CN108546959B - Reduced graphene oxide and preparation method thereof - Google Patents
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Abstract
The invention belongs to the technical field of material preparation, and particularly relates to reduced graphene oxide and a preparation method thereof. The invention provides a preparation method of reduced graphene oxide, which comprises the following steps: a) inserting the paired graphite electrodes into an electrolyte prepared from sodium thiosulfate and sodium hydroxide, and electrifying the paired graphite electrodes for electrolysis; b) collecting the reduced graphene oxide solution obtained after the electrolysis in the step a), and carrying out post-treatment on the reduced graphene oxide solution to obtain the reduced graphene oxide. In the invention, sodium thiosulfate and sodium hydroxide are used as electrolytes, low-concentration electrolysis can be carried out to prepare reduced graphene oxide, sodium thiosulfate with reducibility is used as a main electrolyte, the electrolysis environment is mild, the reduced graphene oxide stripped by electrolysis is broken or oxidized to a low degree, and the salt content of the reduced graphene oxide solution obtained by electrolysis is low.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to reduced graphene oxide and a preparation method thereof.
Background
Reduced graphene oxide can be prepared in large batch by a redox method, but the reduced graphene oxide prepared by the redox method can generate a large amount of oxygen-containing functional groups on the surface layer of the reduced graphene oxide, so that the structure of the reduced graphene oxide is damaged, and the conductivity of the reduced graphene oxide is reduced. The liquid phase stripping method is a hotspot for researching the preparation of reduced graphene oxide in recent years because of simplicity, but the expansion degree of graphite, ultrasonic power, ultrasonic time and the like in the preparation method are difficult to control, and the method has great difficulty in large-scale preparation of reduced graphene oxide. Therefore, it is one of the hot spots in the research on the preparation of reduced graphene oxide to find a green, simple and easily-repeatable method.
When the reduced graphene oxide is prepared by an electrochemical method, a plurality of substances can be used as electrolytes, but in view of the complex synthesis of ionic liquid or polyelectrolyte, the difficult separation of byproducts, concentrated sodium hydroxide, concentrated sulfuric acid or concentrated salt such as K2SO4、Na2SO4When the solution is used as electrolyte, the prepared reduced graphene oxide solution has excessive salt content and is difficult to separate; sulfuric acid asDuring electrolyte, the oxidation degree is too high, and the surface of the prepared reduced graphene oxide contains oxygen-containing functional groups; when strong acid and strong base are used as electrolyte, the current in the solution is too large, so that the power supply short circuit is easily caused in the electrolytic process, the electrolyte has strong corrosivity and has potential harm to the environment and experiment workers, in addition, the high-concentration salt is used as the electrolyte, so that the preparation cost and the later-stage purification cost are greatly increased, and the risk of damaging electrolytic equipment by short circuit easily occurs.
Disclosure of Invention
In view of the above, the invention provides reduced graphene oxide and a preparation method thereof, which are used for solving the problems of more by-products, excessive salt content and difficult salt separation in the conventional electrochemical method for preparing reduced graphene oxide.
The specific technical scheme of the invention is as follows:
a preparation method of reduced graphene oxide comprises the following steps:
a) inserting a pair of graphite electrodes into an electrolyte prepared from sodium thiosulfate and sodium hydroxide, and electrifying the pair of graphite electrodes for electrolysis;
b) collecting the reduced graphene oxide solution obtained after the electrolysis in the step a), and carrying out post-treatment on the reduced graphene oxide solution to obtain the reduced graphene oxide.
Preferably, the concentration of sodium hydroxide in the electrolyte in the step a) is 0.0625M-0.25M;
the concentration of the sodium thiosulfate in the electrolyte is 0.015-0.075M.
Preferably, the molar ratio of sodium hydroxide to sodium thiosulfate in the electrolyte in the step a) is 0.83-3.33.
Preferably, the pH value of the electrolyte in the step a) is 11-13.4.
Preferably, the voltage for the electrolysis in step a) is 7V to 13V.
