CN104250006B - The method of boron doping three-dimensional grapheme prepared by a kind of supercritical co - Google Patents
The method of boron doping three-dimensional grapheme prepared by a kind of supercritical co Download PDFInfo
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The present invention relates to method and the application that boron doping three-dimensional grapheme prepared by a kind of supercritical co, belong to fields of nano material application.It is characterized in that: be under the effect of fluid medium at supercritical co, with boranes compound for reductive agent and boron source, redox graphene, single stage method obtains boron doping three-dimensional grapheme.The method overcome and prepare the complicated of three-dimensional grapheme and boron doped graphene operation at present, the defect of high energy consumption and potential environmental pollution.
Description
Technical field
The present invention relates to method and the application that boron doping three-dimensional grapheme prepared by a kind of supercritical co, belong to fields of nano material application.
Background technology
Graphene is that a kind of carbon atom forms hexangle type with sp2 hybridized orbital, and only has the two-dimensional material of a carbon atom thickness, is the essentially consist unit of other dimension carbonaceous materials such as zero dimension soccerballene, one-dimensional nano carbon pipe, three-dimensional graphite; Compared with other carbon material, Graphene has more outstanding electroconductibility (10
3~ 10
4sm
-1), large specific surface area (about 2630m
2g
-1), higher Young's modulus (being about 1100GPa) and thermal conductivity (be about 5000Wm
-1k
-1); The structure of its uniqueness and the performance of a series of brilliance become one of forward position of current Materials science research, are with a wide range of applications in catalysis, electronics, biology and energy storage field; But due to reactive force strong between each lamella and Van der Waals force, make it easily reunite in preparation process, cause the reduction of its specific surface area, and then affect giving full play to of Graphene performance; People attempt to carry out functionalization by introducing other materials to Graphene and solve this problem, in recent years, it is found that two-dimensional graphene lamella is carried out assembling is prepared into a kind of three-dimensional structure material, effectively can stop the reunion of graphene sheet layer; This three-dimensional structure Graphene is outside the performances such as the original two-dimensional graphene of maintenance excellent electricity, mechanics and calorifics, have more the standby feature such as the distinctive low density of three-dimensional system, high-ratio surface sum high porosity, three-dimensional structure Graphene extends the application space of grapheme material, has more wide application prospect.
At present, the preparation method of the three-dimensional structure Graphene of bibliographical information mainly contains self-assembly method and template two kinds; In self-assembling method, graphene oxide modified by more conventional organic reagent, and produce polymerization or crosslinking reaction, thus acquisition lyogel, or with DNA modification graphene oxide and the assembling carrying out lamella also can obtain lyogel, more just obtain three-dimensional graphene oxide after lyogel is carried out lyophilize or supercritical drying; As Zhuetal modifies and crosslinking-oxidization Graphene acquisition lyogel (Adv.Funct.Mater., 2012,22,4017 – 4022) with NIPA; Xuetal obtains graphene oxide lyogel (ACSNano, 2010,4,7358 – 7362) with after the assembling of DNA modification graphene oxide; But profit obtains three-dimensional graphene oxide in this way still needs special drying means just can obtain aerogel, and if expect that Graphene also needs to carry out reduction reaction as high-temperature heat treatment, may three-dimensional structure be destroyed like this; In template, CVD is conventional method, and the template of three-dimensional is carried out deposition can obtain three-dimensional grapheme, and the method advantage is can the distribution of effective control punch, size, and shortcoming needs design template, etching template, and technique is more complicated, and cost is high; Except these two kinds of methods, can also directly obtain three-dimensional graphene oxide or Graphene, as CN103787326A with freeze-drying.But lyophilize is carried out at low temperatures, time of drying is long, and too low temperature may destroy the structure of Graphene, affects its performance; Congetal. by introducing metal ion as Fe
3+not only can crosslinking-oxidization Graphene, Fe can also be obtained by subsequent disposal
3o
4/ three-dimensional grapheme mixture (ACSNano, 2012,6,2693 – 2703).CN102824883A and CN102910625A discloses and obtains graphene oxide lyogel by introducing metal ion, then three-dimensional structure is obtained by supercritical co drying, this shows in the technique preparing three-dimensional grapheme, supercritical co is just as a kind of means of drying, but not synthesis condition.
