CN107697905A - A kind of preparation method of three-dimensional nitrogen-doped graphene aeroge - Google Patents

A kind of preparation method of three-dimensional nitrogen-doped graphene aeroge Download PDF

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CN107697905A
CN107697905A CN201711035506.6A CN201711035506A CN107697905A CN 107697905 A CN107697905 A CN 107697905A CN 201711035506 A CN201711035506 A CN 201711035506A CN 107697905 A CN107697905 A CN 107697905A
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colloidal sol
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graphene
graphene oxide
nitrogen
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方莉
邢存怀
柳丹丹
王杰
李海涛
程芳琴
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Shanxi University
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Abstract

The present invention relates to a kind of preparation method of three-dimensional nitrogen-doped graphene aeroge, it is therefore an objective to solves the problems such as preparation condition existing for existing three-dimensional nitrogen-doped graphene preparation method is harsh, strict to hydrothermal temperature and time requirement, equipment is expensive.The technical scheme is that:Graphene oxide is formulated as to 0.5~9mg/mL of concentration solution, simultaneously ultrasonic disperse obtains graphene oxide colloidal sol to magnetic agitation at room temperature;Urea and trisodium citrate are added into above-mentioned graphene oxide colloidal sol, at room temperature stirring and ultrasonic disperse;Glacial acetic acid is added dropwise into above-mentioned colloidal sol, continues stirring and ultrasonic disperse;The three-dimensional nitrogen-doped graphene gel that above-mentioned colloidal sol progress hydrothermal synthesis reaction is obtained;Supercritical fluid drying using ethanol as fluid is carried out to obtained three-dimensional nitrogen-doped graphene gel, that is, three-dimensional nitrogen-doped graphene aeroge is made.Method of the invention is simple to operate, cost is cheap, it is easy to accomplish industrialization.

Description

A kind of preparation method of three-dimensional nitrogen-doped graphene aeroge
Technical field
The present invention relates to a kind of preparation method of three-dimensional nitrogen-doped graphene aeroge.
Background technology
Graphene is one kind by individual layer sp2The new carbonaceous nanometer material that hydbridized carbon atoms are formed in the form of closelypacked Material, there is good electricity, mechanics, calorifics and mechanical performance, and greatly (theoretical value reaches 2630m to specific surface area2g-1).From Since 2004 are found by Novoselov and Geim et al., electronics, battery, biology sensor have been widely used to it and have surpassed The fields such as level capacitor.But graphene has strong pi-pi bond effect and Van der Waals force, easily generation interlayer stacks and can not It is inverse to reunite, cause the reduction of its performance.The three-dimensional grapheme of loose structure has bigger specific surface area, can provide multi-dimensional electronic biography Defeated passage, reduce transmission range of the electronics between electrode and electrolyte solution.Further, since graphene has partly leading for zero band gap Body and dirac carrier properties, while its Fermi surface is located at dirac point, causes the property of its semiconductor and Electronic Performance equal Influenceed by certain.
The band gap of graphene can be effectively opened using the doping of hetero atom (such as nitrogen, boron), regulates and controls electronic structure and band The size of gap, improve its electrical properties.When nitrogen atom doping is into graphene, electronics will be transferred to graphene from nitrogen-atoms On, carrier is changed into electron type, Fermi surface is moved on dirac point, and then opens its band gap.Due to the electricity of nitrogen-atoms Negativity is more than carbon atom, and more positive charges can be induced to be effectively improved to adjacent carbon atom in electrochemistry and solar energy Application in terms of battery;Secondly, nitrogen-atoms is close with the atomic radius of carbon atom, can prevent lattice mismatch;In addition, nitrogen-atoms with The length of covalent bond that carbon atom is formed is shorter, can improve the stability of graphene-structured.
The preparation method of three-dimensional nitrogen-doped graphene mainly has chemical vapour deposition technique, heat treating process and hydro-thermal method.
