CN107140632B - Preparation method of large-size graphene oxide lamellar layer with high mechanical strength - Google Patents
Preparation method of large-size graphene oxide lamellar layer with high mechanical strength Download PDFInfo
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Abstract
The invention relates to a preparation method of a large-size graphene oxide lamellar layer with high mechanical strength, which comprises the following steps: firstly, adding potassium persulfate, phosphorus pentoxide and concentrated sulfuric acid to pretreat graphite, then further oxidizing the graphite by potassium permanganate under an ice bath condition, controlling the temperature to be 4-6 ℃, immediately adding deionized water and hydrogen peroxide to react after a period of stirring, diluting and stirring, controlling the temperature to be 14-18 ℃ in the diluting process, finally, carrying out multi-step centrifugation, adding NaCl with the concentration of 5 mol/L into the dispersion solution of the graphene oxide to separate graphene oxide lamella, dissolving the NaCl to 30% of saturation, and separating out a precipitate from the solution; and standing the solution overnight, and removing the supernatant to obtain the large-size graphene oxide sheet layer. The preparation method is safe and simple in preparation process, can be used for preparing the 7-8 mu m large-size graphene oxide lamella, is concentrated in size distribution, high in lamella mechanical strength and short in preparation period, and has a good application prospect.
Description
Technical Field
The invention belongs to the field of preparation of large-size graphene oxide lamella, and particularly relates to a preparation method of a large-size graphene oxide lamella with high mechanical strength.
Background
The performance of the graphene oxide is closely related to the transverse size of the graphene oxide, the smaller the transverse size is, the more hydrophilic groups are, the better the water solubility is, the stronger the biocompatibility is, and the greater the biotoxicity is; the larger the transverse dimension is, the less the surface oxygen-containing functional groups are, the more hydrophobic the surface is, the less surface defects are, and the mechanical strength is therebyIs enhanced. The temperature is an important condition for controlling the size of the graphene oxide layer, the lower the temperature is, the smaller the oxidation degree of the surface of the graphene oxide is, the fewer the oxidation functional groups are contained, and the larger the size of the graphene oxide layer obtained by ultrasonic treatment is. The research history of the preparation method of graphite oxide is long, various improvement methods based on the Hummers method are mainly adopted for preparing graphene oxide at present, but the graphene oxide sheets prepared by the methods have small sizes and are distributed in the range of 0.1-3 mu m, and the graphene oxide sheets need to be subjected to size separation. These improved methods for preparing graphene oxide are in KMnO4The temperature can be heated to 80 ℃ or even higher in the oxidation reaction and deionized water dilution processes, the reaction is violent, certain dangerousness is realized, the preparation period is long, the operation is complex, the yield is low, and the mechanical strength of the prepared graphene oxide is low. At present, a multi-step centrifugation method is adopted to control the size of graphene oxide so as to separate the graphene oxide, but the separation effect of the separation method is poor, and the graphene oxide lamella with the large size is still doped with the graphene oxide lamella with the small size, and the graphene oxide lamella with the large size needs to be further separated by adopting a salting-out method.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a large-size graphene oxide sheet layer with high mechanical strength, and the method is used for preparing KMnO by using an ice bath method4The temperature conditions in the oxidation reaction and deionized water dilution processes are strictly controlled, graphene oxide is prepared through pre-oxidation and oxidation, and the graphene oxide is subjected to size separation by using a multi-step centrifugation method and a salting-out method, so that the finally prepared graphene oxide is large in sheet size, high in mechanical strength, short in preparation period, simple to operate and high in yield.