In recent years, by heterocyclic atom as nitrogen, phosphorus, boron adulterates to Graphene, and it can be made O
2reduction there is good katalysis, be hopeful to substitute expensive nm Pt catalyst; CN103840160A discloses the method preparing nitrogen-doped graphene by microwave method, nitrogenous source and Graphene first carry out blended by the method, then microwave obtains the nitrogen-doped graphene of high-specific surface area, but the common blended nitrogen-atoms Uniform Doped that cannot make is in graphene-structured.
There is following technological deficiency in above-mentioned boron doping three-dimensional grapheme preparation method:
1, synthesis is complicated, restores after usually first obtaining three-dimensional graphene oxide, or first redox graphene is reentried three-dimensional grapheme.
2, cannot single stage method acquisition be that three-dimensional structure has again boron doped Graphene.
3, boron doped homogeneity cannot be ensured.
3, Part Methods method disclosed in CN102910625A, is the lyogel first obtaining graphene oxide or Graphene, needs the three-dimensional structure that could obtain porous again after special drying.
4, obtain three-dimensional grapheme method disclosed in CN103787326A by lyophilize, too low temperature can damage the structure of Graphene or graphene oxide, affects its performance.
In order to overcome prior art defect, the present inventor, on the basis of summing up prior art, by lot of experiments, completes the present invention.
Summary of the invention
The present invention relates to a kind of method that boron doping three-dimensional grapheme prepared by supercritical co, it is characterized in that: be under the effect of fluid medium at supercritical co, with boranes compound for reductive agent and boron source, redox graphene, single stage method obtains boron doping three-dimensional grapheme.
Described boron doping three-dimensional grapheme reduces gained by graphene oxide, and have vesicular structure and pleated structure, aperture is 0.5 ~ 200 μm, and reducing degree is C/O:3.5 ~ 5.4, and specific surface area is 200 ~ 640m
2/ g, boron doping amount is 1.2 ~ 2.8%(atom content).
The preparation method of a kind of graphite oxide aerogel of the present invention, described method steps is as follows:
(1) graphene oxide tetrahydrofuran solution is configured: graphene oxide powder be dissolved in tetrahydrofuran (THF) ultrasonic to disperseing to obtain graphene oxide tetrahydrofuran solution completely.
(2) graphene oxide tetrahydrofuran solution is transferred in autoclave, and add a certain amount of boranes reductive agent and obtain mixing solutions.
(3) in autoclave, pass into volume fraction is 99.9% high-purity CO
2, regulate temperature and pressure, make CO
2reach supercritical state, slow pressure release after constant temperature and pressure certain hour, take out powder, acetone, after washing, after centrifugal drying, obtain boron doping three-dimensional grapheme.
In step (1), graphene oxide tetrahydrofuran (THF) concentration is formulated as 220mg/mL, and preferred 15mg/mL is good.
In step (2), described boranes reductive agent is preferably the tetrahydrofuran (THF) borine having higher solubility in supercritical co, borane dimethyl sulphide, dimethylin borine, trimethylamine borane, pyridine borane, in sodium cyanoborohydride and lutidine borine any one, in mixing solutions, the concentration of boranes reductive agent is 0.3 ~ 1.0mol/L; Preferred tetrahydrofuran (THF) borine is good, and preferred concentration 1.0mol/L is good.
The volume ratio of graphene oxide tetrahydrofuran solution and reactor is 1:10, and when this volume ratio, guarantee reductive agent is dissolved in supercritical co.
Reaction conditions described in step (3) is: temperature is 40 ~ 100 DEG C, and pressure is 80 ~ 200ATM, and the constant temperature and pressure hold-time is 1 ~ 24h; Preferable reaction temperature is 100 DEG C, and pressure is 150ATM, and the reaction times is 24h is good.
The application of described boron doping three-dimensional grapheme is using boron doped three-dimensional grapheme as ultracapacitor, and the cathode material of non-platinum oxygen fuel cell.
The present invention compared with prior art, tool has the following advantages and beneficial effect: the preparation method of boron doping three-dimensional grapheme of the present invention, adopt supercritical co device, under the effect of supercritical carbon dioxide fluid, not only can redox graphene, single stage method can also carry out boron doping and obtain the Graphene of three-dimensional porous pleated structure; Boranes reductive agent can be dissolved in supercritical co, along with fluid can be covered with in any space of graphene oxide, not only can oxygen reduction base functional group, and can also in-situ doped boron; Can be controlled aperture and the specific surface area of Graphene by controlled oxidization Graphene solubility, by controlling reductive agent consumption, reaction pressure, temperature and time can control reducing degree and the boron doping ratio of Graphene; The method is simple, green, and low consumption and low cost are also conducive to industrialization; The method overcome and prepare the complicated of three-dimensional grapheme and boron doped graphene operation at present, the defect of high energy consumption and potential environmental pollution.