The transition metal such as chemical vapour deposition technique (CVD) generally use Ni, Cu are matrix, and carbon source and nitrogen are utilized under high temperature Source gas decomposes in substrate surface and regrows to obtain the nitrogen-doped graphene of multilayer.Feng et al. is using metallic nickel as template, second Diamines is nitrogen source, after three-dimensional nitrogen-doped graphene film is grown in nickel surface at 900 DEG C, then by methyl methacrylate (PMMA) graphenic surface is deposited on, finally PMMA is dissolved with hot hcl corrosion nickel, hot acetone respectively, obtains three-dimensional N doping stone Black alkene, its nitrogen content are 2.71at%, have good detection performance [Feng X, Zhang Y, Zhou in biology sensor J,et al.Three-dimensional nitrogen-doped graphene as an ultrasensitive electrochemical sensor for the detection of dopamine[J].Nanoscale,2015,7(6): 2427-32.].But CVD experiment condition is harsh, equipment is expensive, and due to participating in the source of the gas of deposition reaction and reacted Residual air has certain toxicity, hinders its industrial applications.
Heat treating process is under the high temperature conditions, nitrogen source compound and three-dimensional grapheme to be carried out into high temperature pyrolysis, make nitrogen-atoms It is doped in three-dimensional grapheme.Sun etc. utilizes H2O2Ultrasonic disperse graphene oxide, etch to obtain porous oxygen by oxidation Graphite alkene, three-dimensional grapheme is then obtained by hydro-thermal self assembly, freeze-drying, finally in NH3/N2, 1000 DEG C of 45 points of calcinings Three-dimensional nitrogen-doped graphene is made after clock, its specific surface area is up to 623m2g-1, nitrogen content 3.4at%.The three-dimensional N doping stone Black alkene has excellent reversible lithium storage capacity and good high-rate discharge ability [Sun J, Wang L, Song R, et al.Nitrogen-doped holey graphene foams for high-performance lithium storage [J].Rsc Advances,2015,5(111):91114-91119.].Liu etc., as template, passes through first with polystyrene Polymer template legal system obtains three-dimensional grapheme, finally in 5%NH3/ Ar, it is pyrolyzed at a temperature of 550 DEG C, obtained nitrogen content is 2.02at%, specific surface area 281.42m2g-1Three-dimensional nitrogen-doped graphene, the electrode material as lithium battery has excellent Height ratio capacity performance [Liu X, Wu Y, Yang Z, et al.Nitrogen-doped 3D macroporous graphene frameworks as anode for high performance lithium-ion batteries[J].Journal of Power Sources,2015,293:799-805.].It is three-dimensional that publication No. CN105645403A discloses a kind of high-performance N doping The preparation method of graphene, in acid condition, graphene oxide, aniline and ammonium persulfate are uniformly mixed, aniline is in over cure In the presence of sour ammonium derivant, polymerization generation polyaniline occurs, is then mixed by hydro-thermal reaction three-dimensional grapheme-polyaniline Thing, under nitrogen protection, high-temperature process obtain N doping porous three-dimensional graphene finally.N doping three is prepared using heat treating process When tieing up graphene, if temperature is too low, the reaction time is too short, it may cause to be difficult to bonding between C, N due to energy deficiency;If Temperature is too high, the reaction time is long, then the key generated between C, N may be caused to be broken.Further, since nitrogen in heat treating process The introducing of atom typically occurs in the edge and fault location of three-dimensional grapheme so that the doping rate of nitrogen is relatively low.
