CN109133040B - Preparation method of graphene aerogel with adjustable pore size - Google Patents
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Abstract
A preparation method of graphene aerogel with adjustable pore size. The graphene aerogel is prepared from graphene oxide by a reduction freezing method, and has the characteristics that the aperture size adjustable range is 5-240 mu m, the elastic modulus is up to 327kPa, organic solvents can be adsorbed, and the like; the freezing equipment used in the freezing step consists of a cooling system and a temperature measuring system, the reduction freezing temperature range is-10 ℃ to-196 ℃, and the temperature is reduced by 0.2 ℃ to 20 ℃ per second. According to the method, the morphology of the aerogel is accurately regulated and controlled by using the ice crystals as the template, so that the graphene aerogel with different pore sizes is obtained. The small-aperture graphene aerogel prepared under the high-speed freezing condition has extremely high mechanical property and heat and electricity conducting property, and can be used in the fields of catalysis and batteries. The large-aperture graphene aerogel prepared under the low-speed freezing condition has extremely high directional adsorption performance and can be used for sewage treatment. The ultra-large pore graphene aerogel prepared under the ultra-low-speed freezing condition has extremely high compression recovery performance and can be used for pressure sensors.
Description
Technical Field
The invention belongs to the technical field of carbon materials, and particularly relates to a preparation method of graphene aerogel with adjustable pore size.
Technical Field
Graphene has attracted considerable attention as a novel two-dimensional carbon material because of its excellent physical properties and extremely high specific surface area. The graphene is made into a porous aerogel block material, so that the application field of the graphene can be further widened. The graphene aerogel combines the ultralow density of the aerogel and the excellent physical properties of graphene, and has performance advantages in the fields of catalysis, electrochemistry, sewage treatment, sensing and the like.
At present, the preparation method of the graphene aerogel has great defects, and the performance of the graphene aerogel is limited due to the fact that the morphology of the graphene aerogel can not be accurately regulated and controlled. In a common preparation method, a hydrothermal method is combined with self-assembly and reduction processes to assemble graphene sheets into a three-dimensional structure [1,2], but a porous structure with ordered height and adjustable pore size cannot be prepared. The chemical deposition method can prepare the graphene aerogel [3,4] with high thermal conductivity, but the morphology of the graphene aerogel is limited by the morphology of a deposition matrix, so that the popularization and the application of the method are limited. The shape of the graphene aerogel is regulated and controlled by nucleation and growth of ice crystals [5,6] by the ice template method, but the method is limited by the difficulty in controlling freezing conditions, and the shape of the graphene aerogel is difficult to regulate and control accurately by using the ice template method at present. On the other hand, the ultra-low density and porous structure result in poor mechanical properties of graphene aerogels. Conventional reinforcement methods either greatly increase the density of the aerogel [7] or change the chemical properties of the aerogel [8], which can reduce the performance advantages of the graphene aerogel itself and cannot meet the existing requirements.
Disclosure of Invention
Aiming at the two problems in the prior art, the invention provides the graphene aerogel with the adjustable pore size and the preparation method thereof, the nucleation and growth of an ice template are regulated and controlled by controlling the freezing environment for preparing the sample, the morphology of the graphene aerogel is controlled by the ice template, and the graphene aerogel prepared under different freezing conditions has performance advantages in different aspects. The method is simple to operate and low in cost, does not change the density and chemical properties of the graphene aerogel, and can be directly combined with the existing preparation method.
The preparation method of the graphene aerogel with the adjustable pore size is characterized in that the graphene aerogel is prepared from graphene oxide by a reduction freezing method, and has the characteristics that the adjustable pore size range is 5-240 mu m, the elastic modulus is up to 327kPa, organic solvents can be adsorbed, and the like; the freezing equipment used in the freezing step consists of a cooling system and a temperature measuring system, the reduction freezing temperature range is-10 ℃ to-196 ℃, and the temperature is reduced by 0.2 ℃ to 20 ℃ per second. .