Accompanying drawing explanation
Fig. 1 is that the three-dimensional grapheme SEM obtained in embodiment 1 schemes.
Fig. 2 is that the three-dimensional grapheme SEM obtained in embodiment 2 schemes.
Fig. 3 is that the three-dimensional grapheme SEM obtained in embodiment 3 schemes.
Fig. 4 is that the three-dimensional grapheme SEM obtained in embodiment 4 schemes.
Fig. 5 is that the three-dimensional grapheme SEM obtained in embodiment 5 schemes.
Fig. 6 obtains three-dimensional grapheme SEM to scheme in embodiment 6.
Carbon-to-oxygen ratio (C/O) in the Graphene of table 1 embodiment.
The Graphene specific surface area of table 2 embodiment.
The doping of boron in the Graphene of table 3 embodiment.
Embodiment
Below in conjunction with concrete embodiment, the present invention will be further described.
embodiment 1
(1) graphene oxide solution is configured: graphene oxide powder is dissolved in ultrasonic 2h in tetrahydrofuran (THF) and extremely disperses completely; Graphene oxide concentration is 3mg/mL.
(2) transferred in autoclave by 1ml graphene oxide tetrahydrofuran solution, and add the agent of a certain amount of tetrahydrofuran (THF) borane reduction, the concentration of reductive agent is 0.4mol/L.
(3) in autoclave, pass into volume fraction is 99.9% high-purity CO
2, regulate temperature and pressure, make CO
2reach supercritical state, slow pressure release after constant temperature and pressure certain hour; Take out powder, acetone, after washing after centrifugal drying, obtain boron doping three-dimensional grapheme, reaction conditions is: temperature 80 DEG C, pressure 150ATM, reaction times: 15h.
Structure and shape characteristic characterize:
Gained boron doping three-dimensional grapheme sample of the present invention, by the pattern and the aperture that use field emission scanning electron microscope (SEM, JEOL, 6460) to observe material, uses N
2absorption/desorption curve characterizes porous performance and the specific surface area of Graphene.
The reducing degree of the three-dimensional grapheme obtained is in table 1, and specific surface area is in table 2, and boron doping amount (boron atomic ratio in the sample to which) is in table 3.
As shown in Figure 1, Graphene becomes porous to the pattern of the three-dimensional grapheme obtained in embodiment 1 as we can see from the figure, accordion, and aperture is about 200 μm.In embodiment 1 obtain the reducing degree of three-dimensional grapheme, C/O is about 3.8, and specific surface area is 220m
2/ g, boron doping amount is 1.2%.
embodiment 2
(1) graphene oxide solution is configured: graphene oxide powder is dissolved in ultrasonic 2h in tetrahydrofuran (THF) and extremely disperses completely; Graphene oxide concentration is 5mg/mL.
(2) transferred in autoclave by 1ml graphene oxide tetrahydrofuran solution, and add the agent of a certain amount of tetrahydrofuran (THF) borane reduction, the concentration of reductive agent is 0.4mol/L.
(3) in autoclave, the high-purity CO of volume ratio 99.9% is passed into
2, regulate temperature and pressure, make CO
2reach supercritical state, slow pressure release after constant temperature and pressure certain hour.Take out powder, acetone, after washing after centrifugal drying, obtain boron doping three-dimensional grapheme, reaction conditions is: temperature 80 DEG C, pressure 150ATM, reaction times: 15h.
The pattern of the three-dimensional grapheme obtained in embodiment 2 as shown in Figure 2.Graphene becomes porous as we can see from the figure, accordion.Aperture is about 200 μm.
In embodiment 2 obtain the reducing degree of three-dimensional grapheme, C/O is about 3.5, and specific surface area is 250m
2/ g, boron doping amount is 1.1%.
The SEM figure of comparative example 1, the pattern of Graphene is without significant difference, but its pore structure increases, thus causes its specific surface area to increase, and the reducing degree of the Graphene of embodiment 2 reduces slightly, and reason is that the amount of graphene oxide increases.
embodiment 3
(1) graphene oxide solution is configured: graphene oxide powder is dissolved in ultrasonic 2h in tetrahydrofuran (THF) and extremely disperses completely; Graphene oxide concentration is 10mg/mL.
(2) transferred in autoclave by 1ml graphene oxide tetrahydrofuran solution, and add the agent of a certain amount of tetrahydrofuran (THF) borane reduction, the concentration of reductive agent is 0.8mol/L.