Hydro-thermal method is that graphene oxide and nitrogen-containing compound are carried out into self assembly under hydrothermal conditions, makes oxy radical slowly Disappear, while nitrogen atom doping is into graphene, so as to form three-dimensional nitrogen-doped graphene gel.Liao et al. is using urea as nitrogen Source, dried afterwards by hydro-thermal reaction (180 DEG C reaction 24h) and three-dimensional nitrogen-doped graphene is made, when graphene oxide and urea Mass ratio is 1:When 1, its nitrogen content is up to 7.7wt%, specific surface area 531.9m2g-1, show stronger electric conductivity With good capacitance behavior [Liao Y, Huang Y, Shu D, et al.Three-dimensional nitrogen-doped graphene hydrogels prepared via hydrothermal synthesis as high-performance supercapacitor materials[J].Electrochimica Acta,2016,194:136-142.].Chen et al. profits By the use of organic amine as nitrogen source, amine reacts to form similar acid amides with surface of graphene oxide hydroxy-acid group under hydrothermal conditions Structure, stable aromatic structure and imine structure [Chen P, Yang J J, Li S S, et are then formed by decarbonylation reaction al.Hydrothermal synthesis of macroscopic nitrogen-doped graphene hydrogels for ultrafast supercapacitor[J].Nano Energy,2013,2(2):249-256.].The three-dimensional N doping Material of the graphene as ultracapacitor, its charging and discharging currents density reach 185A/g, and power density can reach 205.0kW/kg.Patent CN102849731B provides a kind of nitrogen-doped graphene hydrogel and its preparation method and application, with Organic amine is nitrogen source, and it is uniformly mixed with graphene oxide solution, nitrogen-doped graphene hydrogel is made by hydro-thermal method.Phase Comparatively, hydro-thermal method process is easier, safer, and reaction condition is gentleer, easy to operate.
The content of the invention
Present invention aim to address preparation condition existing for existing three-dimensional nitrogen-doped graphene preparation method is harsh, right The problems such as hydrothermal temperature and time requirement are strict, equipment is expensive.A kind of system of three-dimensional nitrogen-doped graphene aeroge is provided Preparation Method.
In order to solve the above technical problems, the technical solution adopted by the present invention is:A kind of three-dimensional nitrogen-doped graphene aeroge Preparation method, comprise the following steps:
(1) using natural graphite powder as carbon source, graphene oxide is prepared using Hummer methods, takes the graphene oxide prepared 0.5~9mg/mL of concentration solution is formulated as, solvent is water and ethanol with volume ratio 0.5~5:The mixed solution of 1 composition, Magnetic agitation 0.5~2 hour at room temperature, ultrasonic disperse obtain graphene oxide colloidal sol in 0.5~2 hour;
(2) urea and trisodium citrate, the urea, lemon are added in the graphene oxide colloidal sol obtained to step (1) The mass ratio of sour trisodium and graphene oxide is 1~20:1~5:1, dissolving in 0.5~2 hour and ultrasonic disperse are stirred at room temperature 0.5~2 hour;
(3) glacial acetic acid is added dropwise in the colloidal sol obtained under agitation to step (2), the glacial acetic acid and colloidal sol Volume ratio is 0.25~1:1, continue ultrasonic disperse 0.5~2 hour after stirring 0.5~2 hour, obtain sticky sepia oxidation Graphene sol;
(4) colloidal sol that step (3) obtains is transferred in hydrothermal reaction kettle, 120~180 DEG C of temperature control, reacted 8~12 hours After cool down, obtain three-dimensional nitrogen-doped graphene gel;
(5) the three-dimensional nitrogen-doped graphene gel for being obtained step (4) with ethanol soak repeatedly, wash to pH be 7 after, adopt It is medium with ethanol, carries out the supercritical fluid drying using ethanol as fluid to it in autoclave, that is, three-dimensional N doping is made Graphene aerogel.
Further, the compound concentration of graphene oxide solution is 5mg/mL in the step (1).
The mass ratio of urea, trisodium citrate and graphene oxide is 2 in the step (2):1:1.
The volume ratio of glacial acetic acid and colloidal sol is 0.5 in the step (3):1.
Temperature in the step (4) in hydrothermal reaction kettle is 130 DEG C.