The preparation method of the graphene aerogel with the adjustable pore size comprises the following steps:
(1) preparing a graphene oxide suspension, adding a small amount of sodium nitrate into graphite flakes, adding concentrated sulfuric acid into an ice bath, stirring for several hours, slowly adding a small amount of potassium permanganate, and stirring in a constant-temperature water bath; slowly adding low-temperature deionized water, cooling to room temperature, slowly dropwise adding a small amount of hydrogen peroxide, and stirring for a period of time; adding a small amount of concentrated hydrochloric acid, standing for more than 12h, draining supernatant, repeating the process twice, transferring the remaining dark yellow suspension into a dialysis bag for dialysis until the pH value is more than 6, continuing the process for more than 4 days, performing centrifugal dispersion for multiple times at the rotating speed of 8000-10000rpm to remove unoxidized graphite, and taking out the supernatant, namely the graphene oxide suspension; the amount of the graphite flake, the sodium nitrate, the concentrated sulfuric acid, the potassium permanganate and the hydrogen peroxide used in the reaction process is calculated according to the mass ratio, namely the mass ratio of the graphite flake to the sodium nitrate to the concentrated sulfuric acid to the potassium permanganate to 20-40% of hydrogen peroxide aqueous solution is 4-5.5: 0.8-1.2: 240-270: 19-22;
(2) placing a proper amount of ascorbic acid and graphene oxide suspension into a glass beaker, ultrasonically stirring and uniformly mixing, sealing the beaker, placing the beaker into a box-type resistance furnace, and reacting for more than one hour at 50-90 ℃ to form cylindrical graphene hydrogel; carrying out ion replacement on the graphene hydrogel by using sufficient deionized water and filtering out residual impurities;
(3) starting a freezing device, using liquid nitrogen as a cold source, selecting a proper material as a freezing plate according to the required freezing speed, and fixing the freezing plate at a specific freezing temperature by controlling a cooling source;
(4) inserting a thermocouple connected with a thermodetector into the graphene hydrogel, opening a temperature recording switch, and after a temperature curve is stable, putting the graphene hydrogel on a freezing plate for directional freezing, and observing the temperature change in the hydrogel in real time;
(5) and when the internal temperature of the graphene hydrogel is consistent with the temperature of the freezing plate and does not change any more and the liquid water in the hydrogel is completely changed into ice, putting the graphene hydrogel into a vacuum freeze dryer with the vacuum degree of less than 20kPa for drying treatment for 40-80 h to obtain the black cylindrical graphene aerogel.
Further, in the step (1), the concentration of the graphene oxide suspension is 2-5 mg/ml.
Further, in the step (2), the mass ratio of the ascorbic acid to the graphene oxide is 4: 1.
Further, in step (3), the freezing plate is: PMMA plate, 6061 aluminum alloy plate, pure aluminum plate and pure copper plate.
Further, in the step (3), the preset temperature of the freezing plate is as follows: -10 ℃, -20 ℃, -40 ℃, -70 ℃, -100 ℃, 196 ℃.
Further, the graphene aerogel obtained in a freezing environment at-196 ℃ has extremely high Young's modulus (327kPa) and thermal conductivity (0.062W/mK), and low electrical resistance (1.85k omega).
Further, the graphene aerogel obtained in a freezing environment at-20 ℃ has extremely high adsorption performance (can adsorb organic solvents more than 100 times of the self weight).
Further, the graphene aerogel obtained in a freezing environment at-10 ℃ has extremely high compression recovery (the properties are not changed after more than 10 compression cycles) and thermal insulation performance (0.031W/mK).
The freezing equipment for preparing the graphene aerogel with the adjustable pore size is characterized by comprising the following steps:
(1) the system consists of a refrigeration system and a temperature measurement system;
(2) the freezing system comprises a liquid nitrogen cold source and a freezing plate, the temperature can be regulated and controlled by changing the distance between the freezing plate and the cold source, and the cooling speed can be regulated and controlled by changing the material of the freezing plate;
(3) the temperature measuring system comprises a T-shaped thermocouple, a high-frequency thermometer and a computer, wherein the T-shaped thermocouple can be inserted into a sample to obtain sample temperature data, and the high-frequency thermometer can record the temperature change of the sample and send the data to the computer to draw a temperature change curve;
the specific freezing temperature and the freezing speed can be realized by observing the freezing curve drawn by the temperature measuring system and regulating and controlling the freezing system.