(3) in autoclave, the high-purity CO of volume ratio 99.9% is passed into
2, regulate temperature and pressure, make CO
2reach supercritical state, slow pressure release after constant temperature and pressure certain hour.Take out powder, acetone, after washing after centrifugal drying, obtain boron doping three-dimensional grapheme, reaction conditions is: temperature 80 DEG C, pressure 150ATM, reaction times: 15h.
As shown in Figure 3, Graphene becomes porous to the pattern of the three-dimensional grapheme obtained in embodiment 3 as we can see from the figure, accordion, and aperture is about 100 μm.
In embodiment 3 obtain the reducing degree of three-dimensional grapheme, C/O is about 4.8, and specific surface area is 400m
2/ g, boron doping amount is 2.3%.
The SEM figure of comparative example 1 and 2, the pattern of Graphene is without significant difference, but its pore structure increases, aperture obviously reduces, thus cause its specific surface area to continue obviously to increase, it is because borane reduction agent increases that the reducing degree of the Graphene of embodiment 3 increases to 4.8, and the atomic ratio of boron in Graphene is also increased.
embodiment 4
(1) graphene oxide solution is configured: graphene oxide powder is dissolved in ultrasonic 2h in tetrahydrofuran (THF) and extremely disperses completely; Graphene oxide concentration is 15mg/mL.
(2) transferred in autoclave by 1ml graphene oxide tetrahydrofuran solution, and add the agent of a certain amount of tetrahydrofuran (THF) borane reduction, the concentration of reductive agent is 1.0mol/L.
(3) in autoclave, pass into volume ratio is 99.9% high-purity CO
2, regulate temperature and pressure, make CO
2reach supercritical state, slow pressure release after constant temperature and pressure certain hour, take out powder, acetone, after washing after centrifugal drying, obtain boron doping three-dimensional grapheme, reaction conditions is: temperature 100 DEG C, pressure 150ATM, reaction times: 15h.
As shown in Figure 4, Graphene becomes porous to the pattern of the three-dimensional grapheme obtained in embodiment 4 as we can see from the figure, accordion, and aperture is about 45 μm.
In embodiment 4 obtain the reducing degree of three-dimensional grapheme, C/O is about 4.7, and specific surface area is 640m
2/ g, boron doping amount is 2.2%.
The SEM figure of comparative example 1 ~ 3, the graphene sheet layer of the three-dimensional grapheme that embodiment 4 obtains forms three-dimensional porous network structure, and its hole number increases, and aperture obviously declines, and causes its specific surface area to increase to 640m
2/ g, the reducing degree of the Graphene of embodiment 3 increases to 4.7, be because borane reduction agent increases, and the atomic ratio of boron in Graphene is also increased.
embodiment 5
(1) graphene oxide solution is configured: graphene oxide powder is dissolved in ultrasonic 2h in tetrahydrofuran (THF) and extremely disperses completely; Graphene oxide concentration is 20mg/mL.
(2) transferred in autoclave by 1ml graphene oxide tetrahydrofuran solution, and add the agent of a certain amount of tetrahydrofuran (THF) borane reduction, the concentration of reductive agent is 1.0mol/L.
(3) in autoclave, the high-purity CO of volume ratio 99.9% is passed into
2, regulate temperature and pressure, make CO
2reach supercritical state, slow pressure release after constant temperature and pressure certain hour, take out powder, acetone, after washing after centrifugal drying, obtain boron doping three-dimensional grapheme, reaction conditions is: temperature 100 DEG C, pressure 150ATM, reaction times: 15h.
As shown in Figure 5, Graphene mostly is accordion to the pattern of the three-dimensional grapheme obtained in embodiment 5 as we can see from the figure.Vesicular structure is die-offed.
In embodiment 5 obtain the reducing degree of three-dimensional grapheme, C/O is about 4.3, and specific surface area is 200m
2/ g, boron doping amount is 1.8%.
The SEM figure of comparative example 4, the reason that the Graphene vesicular structure of the three-dimensional grapheme causing embodiment 5 to obtain disappears is that the concentration of initial oxidation Graphene is excessive, serious reunion is caused to pile up, after graphene oxide is reduced, its pattern is fixed, thus causing Graphene to be serious agglomeration state, specific surface area also sharply reduces.
embodiment 6
(1) graphene oxide solution is configured: graphene oxide powder is dissolved in ultrasonic 2h in tetrahydrofuran (THF) and extremely disperses completely; Graphene oxide concentration is 15mg/mL.