Preferably, the time for the electrolysis in the step a) is 0.5h to 4 h.
Preferably, the post-treatment of step b) comprises:
centrifuging, collecting supernatant, and sequentially washing and drying the supernatant.
Preferably, the washing comprises:
adding water and ethanol into the supernatant, centrifuging, and removing precipitate.
Preferably, the drying temperature is 60-80 ℃;
the drying time is 5-12 h.
The invention also provides reduced graphene oxide prepared by the preparation method.
In summary, the invention provides a preparation method of reduced graphene oxide, which comprises the following steps: a) inserting a pair of graphite electrodes into an electrolyte prepared from sodium thiosulfate and sodium hydroxide, and electrifying the pair of graphite electrodes for electrolysis; b) collecting the reduced graphene oxide solution obtained after the electrolysis in the step a), and carrying out post-treatment on the reduced graphene oxide solution to obtain the reduced graphene oxide. In the invention, sodium thiosulfate and sodium hydroxide are used as electrolytes, low concentration can be adopted for electrolyzing to prepare reduced graphene oxide, the concentration of sodium hydroxide is low and is used for adjusting the pH value of an electrolyte, the sodium thiosulfate with reducibility is used as a main electrolyte, the electrolysis environment is mild, and the reduced graphene oxide stripped by electrolysis is damaged or oxidized to a low degree; the concentration of the electrolyte is low, the salt content of the reduced graphene oxide solution obtained by electrolysis is low, so that the separation and purification processes of the reduced graphene oxide in the subsequent reduced graphene oxide solution are simple, and the problems of more by-products, excessive salt content and difficult salt separation of the reduced graphene oxide prepared by an electrochemical method are solved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a UV spectrum of reduced graphene oxide prepared in example 1 of the present invention;
FIG. 2 is an ultraviolet spectrum of reduced graphene oxide prepared in example 2 of the present invention;
FIG. 3 is an ultraviolet spectrum of reduced graphene oxide prepared in example 3 of the present invention;
fig. 4 is a raman spectrum of reduced graphene oxide prepared in example 1 of the present invention;
fig. 5 is a raman spectrum of reduced graphene oxide prepared in example 2 of the present invention;
fig. 6 is a raman spectrum of reduced graphene oxide prepared in example 3 of the present invention.
Detailed Description
The invention provides reduced graphene oxide and a preparation method thereof, which are used for solving the problems of more by-products, excessive salt content and difficult salt separation in the existing electrochemical method for preparing the reduced graphene oxide.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. 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.
A preparation method of reduced graphene oxide comprises the following steps:
a) inserting the paired graphite electrodes into an electrolyte prepared from sodium thiosulfate and sodium hydroxide, and electrifying the paired graphite electrodes for electrolysis;
b) collecting the reduced graphene oxide solution obtained after the electrolysis in the step a), and carrying out post-treatment on the reduced graphene oxide solution to obtain the reduced graphene oxide.
In the invention, the concentration of sodium hydroxide in the electrolyte in the step a) is 0.0625M-0.25M;
the concentration of the sodium thiosulfate in the electrolyte in the step a) is 0.015-0.075M.
The molar ratio of the sodium hydroxide to the sodium thiosulfate in the electrolyte in the step a) is 0.83-3.33.
The pH value of the electrolyte in the step a) is 11-13.4.
In the invention, the distance between the two electrodes in the pair of graphite electrodes in the step a) is 3 cm.
In the invention, the voltage for electrolysis in the step a) is 7V-13V.
The electrolysis time of the step a) is 0.5-4 h.
In the invention, the post-treatment in the step b) comprises the following steps:
centrifuging, collecting supernatant, and sequentially washing and drying the supernatant.
The centrifugation comprises a first centrifugation and a second centrifugation;
the rotating speed of the first centrifugation is 2000 rpm-4000 rpm, and the time of the first centrifugation is 5 min-10 min so as to remove large-particle sediments;
the rotating speed of the second centrifugation is 8000 rpm-10000 rpm, and the time of the second centrifugation is 5 min-10 min, so that small particle sediments are removed.
