to finish the washing process.
The further technical scheme is that in the step S2, the washing times with deionized water and absolute ethyl alcohol are 1-20 times. For example, in other embodiments, the number of repeated washing with deionized water and absolute ethanol in step S2 is 1, 3, 5, 7, 9, 13, 15, 17, or 20.
The further technical scheme is that the organic acid is monobasic organic acid, dibasic organic acid and/or tribasic organic acid.
The further technical scheme is that the organic acid is one or more of formic acid, acetic acid, oxalic acid, lactic acid, citric acid and gluconic acid.
The further technical scheme is that when the organic acid is a mixture of multiple acids, the mixing proportion is arbitrary.
For example, in other embodiments, the organic acid is any one of formic acid, acetic acid, oxalic acid, lactic acid, citric acid, and gluconic acid.
For example, in other embodiments, the organic acid is any two of formic acid, acetic acid, oxalic acid, lactic acid, citric acid, and gluconic acid, and the mixing ratio is any ratio.
For example, in other embodiments, the organic acid is any three or more of formic acid, acetic acid, oxalic acid, lactic acid, citric acid, and gluconic acid, and the mixing ratio is any ratio.
The method further comprises the step S1 of detecting the pH value of the suspension.
The further technical scheme is that the mixed product containing the graphene crude product is prepared by the following method:
the preparation method comprises the steps of crushing and sieving biochar to obtain charcoal powder, mixing the charcoal powder with potassium metal salt, grinding to obtain a mixture, carrying out temperature programming and activation treatment under the nitrogen atmosphere, and cooling to room temperature to obtain a mixed product containing a graphene crude product.
It should be noted that, in the preparation method of the mixed product containing the crude graphene product in the present invention, reference may be made to the method for preparing the crude graphene product in patent CN111686761A, and a person skilled in the art may also adopt other manners, such as an oxidation-reduction method, a combustion reaction method, etc., to prepare the crude graphene product, and then adopt the steps S1-S2 of the present invention to wash the crude graphene product with an organic acid to obtain a final graphene product.
The further technical scheme is that in the step S2, the centrifugal speed is 10000-12000/min. For example, in other embodiments, the centrifugation speed of step S2 is 10000/min, 10500/min, 11000/min, 11500/min, or 12000/min.
The further technical scheme is that in the step S2, the drying temperature is 90-100 ℃. For example, in other embodiments, the drying temperature of step S2 is 90 ℃, 94 ℃, 98 ℃, or 100 ℃.
The invention also provides a preparation method of graphene, which comprises the method for applying the organic acid in the graphene preparation process.
Compared with the prior art, the invention can achieve the following technical effects:
according to the method, in the preparation process of the graphene, organic acid is adopted to neutralize the crude graphene, the principle is shown in figure 7, deionized water and absolute ethyl alcohol are used to wash the precipitate, the final graphene product is obtained, and the neutralization and washing process can completely avoid the use of inorganic acid such as strong acid such as hydrochloric acid. The organic acid (monobasic organic acid, dibasic organic acid, tribasic organic acid and the like) used in the invention has wide sources and various choices, for example, acetic acid is widely distributed in the nature, and generally exists in the form of ester in fruit or vegetable oil. Oxalic acid is an organic substance, a metabolite of an organism, is a binary weak acid, is widely distributed in plants, animals and fungi, and plays different functions in different organisms. Compared with the use of strong acid (hydrochloric acid, nitric acid and sulfuric acid) and strong base (sodium hydroxide and potassium hydroxide), the organic acid adopted by the invention has the advantage of environmental friendliness, at least, the natural environment is acceptable, and the sewage treatment cost is greatly reduced. The production process disclosed by the invention is green and environment-friendly, and reduces the production cost of the graphene.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the description below are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
Fig. 1 is an SEM image of graphene prepared in example 1;
fig. 2 is an EDS spectrum of graphene prepared in example 2;
fig. 3 is a raman spectrum of graphene prepared in example 3;
fig. 4 is an XRD spectrum of graphene prepared in example 4;
FIG. 5 is an AFM spectrum of graphene prepared in example 5;
FIG. 6 is an HRTEM spectrum of graphene prepared in example 6;
fig. 7 is a schematic diagram of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the drawings in the embodiments of the present invention, in which like reference numerals represent like elements. It is apparent that the embodiments to be described below are only a part of the embodiments of the present invention, and not all of them. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It will be understood that the terms "comprises" and/or "comprising," when used in this specification and the appended claims, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
It is also to be understood that the terminology used in the description of the embodiments of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of embodiments of the invention. As used in this description of embodiments of the invention and the appended claims, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
Example 1
Pulverizing biochar, sieving, mixing with potassium metal salt, and adding N 2 Carrying out high-temperature treatment under an atmosphere condition, and then reducing the temperature to room temperature to obtain a mixed product containing a graphene crude product; soaking 1 g of the mixed product in 5 ml of deionized water, detecting the pH value to be 10, slowly adding acetic acid into the mixed product to generate a large amount of bubbles until the acetic acid is added and bubbles do not exist any more, and stopping adding the acetic acid when the pH value of the suspension is adjusted to 6-7; and then, repeatedly washing the precipitate with deionized water and ethanol for 5 times, performing high-speed centrifugal separation to obtain the precipitate, and drying in a vacuum drying oven to obtain the final graphene product. The graphene product was flaky as detected by SEM, see fig. 1.