(2) transferred in autoclave by 1ml graphene oxide tetrahydrofuran solution, and add the agent of a certain amount of tetrahydrofuran (THF) borane reduction, the concentration of reductive agent is 1.0mol/L.
(3) in autoclave, the high-purity CO of volume ratio 99.9% is passed into
2, regulate temperature and pressure, make CO
2reach supercritical state, slow pressure release after constant temperature and pressure certain hour, take out powder, acetone, after washing after centrifugal drying, obtain boron doping three-dimensional grapheme, reaction conditions is: temperature 100 DEG C, pressure 100ATM, reaction times: 15h.
In contrast to embodiment 4, the pressure in the step (3) of embodiment 6 is reduced to 100ATM.
The pattern of the Graphene that embodiment 6 obtains is shown in Fig. 6, and comparative example 4, can see that the aperture of embodiment 6 obviously increases, and this is due to after pressure reduction, supercritical CO
2to the stripping declines of Graphene, pressure reduces to make the specific surface area of Graphene drop to 300m
2/ g.
embodiment 7
(1) graphene oxide solution is configured: graphene oxide powder is dissolved in ultrasonic 2h in tetrahydrofuran (THF) and extremely disperses completely; Graphene oxide concentration is 15mg/mL.
(2) transferred in autoclave by 1ml graphene oxide tetrahydrofuran solution, and add the agent of a certain amount of tetrahydrofuran (THF) borane reduction, the concentration of reductive agent is 1.0mol/L.
(3) in autoclave, pass into volume ratio is 99.9% high-purity CO
2, regulate temperature and pressure, make CO
2reach supercritical state, slow pressure release after constant temperature and pressure certain hour, take out powder, acetone, after washing after centrifugal drying, obtain boron doping three-dimensional grapheme, reaction conditions is: temperature 100 DEG C, pressure 150ATM, reaction times: 24h.
In contrast to embodiment 4, the recovery time in the step (3) of embodiment 7 extends to 24h.
The Graphene pattern that example 7 obtains is in the same manner as in Example 4, but along with the increase in reaction times, the reducing degree of Graphene increases, and C/O increases to 5.4.The doping of boron also rises to 2.5%.
embodiment 8
(1) graphene oxide solution is configured: graphene oxide powder is dissolved in ultrasonic 2h in tetrahydrofuran (THF) and extremely disperses completely; Graphene oxide concentration is 15mg/mL.
(2) transferred in autoclave by 1ml graphene oxide tetrahydrofuran solution, and add a certain amount of sodium cyanoborohydride reductive agent, the concentration of reductive agent is 1.0mol/L.
(3) in autoclave, the high-purity CO of volume ratio 99.9% is passed into
2, regulate temperature and pressure, make CO
2reach supercritical state, slow pressure release after constant temperature and pressure certain hour, take out powder, acetone, after washing after centrifugal drying, obtain boron doping three-dimensional grapheme, reaction conditions is: temperature 100 DEG C, pressure 150ATM, reaction times: 15h.
In contrast to embodiment 4, the reductive agent in the step (2) of embodiment 8 changes to sodium cyanoborohydride.
The Graphene pattern that example 8 obtains is in the same manner as in Example 4, but the reducing degree of Graphene reduces, and C/O is 4.6.This is that the doping of boron also reduces slightly, is 2.0% due to weak compared with tetrahydrofuran (THF) borine of the reductibility of sodium cyanoborohydride.
Above embodiment shows, the Graphene that the present invention adopts supercritical co to prepare possesses three-dimensional porous and pleated structure, and can doped with boron element.
The pattern of boron doping three-dimensional grapheme, aperture, the specific surface area concentration initial with graphene oxide is relevant, along with concentration increases, sample forms vesicular gradually, and now the specific surface area of Graphene increases, but after being above finite concentration, cell texture fades away, based on fold-like structures, specific surface area sharply reduces.
The kind of the reducing degree of Graphene and boron doping amount and borane reduction agent, dosage, temperature of reaction is closely related with the time, but is all controlled.
The singularity of this preparation method embodies following three aspects:
1) singularity of reaction mechanism, adopt supercritical carbon dioxide process, under the effect of CO 2 fluid, can effectively peel off Graphene and form vesicular, boranes reductive agent can be dissolved in CO 2 fluid, implement whole vesicular structure, effectively graphene oxide is reduced, and be conducive to Uniform Doped boron.