The washing comprises the following steps: adding water and ethanol into the supernatant, centrifuging, and removing precipitate. Wherein, the centrifugation is repeated for many times, the rotation speed of the centrifugation is 8000 rpm-10000 rpm, and the centrifugation time is 30 min.
In the invention, the drying temperature is 60-80 ℃;
the drying time is 5-12 h.
In the present invention, after the step b) of collecting the reduced graphene oxide solution obtained after the step a) of electrolyzing, before the step b of post-treating the reduced graphene oxide solution, the method further includes:
and (4) carrying out ultrasonic oscillation. The power of ultrasonic oscillation is 80W-120W, and the time of ultrasonic oscillation is 10 min-15 min.
The invention also provides reduced graphene oxide prepared by the preparation method.
In the invention, sodium thiosulfate and sodium hydroxide are used as electrolytes, low concentration can be adopted for electrolyzing to prepare reduced graphene oxide, the concentration of sodium hydroxide is low and is used for adjusting the pH value of an electrolyte, the sodium thiosulfate with reducibility is used as a main electrolyte, the electrolysis environment is mild, and the reduced graphene oxide stripped by electrolysis is damaged or oxidized to a low degree; the concentration of the electrolyte is low, the salt content of the reduced graphene oxide solution obtained by electrolysis is low, and the subsequent separation and purification processes of the reduced graphene oxide in the reduced graphene oxide solution are simple, so that the cost of the preparation method of the reduced graphene oxide is low; the preparation method of the reduced graphene oxide has strong adaptability, can use a wider voltage range, and in addition, the concentration of the electrolyte is low, the voltage range is wider, so that short circuit is not easy to occur in the electrolytic process.
For a further understanding of the invention, reference will now be made in detail to the following examples.
Example 1
Weighing sodium hydroxide and sodium thiosulfate, adding the sodium hydroxide and the sodium thiosulfate into water to dissolve to obtain electrolyte, adding the electrolyte into a beaker, the concentration of sodium hydroxide in the electrolyte is 0.125M, the concentration of sodium thiosulfate in the electrolyte is 0.075M, two graphite rods with the purity of 99.9 percent are inserted into the electrolyte in parallel, adding 7V direct current voltage to 3cm between two electrodes in the pair of graphite electrodes, continuously electrolyzing for 4h to obtain reduced graphene oxide solution, placing the upper layer reduced graphene oxide solution after standing in an ultrasonic cleaner, ultrasonically oscillating for 5min, centrifuging at 4000r/min for 5min in a high-speed centrifuge to remove large granule sediment at the bottom of the centrifuge tube, centrifuging at 8000r/min for 5min to remove small granule sediment at the bottom of the centrifuge tube, collecting supernatant, then, water and ethanol are respectively added into the supernatant, and the supernatant is repeatedly centrifuged for 30min at the rotating speed of 10000r/min to remove salt substances in the supernatant. And drying the washed supernatant at 60 ℃ for 6h to obtain 7.9mg of reduced graphene oxide.
Example 2
Weighing sodium hydroxide and sodium thiosulfate, adding the sodium hydroxide and the sodium thiosulfate into water to dissolve to obtain electrolyte, adding the electrolyte into a beaker, the concentration of sodium hydroxide in the electrolyte is 0.14375M, the concentration of sodium thiosulfate in the electrolyte is 0.075M, two graphite rods with the purity of 99.9 percent are inserted into the electrolyte in parallel, adding 7V direct current voltage to 3cm between two electrodes in the pair of graphite electrodes, continuously electrolyzing for 4h to obtain reduced graphene oxide solution, placing the upper layer reduced graphene oxide solution after standing in an ultrasonic cleaner, ultrasonically oscillating for 5min, centrifuging at 4000r/min for 5min in a high-speed centrifuge to remove large granule sediment at the bottom of the centrifuge tube, centrifuging at 8000r/min for 5min to remove small granule sediment at the bottom of the centrifuge tube, collecting supernatant, then, water and ethanol are respectively added into the supernatant, and the supernatant is repeatedly centrifuged for 30min at the rotating speed of 10000r/min to remove salt substances in the supernatant. And drying the washed supernatant at 60 ℃ for 6h to obtain 6.2mg of reduced graphene oxide.