The beneficial effects of the invention are as follows:
(1) present invention uses the decentralized medium of water and alcohol mixed solution as graphene oxide.If using pure water as medium, Strong hydrogen bond is formd because the surface tension of water is larger, and between the oxygen-containing functional group and hydrone of surface of graphene oxide to make With polycondensation occurs for the gel formed in hydrothermal treatment process, causes prepared Graphene gel small volume;With straight alcohol For medium when, due to graphene oxide in ethanol dispersed poor, sedimentation of easily reuniting, it is difficult to obtain complete graphene and coagulate Glue;During using water and alcohol mixed solution as medium, the dispersiveness of graphene oxide in a solvent was both ensure that, turn avoid Due to gel polycondensation phenomenon caused by strong interaction.
(2) trisodium citrate of the present invention is both reducing agent, is crosslinking agent again.Under trisodium citrate effect, Graphene oxide can issue raw reduction reaction in the hydrothermal condition of milder, reduce the requirement to equipment;In water-heat process, With graphene oxide and urea condensation reaction can occur for trisodium citrate simultaneously, generate three-dimensional porous nitrogen-doped graphene gel, Specific surface area and structural stability significantly improve.
(3) present invention uses catalyst of the acetic acid as graphenic surface hydrolysis-sol-gel.With strong acid (such as HCl and HBr) compare, slowly ionization produces H to acetic acid in water-heat process+, slow down graphene oxide intramolecular and intermolecular dehydration be anti- Should, reduce the formation of ether and ester, improve the reduction degree of graphene oxide;In addition, acetic acid is as a kind of weak acid, it is rotten to equipment Corrosion is small.
(4) present invention prepares graphene aerogel using ethanol supercritical drying method.Dried according to common, it is three-dimensional porous Solvent in Graphene gel space due to the effect of its surface tension, can cause the contraction in hole, or even lead in volatilization process Cause structure collapse.Using ethanol supercritical drying, gas-liquid interface is disappeared, surface tension zero, and aperture will not be caused to shrink and tie Structure destroys, so as to obtain the three-dimensional porous graphene aerogel of Stability Analysis of Structures and high-specific surface area.
Brief description of the drawings
Fig. 1 is the SEM figures that three-dimensional nitrogen-doped graphene aeroge made from the embodiment of the present invention 4 amplifies 10000 times;
Fig. 2 is the SEM figures that three-dimensional nitrogen-doped graphene aeroge made from the embodiment of the present invention 4 amplifies 100000 times;
Fig. 3 is that the XPS of three-dimensional nitrogen-doped graphene aeroge made from the embodiment of the present invention 4 schemes, and wherein 3a is full spectrum Scanning figure, 3b N1sSpectrogram, Fig. 3 c are C1sSpectrogram;
Fig. 4 is three-dimensional grapheme aeroge photo made from the embodiment of the present invention 4 and comparative example 1~3;
Fig. 5 is the N of three-dimensional grapheme aeroge made from the embodiment of the present invention 4 and comparative example 1~32Adsorption and desorption isotherms With BJH pore size distribution curve figures.
Embodiment
The present invention is further described with reference to the accompanying drawings and examples.
Embodiment 1
A kind of preparation method of three-dimensional nitrogen-doped graphene aeroge in the present embodiment, comprises the following steps:
(1) using natural graphite powder as carbon source, graphene oxide is prepared using Hummer methods, takes the graphene oxide prepared 100mg is added in 10mL water and the solution of 10mL ethanol mixing, is formulated as concentration 5mg/mL solution, at room temperature magnetic force Stirring 0.5 hour, ultrasonic disperse obtains graphene oxide colloidal sol in 0.5 hour;
(2) 1000mg urea and 200mg trisodium citrates, room are added in the graphene oxide colloidal sol obtained to step (1) Simultaneously ultrasonic disperse 0.5 hour is dissolved in the lower stirring of temperature for 0.5 hour;
(3) 10ml glacial acetic acid is added dropwise in the colloidal sol obtained under agitation to step (2), it is small continues stirring 0.5 When after ultrasonic disperse 0.5 hour, obtain sticky sepia graphene oxide colloidal sol;
(4) colloidal sol that step (3) obtains being transferred in hydrothermal reaction kettle, 130 DEG C of temperature control, reaction cools down after 12 hours, Obtain three-dimensional nitrogen-doped graphene gel;
(5) the three-dimensional nitrogen-doped graphene gel for being obtained step (4) with ethanol soak repeatedly, wash to pH be 7 after, adopt It is medium with ethanol, carries out the supercritical fluid drying using ethanol as fluid to it in autoclave, that is, three-dimensional N doping is made Graphene aerogel.