2) method is simple and green, can reduce the pollution to environment.
3) single stage method can obtain boron doped three-dimensional grapheme, reduces energy consumption cost-saving, is conducive to industrialization.
Claims (11)
1. the method for boron doping three-dimensional grapheme prepared by a supercritical co, it is characterized in that: be under the effect of fluid medium at supercritical co, with boranes compound for reductive agent and boron source, redox graphene, single stage method obtains boron doping three-dimensional grapheme.
2. the method for boron doping three-dimensional grapheme prepared by a kind of supercritical co according to claim 1, it is characterized in that: described boron doping three-dimensional grapheme reduces gained by graphene oxide, there is vesicular structure and pleated structure, aperture is 0.5 ~ 200 μm, reducing degree is C/O:3.5 ~ 5.4, and specific surface area is 200 ~ 640m
2/ g, boron doping amount is 1.2 ~ 2.8%(atom content).
3. the method for boron doping three-dimensional grapheme prepared by a kind of supercritical co as claimed in claim 1, it is characterized in that step is as follows:
(1) graphene oxide tetrahydrofuran solution is configured: graphene oxide powder be dissolved in tetrahydrofuran (THF) ultrasonic to disperseing to obtain graphene oxide tetrahydrofuran solution completely;
(2) graphene oxide tetrahydrofuran solution is transferred in autoclave, and add a certain amount of boranes reductive agent and obtain mixing solutions;
(3) in autoclave, pass into volume fraction is 99.9% high-purity CO
2, regulate temperature and pressure, make CO
2reach supercritical state, slow pressure release after constant temperature and pressure certain hour, take out powder, acetone, after washing, after centrifugal drying, obtain boron doping three-dimensional grapheme.
4. the method for boron doping three-dimensional grapheme prepared by a kind of supercritical co as claimed in claim 3, it is characterized in that: in step (1), graphene oxide tetrahydrofuran (THF) concentration is formulated as 2 20mg/mL.
5. the method for boron doping three-dimensional grapheme prepared by a kind of supercritical co as claimed in claim 4, it is characterized in that: in step (1), graphene oxide tetrahydrofuran (THF) concentration is formulated as 15mg/mL.
6. the method for boron doping three-dimensional grapheme prepared by a kind of supercritical co as claimed in claim 3, it is characterized in that: in step (2), described boranes reductive agent is the tetrahydrofuran (THF) borine having higher solubility in supercritical co, borane dimethyl sulphide, dimethylin borine, trimethylamine borane, pyridine borane, in sodium cyanoborohydride and lutidine borine any one, in mixing solutions, the concentration of boranes reductive agent is 0.3 ~ 1.0mol/L.
7. the method for boron doping three-dimensional grapheme prepared by a kind of supercritical co as claimed in claim 6, and it is characterized in that: described boranes reductive agent is tetrahydrofuran (THF) borine, concentration is 1.0mol/L.
8. the method for boron doping three-dimensional grapheme prepared by a kind of supercritical co as claimed in claim 3, it is characterized in that: the volume ratio of graphene oxide tetrahydrofuran solution and reactor is 1:10, and when this volume ratio, guarantee reductive agent is dissolved in supercritical co.
9. the method for boron doping three-dimensional grapheme prepared by a kind of supercritical co as claimed in claim 3, it is characterized in that: the reaction conditions described in step (3) is: temperature is 40 ~ 100 DEG C, pressure is 80 ~ 200atm, and the constant temperature and pressure hold-time is 1 ~ 24h.
10. the method for boron doping three-dimensional grapheme prepared by a kind of supercritical co as claimed in claim 9, and it is characterized in that: the reaction conditions described in step (3) is: temperature of reaction is 100 DEG C, pressure is 150atm, and the reaction times is 24h.
11. boron that as described in claim 1 or 3 prepared by method doping three-dimensional graphemes are as the purposes of the cathode material of ultracapacitor or non-platinum oxygen fuel cell.
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| CN106732515B (en) * | 2016-12-12 | 2019-06-07 | 安徽大学 | A kind of preparation method and its usage of the BG/ZnO nanocomposite with p-n heterojunction |
| US10814021B2 (en) | 2017-12-15 | 2020-10-27 | University Of Washington | Paramagnetic boron-doped graphene quantum dots and their application for safe magnetic resonance imaging |
| CN110255534A (en) * | 2019-06-06 | 2019-09-20 | 江苏大学 | It is a kind of to adulterate three-dimensional porous graphene aerogel and preparation method and application |
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