The invention relates to a preparation method of a large-size graphene oxide lamellar layer with high mechanical strength, which comprises the following steps:
(1) adding potassium persulfate (K) to the concentrated sulfuric acid2S2O8) And phosphorus pentoxide (P)2O5) Performing ultrasonic treatment for 0.5 h; then adding the natural graphite into the dispersed solution at 78-82 ℃, stirring for 4.5 hours by using a magnetic stirrer at the temperature of 78-82 ℃, and coolingCooling to room temperature, diluting with deionized water, and standing overnight; removing supernatant, carrying out suction filtration on the precipitate by using a 0.2mm filter, drying the precipitate for 12 hours in a vacuum drying oven after removing impurities, and grinding to obtain pre-oxide after drying;
(2) taking out the dried preoxidate, grinding the preoxidate into powder, and adding the powder into 120ml of concentrated sulfuric acid for stirring, wherein the temperature in the process is controlled to be 4-6 ℃; taking 15g of potassium permanganate (KMnO)4) Grinding the raw materials into powder, and slowly adding the powder into concentrated sulfuric acid, wherein the process is carried out in an ice bath, and the temperature is controlled to be 4-6 ℃; then controlling the temperature to be 33-37 ℃, stirring and reacting for 2H, slowly dropwise adding 250mL of deionized water to dilute the solution, stirring for 2H in an ice bath during the dilution process, controlling the dilution temperature to be 14-18 ℃, then adding 0.7L of deionized water, and immediately adding 20mL of 30% hydrogen peroxide (H)2O2) The mixture reacts to generate bubbles, and the color changes from brown to bright yellow;
(3) standing the mixture solution overnight, removing supernatant, diluting with 1L of deionized water, subpackaging the diluted solution into 35 50ml centrifuge tubes, centrifuging in a centrifuge with a centrifugation rate of 10000RPM for 10min, and removing supernatant; the precipitate a obtained after centrifugation was placed in a beaker and concentrated again at a concentration of 1: diluting and cleaning with 10L hydrochloric acid, subpackaging the cleaned precipitate A into 30 50ml centrifuge tubes, centrifuging for 10min in a centrifuge with a centrifugation rate of 10000RPM, and removing the supernatant; washing the precipitate B obtained after centrifugation with deionized water, subpackaging the washed precipitate B into 30 50ml centrifuge tubes, adding deionized water, and centrifuging for 10min in a centrifuge with a centrifugation speed of 10000 RPM; diluting the precipitate C obtained after centrifugation with deionized water, and performing ultrasonic treatment for 0.5 h;
(4) adding NaCl with the concentration of 5 mol/L into the dispersion solution of the graphene oxide for salting out and precipitating, wherein the NaCl is dissolved to 30% of saturation degree, and precipitates are separated out from the solution; and standing the solution overnight, and removing the supernatant to obtain the large-size graphene oxide sheet layer.
The mass ratio of the potassium persulfate to the phosphorus pentoxide to the natural graphite in the step (1) is 2.5: 2.5: 3.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method disclosed by the invention is simple in preparation process and easy to operate, can be used for preparing the large-size graphene oxide lamella with the thickness of 7-8 microns, and has the advantages of high lamella mechanical strength, short preparation period and good application prospect.
Drawings
FIG. 1 is an Atomic Force Microscope (AFM) image of the large-sized graphene oxide sheet prepared in this example before salting out.
FIG. 2 is an Atomic Force Microscope (AFM) image of the salted-out large-size graphene oxide sheet prepared in this example.
Detailed Description
The invention is further illustrated by the following specific examples.
Example 1
A preparation method of a large-size graphene oxide lamellar layer with high mechanical strength comprises the following steps:
(1) to 12ml of concentrated sulfuric acid was added 2.5g of potassium persulfate (K)2S2O8) And 2.5g of phosphorus pentoxide (P)2O5) Performing ultrasonic treatment for 0.5 h; then, adding 3g of natural graphite into the dispersed solution at 78-82 ℃, stirring for 4.5 hours by using a magnetic stirrer at the temperature of 80 ℃, cooling to room temperature, diluting with 500ml of deionized water, and standing overnight; removing supernatant, performing suction filtration on the precipitate by using a 0.2mm filter, removing impurities, drying the precipitate in a vacuum drying oven at 60 ℃ for 12 hours, and grinding to obtain a pre-oxide after drying;
(2) taking out the dried preoxidate, grinding the preoxidate into powder, adding the powder into 120ml of concentrated sulfuric acid, and stirring, wherein the temperature in the process is controlled to be 5 ℃; taking 15g of potassium permanganate (KMnO)4) Grinding the raw materials into powder, and slowly adding the powder into concentrated sulfuric acid, wherein the process is carried out in an ice bath, and the temperature is controlled at 6 ℃; then the temperature is controlled to be 35 ℃ and stirred for reaction for 2h, 250ml of deionized water is slowly dripped to dilute the solution, the solution is also stirred for 2h in an ice bath during the dilution process, and the dilution temperature is controlledControlled at 18 deg.C, a further 0.7L of deionized water was added and immediately 20mL of 30% hydrogen peroxide (H)2O2) The mixture reacts to generate bubbles, and the color changes from brown to bright yellow;
(3) standing the mixture solution overnight, removing supernatant, diluting with 1L of deionized water, subpackaging the diluted solution into 35 50ml centrifuge tubes, centrifuging in a centrifuge with a centrifugation rate of 10000RPM for 10min, and removing supernatant; the precipitate a obtained after centrifugation was placed in a beaker and concentrated again at a concentration of 1: diluting and cleaning with 10L hydrochloric acid, subpackaging the cleaned precipitate A into 30 50ml centrifuge tubes, centrifuging for 10min in a centrifuge with a centrifugation rate of 10000RPM, and removing the supernatant; washing the precipitate B obtained after centrifugation with deionized water, subpackaging the washed precipitate B into 30 50ml centrifuge tubes, adding deionized water, and centrifuging for 10min in a centrifuge with a centrifugation speed of 10000 RPM; diluting the precipitate C obtained after centrifugation with deionized water, and performing ultrasonic treatment for 0.5 h;
(4) adding NaCl with the concentration of 5 mol/L into the dispersion solution of the graphene oxide for salting out and precipitating, wherein the NaCl is dissolved to 30% of saturation degree, and precipitates are separated out from the solution; and standing the solution overnight, and removing the supernatant to obtain the large-size graphene oxide sheet layer.