The invention provides a graphene aerogel with adjustable pore size and a preparation method thereof. The small-aperture graphene aerogel prepared under the high-speed freezing condition has extremely high mechanical property and heat and electricity conducting property, and can be used in the fields of catalysis and batteries. The large-aperture graphene aerogel prepared under the low-speed freezing condition has extremely high directional adsorption performance and can be used for sewage treatment. The ultra-large pore graphene aerogel prepared under the ultra-low-speed freezing condition has extremely high compression recovery performance and can be used for pressure sensors. The preparation method of the graphene aerogel, which is simple and feasible without changing the chemical properties of graphene, has a good application prospect.
Drawings
FIG. 1 shows the micro-morphology of graphene aerogel prepared under different freezing conditions,
(a) preparing graphene aerogel under a freezing condition of-10 ℃; (b) preparing graphene aerogel under a freezing condition of-20 ℃; (c) preparing graphene aerogel under a freezing condition of-40 ℃; (d) preparing graphene aerogel under a freezing condition of-70 ℃; (e) preparing graphene aerogel under the freezing condition of-100 ℃; (f) graphene aerogel prepared under-196 ℃ freezing condition.
Detailed Description
The object and technical solution of the present invention will be further illustrated by the following specific examples in conjunction with the accompanying drawings, but the present invention is not limited thereto.
Example 1
A method for preparing graphene aerogel with high electric and thermal conductivity and high mechanical properties by using specific refrigeration equipment comprises the following steps:
(1) preparing a graphene oxide suspension, adding 1.5g of sodium nitrate into 3g of graphite flakes, adding 90ml of concentrated sulfuric acid into an ice bath, stirring for 4 hours, slowly adding 9g of potassium permanganate, and stirring for 24 hours at 30 ℃; slowly adding 200ml of 40 ℃ deionized water, cooling to room temperature, slowly adding 10ml of hydrogen peroxide dropwise, and stirring for 15 min; adding 30ml of concentrated hydrochloric acid, standing for more than 12 hours, draining supernatant, repeating the process twice, transferring the remaining dark yellow suspension into a dialysis bag for dialysis until the pH value is more than 6, continuing the process for more than 4 days, performing centrifugal dispersion for multiple times at the rotating speed of 8000-10000rpm to remove unoxidized graphite, and taking out the supernatant, namely the graphene oxide suspension;
(2) placing a proper amount of ascorbic acid and 5ml of graphene oxide suspension into a 10ml glass beaker, ultrasonically stirring for 15min, uniformly mixing, sealing the beaker, placing the beaker into a box-type resistance furnace, and reacting for 120min at 70 ℃ to form cylindrical graphene hydrogel; carrying out ion replacement on the graphene hydrogel by using sufficient deionized water and filtering out residual impurities;
(3) starting a freezing device, using liquid nitrogen as a cold source, selecting a pure copper plate as a freezing plate, and fixing the freezing plate at-196 ℃ by controlling the cold source;
(4) inserting a thermocouple connected with a thermodetector into the graphene hydrogel, opening a temperature recording switch, placing the graphene hydrogel on a freezing plate for directional freezing after a temperature curve is stable, keeping temperature recording and observing the temperature change in the hydrogel in real time;
(5) when the internal temperature of the graphene hydrogel is consistent with the temperature of the freezing plate and does not change any more and liquid water in the hydrogel is completely changed into ice, putting the graphene hydrogel into a vacuum freeze dryer with the vacuum degree of less than 20kPa for drying treatment for 72 hours to obtain black cylindrical graphene aerogel;
(6) the material phase is tested by using characterization means such as XRD \ XPS \ Raman and the like, so that the phase of the reduced graphene oxide is changed, the C-C bond is repaired, and the functional group is removed;
(7) the microscopic morphology of the material is represented by using SEM, and as can be seen from figure 1, in the graphene aerogel prepared by freezing at-196 ℃, the graphene sheets are dense and uniform, and the morphology endows the aerogel with higher mechanical property and heat and electricity conductivity.