Example 2
Pulverizing biochar, sieving, mixing with potassium metal salt, and adding N 2 Carrying out high-temperature treatment under an atmosphere condition, and then reducing the temperature to room temperature to obtain a mixed product containing a graphene crude product; soaking 1 g of the mixed product in 5 ml of deionized water, detecting the pH value to be 10, and slowly adding mixed organic acid of formic acid and acetic acid into the mixed product, wherein the volume ratio of formic acid to acetic acid is 1:1, generating a large amount of bubbles until no more bubbles are formed by adding the organic acid, and adjusting the suspensionStopping adding the organic acid when the pH value is 6-7; and then, repeatedly washing the precipitate with deionized water and ethanol for 7 times, performing high-speed centrifugal separation to obtain the precipitate, and drying in a vacuum drying oven to obtain the graphene product. EDS detection is carried out, the result is shown in figure 2, the carbon content of the graphene product is 96.06wt%, and the oxygen content is 3.94wt%; the atomic percentages are C97.02% and O2.98%.
Example 3
Pulverizing biochar, sieving, mixing with potassium metal salt, and adding N 2 Carrying out high-temperature treatment under an atmosphere condition, and then reducing the temperature to room temperature to obtain a mixed product containing a graphene crude product; 1 g of the mixed product is soaked in 5 ml of deionized water, the pH value is detected to be 10, and mixed organic acid of formic acid and acetic acid is slowly added into the mixed product, wherein the ratio of formic acid: the volume ratio of oxalic acid is 1; and then, repeatedly washing with deionized water and washing with ethanol for 5 times, carrying out high-speed centrifugal separation to obtain a precipitate, and drying in a vacuum drying oven to obtain a graphene product. ID/IG =0.0677 for this graphene product; IG/I2D =0.979 is shown in fig. 3.
Example 4
Pulverizing biochar, sieving, mixing with potassium metal salt, and adding N 2 Carrying out high-temperature treatment under an atmosphere condition, and then reducing the temperature to room temperature to obtain a mixed product containing a graphene crude product; 1 g of the mixed product is soaked in 5 ml of deionized water, the pH value is detected to be 10, and mixed organic acid of formic acid and lactic acid is slowly added into the mixed product, wherein the ratio of formic acid: the volume ratio of lactic acid is 1. The XRD pattern of the graphene product is shown as figure 4. The peak is sharp at 26.02 shown in FIG. 4.
Example 5
Pulverizing biochar, sieving, mixing with potassium metal salt, and adding N 2 Treating at high temperature under atmosphere, and cooling to room temperature to obtain stone-containing productA mixed product of crude myrcene; soaking 1 g of the mixed product in 5 ml of deionized water, detecting the pH value to be 10, and slowly adding mixed organic acid of formic acid and gluconic acid into the mixed product, wherein the ratio of formic acid: the volume ratio of the gluconic acid is 1. The AFM spectrum of the graphene product is shown in figure 5 by Raman spectrum detection.