Example 3
Weighing sodium hydroxide and sodium thiosulfate, adding the sodium hydroxide and the sodium thiosulfate into water to dissolve to obtain electrolyte, adding the electrolyte into a beaker, the concentration of sodium hydroxide in the electrolyte is 0.25M, the concentration of sodium thiosulfate in the electrolyte is 0.075M, two graphite rods with the purity of 99.9 percent are inserted into the electrolyte in parallel, adding 7V direct current voltage to 3cm between two electrodes in the pair of graphite electrodes, continuously electrolyzing for 4h to obtain reduced graphene oxide solution, placing the upper layer reduced graphene oxide solution after standing in an ultrasonic cleaner, ultrasonically oscillating for 5min, centrifuging at 4000r/min for 5min in a high-speed centrifuge to remove large granule sediment at the bottom of the centrifuge tube, centrifuging at 8000r/min for 5min to remove small granule sediment at the bottom of the centrifuge tube, collecting supernatant, then, water and ethanol are respectively added into the supernatant, and the supernatant is repeatedly centrifuged for 30min at the rotating speed of 10000r/min to remove salt substances in the supernatant. And drying the washed supernatant at 60 ℃ for 6 hours to obtain 11.9mg of reduced graphene oxide.
Comparative example 1
Weighing 0.4g of sodium hydroxide and 0g of sodium thiosulfate, adding the sodium hydroxide and the sodium thiosulfate into water to dissolve to obtain electrolyte, adding the electrolyte into a beaker, the concentration of sodium hydroxide in the electrolyte is 0.5M, the concentration of sodium thiosulfate in the electrolyte is 0M, two graphite rods with the purity of 99.9 percent are inserted into the electrolyte in parallel, adding 7V direct current voltage to 3cm between two electrodes in the pair of graphite electrodes, continuously electrolyzing for 4h to obtain reduced graphene oxide solution, placing the upper layer reduced graphene oxide solution after standing in an ultrasonic cleaner, ultrasonically oscillating for 5min, centrifuging at 4000r/min for 5min in a high-speed centrifuge to remove large granule sediment at the bottom of the centrifuge tube, centrifuging at 8000r/min for 5min to remove small granule sediment at the bottom of the centrifuge tube, collecting supernatant, then, water and ethanol are respectively added into the supernatant, and the supernatant is repeatedly centrifuged for 30min at the rotating speed of 10000r/min to remove salt substances in the supernatant. And drying the washed supernatant at 60 ℃ for 6h to obtain 2.1mg of reduced graphene oxide.
The concentration of sodium hydroxide in the primary electrolyte of the embodiment is large and is between 0.5M and 5M, a power supply is easy to be short-circuited when the reduced graphene oxide is prepared at the concentration, and the salt content of the reduced graphene oxide solution is very large, so that the separation is difficult. The result shows that the addition of sodium thiosulfate in the preparation method can increase the conductivity of the electrolyte, prevent short circuit, promote the stripping of reduced graphene oxide, and correspondingly reduce the salt content of the reduced graphene oxide solution.
Comparative example 2
Weighing 0g of sodium hydroxide and 0.5g of sodium thiosulfate, adding the sodium hydroxide and the sodium thiosulfate into water to dissolve the sodium hydroxide and the sodium thiosulfate to obtain electrolyte, adding the electrolyte into a beaker, enabling the concentration of the sodium hydroxide in the electrolyte to be 0M and the concentration of the sodium thiosulfate in the electrolyte to be 0.075M, then inserting two graphite rods with the purity of 99.9% into the electrolyte in parallel, enabling the distance between two electrodes in a pair of graphite electrodes to be 3cm, adding 7V direct-current voltage, continuously electrolyzing for 4 hours, and generating a large amount of white sulfur elementary substance precipitates in the electrolytic process without generating black reduced graphene oxide because no sodium hydroxide provides an alkaline environment and cannot be electrolyzed.