Example 2
A method for preparing graphene aerogel with high electric and thermal conductivity and high mechanical properties by using specific refrigeration equipment comprises the following steps:
(1) preparing a graphene oxide suspension, adding 1.5g of sodium nitrate into 3g of graphite flakes, adding 90ml of concentrated sulfuric acid into an ice bath, stirring for 4 hours, slowly adding 9g of potassium permanganate, and stirring for 24 hours at 30 ℃; slowly adding 200ml of 40 ℃ deionized water, cooling to room temperature, slowly adding 10ml of hydrogen peroxide dropwise, and stirring for 15 min; adding 30ml of concentrated hydrochloric acid, standing for more than 12 hours, draining supernatant, repeating the process twice, transferring the remaining dark yellow suspension into a dialysis bag for dialysis until the pH value is more than 6, continuing the process for more than 4 days, performing centrifugal dispersion for multiple times at the rotating speed of 8000-10000rpm to remove unoxidized graphite, and taking out the supernatant, namely the graphene oxide suspension;
(2) placing a proper amount of ascorbic acid and 5ml of graphene oxide suspension into a 10ml glass beaker, ultrasonically stirring for 15min, uniformly mixing, sealing the beaker, placing the beaker into a box-type resistance furnace, and reacting for 120min at 70 ℃ to form cylindrical graphene hydrogel; carrying out ion replacement on the graphene hydrogel by using sufficient deionized water and filtering out residual impurities;
(3) starting the freezing equipment, using liquid nitrogen as a cold source, selecting a 6061 aluminum plate as a freezing plate, and fixing the freezing plate at-20 ℃ by controlling the cold source;
(4) inserting a thermocouple connected with a thermodetector into the graphene hydrogel, opening a temperature recording switch, placing the graphene hydrogel on a freezing plate for directional freezing after a temperature curve is stable, keeping temperature recording and observing the temperature change in the hydrogel in real time;
(5) when the internal temperature of the graphene hydrogel is consistent with the temperature of the freezing plate and does not change any more and liquid water in the hydrogel is completely changed into ice, putting the graphene hydrogel into a vacuum freeze dryer with the vacuum degree of less than 20kPa for drying treatment for 72 hours to obtain black cylindrical graphene aerogel;
(6) when the material is tested by using object image characterization methods such as XRD \ XPS \ Raman and the like, the object image of reduced graphene oxide is changed, a C-C bond is repaired, and a functional group is removed;
(7) the microscopic morphology of the sample is characterized by using SEM, and as shown in FIG. 1, the graphene thin film of the graphene aerogel frozen at-20 ℃ is in a tubular structure, so that the graphene aerogel has higher adsorption performance.