Example 6
Pulverizing biochar, sieving, mixing with potassium metal salt, and adding N 2 Carrying out high-temperature treatment under an atmosphere condition, and then reducing the temperature to room temperature to obtain a mixed product containing a graphene crude product; 1 g of the mixed product is soaked in 5 ml of deionized water, the pH value is detected to be 10, and mixed organic acid of acetic acid and citric acid is slowly added into the mixed product, wherein the weight ratio of acetic acid: the volume ratio of citric acid is 1. The HRTEM spectrum of this graphene product is shown in fig. 6.
In the above embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
While the invention has been described with reference to specific embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A method for applying organic acid in a graphene preparation process is characterized by comprising the following steps:
s1, soaking a mixed product containing a graphene crude product in deionized water to obtain a suspension;
s2, adding organic acid into the suspension obtained in the S1 until the pH value of the suspension is 6-7; repeatedly washing with deionized water and absolute ethyl alcohol for many times; and after high-speed centrifugal separation, placing the precipitate in an oven and drying to obtain the graphene product.
2. The method of applying an organic acid in a process for preparing graphene according to claim 1, wherein the organic acid is a mono-organic acid, a di-organic acid and/or a tri-organic acid.
3. The method of claim 2, wherein the organic acid is one or more of formic acid, acetic acid, oxalic acid, lactic acid, citric acid, and gluconic acid.
4. The method of claim 3, wherein the organic acid is mixed in any ratio when the organic acid is a mixture of a plurality of acids.
5. The method of claim 1, wherein the step S1 further comprises detecting a pH of the suspension.
6. The method of applying an organic acid in a process for preparing graphene according to claim 1, wherein the number of the repeated washing with deionized water and absolute ethanol in step S2 is 1 to 20.
7. The method of claim 1, wherein the mixed product containing crude graphene is prepared by the following steps:
the preparation method comprises the steps of crushing and sieving biochar to obtain charcoal powder, mixing the charcoal powder with potassium metal salt, grinding to obtain a mixture, carrying out temperature programming and activation treatment under the nitrogen atmosphere, and cooling to room temperature to obtain a mixed product containing a graphene crude product.
8. The method of claim 1, wherein in the step S2, the centrifugal speed is 10000-12000/min.
9. The method of applying an organic acid in a process of preparing graphene according to claim 1, wherein the drying temperature in the step S2 is 90-100 ℃.
10. A method for producing graphene, comprising the method according to any one of claims 1 to 9.
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Citations (7)
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| CN103833014A (en) * | 2012-11-23 | 2014-06-04 | 海洋王照明科技股份有限公司 | Graphene and preparation method thereof |
| CN104058399A (en) * | 2014-07-17 | 2014-09-24 | 山东理工大学 | Direct preparation method of high-purity high-quality graphene |
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| WO2016114617A1 (en) * | 2015-01-15 | 2016-07-21 | 주식회사 그래핀올 | Purification method for graphene oxide |
| WO2017181826A1 (en) * | 2016-04-19 | 2017-10-26 | 广西大学 | Method for manufacturing three-dimensional hierarchical porous graphene powder |
| CN108314034A (en) * | 2018-05-16 | 2018-07-24 | 曾功昶 | A kind of porous coconut husk charcoal method for graphitizing |
| CN109336097A (en) * | 2018-09-07 | 2019-02-15 | 北京若水金枫科技有限公司 | A kind of preparation method and mass production device of graphene |
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- 2022-11-04 CN CN202211378454.3A patent/CN115650222A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103833014A (en) * | 2012-11-23 | 2014-06-04 | 海洋王照明科技股份有限公司 | Graphene and preparation method thereof |
| CN104058399A (en) * | 2014-07-17 | 2014-09-24 | 山东理工大学 | Direct preparation method of high-purity high-quality graphene |
| CN104445167A (en) * | 2014-11-28 | 2015-03-25 | 湖南科技大学 | Preparation method of water-soluble graphene |
| WO2016114617A1 (en) * | 2015-01-15 | 2016-07-21 | 주식회사 그래핀올 | Purification method for graphene oxide |
| WO2017181826A1 (en) * | 2016-04-19 | 2017-10-26 | 广西大学 | Method for manufacturing three-dimensional hierarchical porous graphene powder |
| CN108314034A (en) * | 2018-05-16 | 2018-07-24 | 曾功昶 | A kind of porous coconut husk charcoal method for graphitizing |
| CN109336097A (en) * | 2018-09-07 | 2019-02-15 | 北京若水金枫科技有限公司 | A kind of preparation method and mass production device of graphene |
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