Scanning the surface of the large-size graphene oxide lamella layer prepared in the embodiment before salting out and the surface after salting out by using an Atomic Force Microscope (AFM) graphene oxide, as shown in fig. 1 and 2, as can be seen from fig. 1, the surface appearance of the large-size graphene oxide lamella layer before salting out is shown in the invention; FIG. 1 shows that the surface of the large-size graphene oxide sheet layer of the present invention is mainly composed of graphene oxide sheets larger than 5um and contains a small amount of graphene oxide sheets smaller than 5 um; as can be seen from FIG. 2, the salted-out surface appearance of the large-size graphene oxide sheet layer is shown; FIG. 2 shows that the surface of the large-size graphene oxide sheet layer of the present invention is mainly composed of 7-8 μm graphene oxide sheets.
Claims (2)
1. A preparation method of a large-size graphene oxide sheet layer with high mechanical strength is characterized by comprising the following steps:
(1) adding potassium persulfate (K) into concentrated sulfuric acid2S2O8) And phosphorus pentoxide (P)2O5) Performing ultrasonic treatment for 0.5 h; then, adding natural graphite into the dispersed solution at 78-82 ℃, stirring for 4.5 hours by using a magnetic stirrer at 78-82 ℃, cooling to room temperature, diluting with deionized water, and standing overnight; removing supernatant, carrying out suction filtration on the precipitate by using a 0.2mm filter, drying the precipitate for 12 hours in a vacuum drying oven after removing impurities, and grinding to obtain pre-oxide after drying;
(2) taking out the dried preoxidate, grinding the preoxidate into powder, and then adding the powder into 120ml of concentrated sulfuric acid for stirring, wherein the temperature in the process is controlled to be 4-6 ℃; taking 15g of potassium permanganate (KMnO)4) Grinding the raw materials into powder, and slowly adding the powder into concentrated sulfuric acid, wherein the process is carried out in an ice bath, and the temperature is controlled to be 4-6 ℃; then stirring and reacting for 2H at the temperature of 33-37 ℃, slowly dropwise adding 250mL of deionized water to dilute the solution, stirring for 2H in an ice bath during dilution, controlling the dilution temperature to be 14-18 ℃, then adding 0.7L of deionized water, and immediately adding 20mL of 30% hydrogen peroxide (H)2O2) The mixture reacts to generate bubbles, and the color changes from brown to bright yellow;
(3) standing the mixture solution overnight, removing supernatant, diluting with 1L deionized water, subpackaging the diluted solution into 35 50ml centrifuge tubes, centrifuging in a centrifuge with centrifugation rate of 10000RPM for 10min, and removing supernatant; the precipitate a obtained after centrifugation was placed in a beaker and concentrated again at a concentration of 1: diluting and cleaning with 10L hydrochloric acid, subpackaging the cleaned precipitate A into 30 50ml centrifuge tubes, centrifuging for 10min in a centrifuge with a centrifugation rate of 10000RPM, and removing the supernatant; washing the precipitate B obtained after centrifugation with deionized water, subpackaging the washed precipitate B into 30 50ml centrifuge tubes, adding deionized water, and centrifuging for 10min in a centrifuge with a centrifugation speed of 10000 RPM; diluting the precipitate C obtained after centrifugation with deionized water, and performing ultrasonic treatment for 0.5 h;
(4) adding NaCl with the concentration of 5 mol/L into the dispersion solution of the graphene oxide for salting out and precipitating, wherein the NaCl is dissolved to 30% of saturation, and precipitates are separated out from the solution; standing the solution overnight, and removing supernatant to obtain a large-size graphene oxide sheet layer; the surface of the prepared large-size graphene oxide sheet layer is mainly provided with graphene oxide sheets larger than 5um, and a small amount of graphene oxide sheets smaller than 5um are contained; wherein the surface of the large-size graphene oxide sheet layer is mainly a 7-8 mu m graphene oxide sheet layer.
2. The method for preparing large-size graphene oxide sheets with high mechanical strength according to claim 1, wherein the mass ratio of potassium persulfate, phosphorus pentoxide and natural graphite in the step (1) is 2.5: 2.5: 3.
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