Example 3
A method for preparing graphene aerogel with high electric and thermal conductivity and high mechanical properties by using specific refrigeration equipment comprises the following steps:
(1) preparing a graphene oxide suspension, adding 1.5g of sodium nitrate into 3g of graphite flakes, adding 90ml of concentrated sulfuric acid into an ice bath, stirring for 4 hours, slowly adding 9g of potassium permanganate, and stirring for 24 hours at 30 ℃; slowly adding 200ml of 40 ℃ deionized water, cooling to room temperature, slowly adding 10ml of hydrogen peroxide dropwise, and stirring for 15 min; adding 30ml of concentrated hydrochloric acid, standing for more than 12 hours, draining supernatant, repeating the process twice, transferring the remaining dark yellow suspension into a dialysis bag for dialysis until the pH value is more than 6, continuing the process for more than 4 days, performing centrifugal dispersion for multiple times at the rotating speed of 8000-10000rpm to remove unoxidized graphite, and taking out the supernatant, namely the graphene oxide suspension;
(2) placing a proper amount of ascorbic acid and 5ml of graphene oxide suspension into a 10ml glass beaker, ultrasonically stirring for 15min, uniformly mixing, sealing the beaker, placing the beaker into a box-type resistance furnace, and reacting for 120min at 70 ℃ to form cylindrical graphene hydrogel; carrying out ion replacement on the graphene hydrogel by using sufficient deionized water and filtering out residual impurities;
(3) starting a freezing device, using liquid nitrogen as a cold source, selecting a PMMA plate as a freezing plate, and fixing the freezing plate at-10 ℃ by controlling the cold source;
(4) inserting a thermocouple connected with a thermodetector into the graphene hydrogel, opening a temperature recording switch, placing the graphene hydrogel on a freezing plate for directional freezing after a temperature curve is stable, keeping temperature recording and observing the temperature change in the hydrogel in real time;
(5) when the internal temperature of the graphene hydrogel is consistent with the temperature of the freezing plate and does not change any more and liquid water in the hydrogel is completely changed into ice, putting the graphene hydrogel into a vacuum freeze dryer with the vacuum degree of less than 20kPa for drying treatment for 72 hours to obtain black cylindrical graphene aerogel;
(6) when the material is tested by using object image characterization methods such as XRD \ XPS \ Raman and the like, the object image of reduced graphene oxide is changed, a C-C bond is repaired, and a functional group is removed;
(7) the microscopic morphology of the sample is represented by using SEM, and as shown in figure 1, the graphene aerogel graphene sheet frozen at-10 ℃ is in a rod-like structure, so that the graphene aerogel has high compression cycle performance and still has strong mechanical properties after repeated compression cycles.
Citations
[1] Mohanping, yu ting, wangkun, etc. a preparation method and application of graphene aerogel, CN104973594A [ P ],2015.
[2] Weidongshan, Zhou Li Na, Sun Tai, etc. a preparation method of three-dimensional graphene oxide aerogel with high specific surface area, CN104828807A [ P ],2015.
[3] Li Feng, Hu Guang Jian, Yan Chuanwei, etc. a reduced graphene oxide/graphene foam composite material with gradient distribution of oxygen-containing functional groups and application thereof in vanadium batteries, CN 106207201A [ P ],2016.
[4] Anyhow, xuchuan, huguangde, etc. graphene/reduced graphene oxide hybrid nested porous network structure material and preparation and application thereof, CN106803592A [ P ],2017.
[5] A preparation method of graphene aerogel, CN104843676A [ P ],2015.
[6] Liujiaqi, Luoqiao, Zhang Yimeng, etc. a preparation method of spongy light graphene aerogel, CN105384165A [ P ],2016.
[7] A process for preparing high-strength graphene oxide aerogel, CN 102887508A [ P ],2013.
[8] Nilerie, Gaoying, Hehe, et al, a method for preparing bulk graphene aerogels, CN 105819440A [ P ],2016.
Claims (9)
1. The preparation method of the graphene aerogel with the adjustable pore size is characterized in that the graphene aerogel is prepared from graphene oxide by a reduction freezing method, and has the characteristics that the adjustable range of the pore size is 5-240 mu m, the elastic modulus is up to 327kPa, and an organic solvent can be adsorbed; the freezing equipment used in the freezing step consists of a cooling system and a temperature measuring system, the reduction freezing temperature range is-10 ℃ to-196 ℃, and the temperature is reduced by 0.2 ℃ to 20 ℃ per second;
the freezing equipment for preparing the graphene aerogel with the adjustable pore size comprises the following steps:
(1) the system consists of a refrigeration system and a temperature measurement system;
(2) the freezing system comprises a liquid nitrogen cold source and a freezing plate, the temperature can be regulated and controlled by changing the distance between the freezing plate and the cold source, and the cooling speed can be regulated and controlled by changing the material of the freezing plate;
(3) the temperature measuring system comprises a T-shaped thermocouple, a high-frequency thermometer and a computer, wherein the T-shaped thermocouple can be inserted into a sample to obtain sample temperature data, and the high-frequency thermometer can record the temperature change of the sample and send the data to the computer to draw a temperature change curve;
(4) the specific freezing temperature and the freezing speed can be realized by observing the freezing curve drawn by the temperature measuring system and regulating and controlling the freezing system.