Example 4
The reduced graphene oxide prepared in examples 1 to 3 is detected, and the detection results refer to fig. 1 to 6.
Fig. 1 to 3 are ultraviolet spectra of reduced graphene oxide prepared in examples 1, 2 and 3 of the present invention, respectively, and the ultraviolet spectra can analyze, measure and infer the composition, content and structure of a substance by using the ultraviolet-visible spectrum and absorption degree generated by the absorption of ultraviolet and visible light by molecules or ions of the substance, and the characteristic absorption peak of reduced graphene oxide is about 270nm, which corresponds to the transition of an aromatic C — C bond. All of fig. 1 to 3 have absorption peaks at 270nm, which indicates that the substances prepared in examples 1, 2 and 3 of the present invention are reduced graphene oxide.
Fig. 4 to 6 are raman spectra of reduced graphene oxide prepared in examples 1, 2 and 3 of the present invention, which are generated by using lattice vibration interaction of incident photons and a test object to generate inelastic collision, causing the frequency of emergent photons and the frequency of incident photons to change, so as to analyze the molecular structure of a sample according to the spectral line characteristics of a raman spectrum, wherein the raman spectra are 1570cm-1The G peak, which is a peak appearing on the left and right sides, represents SP in graphite2In-plane vibration mode of hybridized carbon atoms, the intact reduction-state graphene oxide layer sheet is completely composed of hexagons of the carbon atoms, and when pentagons and heptagons or other local defects exist, a defect peak, namely a D peak, can be generated and is positioned at 1352cm-1To (3). And 2700cm-1The 2D peak is derived from two phonon inelastic scattering, the 2D peak intensity of the reduced graphene oxide is generally higher than that of the G peak, and the thinner the layer number is, the higher the 2D peak is. Fig. 4 to 6 show that no crystal peak of other salts exists except the characteristic peak of the reduced graphene oxide, which indicates that the reduced graphene oxide prepared in examples 1 to 3 has low salt content, and the preparation method of the present invention solves the problems of more by-products, excessive salt content, and difficult salt separation of the reduced graphene oxide prepared by the conventional electrochemical method.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A preparation method of reduced graphene oxide is characterized by comprising the following steps:
a) inserting a pair of graphite electrodes into an electrolyte prepared from sodium thiosulfate and sodium hydroxide, and electrifying the pair of graphite electrodes for electrolysis;
b) collecting the reduced graphene oxide solution obtained after the electrolysis in the step a), and carrying out post-treatment on the reduced graphene oxide solution to obtain the reduced graphene oxide.
2. The method according to claim 1, wherein the concentration of sodium hydroxide in the electrolyte of step a) is 0.0625M to 0.25M;
the concentration of the sodium thiosulfate in the electrolyte is 0.015-0.075M.
3. The preparation method of claim 1, wherein the molar ratio of sodium hydroxide to sodium thiosulfate in the electrolyte in the step a) is 0.83-3.33.
4. The preparation method according to claim 1, wherein the pH value of the electrolyte in the step a) is 11-13.4.
5. The method according to claim 1, wherein the voltage for the electrolysis in step a) is 7 to 13V.
6. The method according to claim 1, wherein the electrolysis time in step a) is 0.5 to 4 hours.
7. The method of claim 1, wherein the post-treating of step b) comprises:
centrifuging, collecting supernatant, and sequentially washing and drying the supernatant.
8. The method of claim 7, wherein the washing comprises:
adding water and ethanol into the supernatant, centrifuging, and removing precipitate.
9. The method according to claim 7, wherein the drying temperature is 60 ℃ to 80 ℃;
the drying time is 5-12 h.
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