2. The preparation method of the graphene aerogel with the adjustable pore size, which is characterized by comprising the following steps of:
(1) preparing a graphene oxide suspension, adding a small amount of sodium nitrate into graphite flakes, adding concentrated sulfuric acid into an ice bath, stirring for several hours, slowly adding a small amount of potassium permanganate, and stirring in a constant-temperature water bath; slowly adding low-temperature deionized water, cooling to room temperature, slowly dropwise adding a small amount of hydrogen peroxide, and stirring for a period of time; adding a small amount of concentrated hydrochloric acid, standing for more than 12h, draining supernatant, repeating the process twice, transferring the remaining dark yellow suspension into a dialysis bag for dialysis until the pH value is more than 6, continuing the process for more than 4 days, performing centrifugal dispersion for multiple times at the rotating speed of 8000-10000rpm to remove unoxidized graphite, and taking out the supernatant, namely the graphene oxide suspension; the amount of the graphite flake, the sodium nitrate, the concentrated sulfuric acid, the potassium permanganate and the hydrogen peroxide is calculated according to the mass ratio, namely the amount of the graphite flake, the sodium nitrate, the concentrated sulfuric acid, the potassium permanganate and the 20-40% hydrogen peroxide aqueous solution is 4-5.5: 0.8-1.2: 240-270: 19-22;
(2) placing a proper amount of ascorbic acid and graphene oxide suspension into a glass beaker, ultrasonically stirring and uniformly mixing, sealing the beaker, placing the beaker into a box-type resistance furnace, and reacting for more than one hour at 50-90 ℃ to form cylindrical graphene hydrogel; carrying out ion replacement on the graphene hydrogel by using sufficient deionized water and filtering out residual impurities;
(3) starting a freezing device, using liquid nitrogen as a cold source, selecting a proper material as a freezing plate according to the required freezing speed, and fixing the freezing plate at a specific freezing temperature by controlling a cooling source;
(4) inserting a thermocouple connected with a thermodetector into the graphene hydrogel, opening a temperature recording switch, and after a temperature curve is stable, putting the graphene hydrogel on a freezing plate for directional freezing, and observing the temperature change in the hydrogel in real time;
(5) and when the internal temperature of the graphene hydrogel is consistent with the temperature of the freezing plate and does not change any more and the liquid water in the hydrogel is completely changed into ice, putting the graphene hydrogel into a vacuum freeze dryer with the vacuum degree of less than 20kPa for drying treatment for 40-80 h to obtain the black cylindrical graphene aerogel.
3. The method according to claim 2, wherein in the step (1), the concentration of the graphene oxide suspension is 2-5 mg/ml.
4. The preparation method according to claim 2, wherein in the step (2), the mass ratio of the ascorbic acid to the graphene oxide is 4: 1.
5. The method according to claim 2, wherein in the step (3), the freezing plate is: PMMA plate, 6061 aluminum alloy plate, pure aluminum plate and pure copper plate.
6. The method according to claim 2, wherein in the step (3), the preset temperature of the freezing plate is: -10 ℃, -20 ℃, -40 ℃, -70 ℃, -100 ℃, 196 ℃.
7. The preparation method of claim 2, wherein the young modulus, the thermal conductivity and the electric resistance of the graphene aerogel obtained in a freezing environment at-196 ℃ are respectively up to 327kPa, 0.062W/mK and 1.85k Ω.
8. The preparation method according to claim 2, wherein the graphene aerogel obtained in a freezing environment at-20 ℃ can adsorb more than 100 times of the organic solvent by its own weight.
9. According to the preparation method of claim 2, the graphene aerogel obtained in a freezing environment at-10 ℃ is compressed for more than 10 times without changing the properties, and the thermal insulation performance reaches 0.031W/mK.
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