Embodiment 2
A kind of preparation method of three-dimensional nitrogen-doped graphene aeroge in the present embodiment, comprises the following steps:
(1) using natural graphite powder as carbon source, graphene oxide is prepared using Hummer methods, takes the graphene oxide prepared 100mg is added in 67mL water and the solution of 133mL ethanol mixing, is formulated as concentration 0.5mg/mL solution, at room temperature Magnetic agitation 1 hour, ultrasonic disperse obtain graphene oxide colloidal sol in 1 hour;
(2) 2000mg urea and 500mg trisodium citrates, room are added in the graphene oxide colloidal sol obtained to step (1) Simultaneously ultrasonic disperse 1 hour is dissolved in the lower stirring of temperature for 1 hour;
(3) 50ml glacial acetic acid is added dropwise in the colloidal sol obtained under agitation to step (2), continues stirring 1 hour Ultrasonic disperse 1 hour afterwards, obtain sticky sepia graphene oxide colloidal sol;
(4) colloidal sol that step (3) obtains being transferred in hydrothermal reaction kettle, 120 DEG C of temperature control, reaction cools down after 10 hours, Obtain three-dimensional nitrogen-doped graphene gel;
(5) the three-dimensional nitrogen-doped graphene gel for being obtained step (4) with ethanol soak repeatedly, wash to pH be 7 after, adopt It is medium with ethanol, carries out the supercritical fluid drying using ethanol as fluid to it in autoclave, that is, three-dimensional N doping is made Graphene aerogel.
Embodiment 3
A kind of preparation method of three-dimensional nitrogen-doped graphene aeroge in the present embodiment, comprises the following steps:
(1) using natural graphite powder as carbon source, graphene oxide is prepared using Hummer methods, takes the graphene oxide prepared 100mg is added in 9.2mL water and the solution of 1.8mL ethanol mixing, is formulated as concentration 9mg/mL solution, at room temperature magnetic Power stirs 2 hours, and ultrasonic disperse obtains graphene oxide colloidal sol in 2 hours;
(2) 100mg urea and 100mg trisodium citrates, room temperature are added in the graphene oxide colloidal sol obtained to step (1) Simultaneously ultrasonic disperse 2 hours are dissolved in lower stirring for 2 hours;
(3) 11ml glacial acetic acid is added dropwise in the colloidal sol obtained under agitation to step (2), continues stirring 2 hours Ultrasonic disperse 2 hours afterwards, obtain sticky sepia graphene oxide colloidal sol;
(4) colloidal sol that step (3) obtains is transferred in hydrothermal reaction kettle, 180 DEG C of temperature control, reaction cools down after 8 hours, obtains To three-dimensional nitrogen-doped graphene gel;
(5) the three-dimensional nitrogen-doped graphene gel for being obtained step (4) with ethanol soak repeatedly, wash to pH be 7 after, adopt It is medium with ethanol, carries out the supercritical fluid drying using ethanol as fluid to it in autoclave, that is, three-dimensional N doping is made Graphene aerogel.
Embodiment 4
A kind of preparation method of three-dimensional nitrogen-doped graphene aeroge in the present embodiment, comprises the following steps:
(1) using natural graphite powder as carbon source, graphene oxide is prepared using Hummer methods, takes the graphene oxide prepared 100mg is added in 10mL water and the solution of 10mL ethanol mixing, is formulated as concentration 5mg/mL solution, at room temperature magnetic force Stirring 0.5 hour, ultrasonic disperse obtains graphene oxide colloidal sol in 0.5 hour;
(2) 200mg urea and 100mg trisodium citrates, room temperature are added in the graphene oxide colloidal sol obtained to step (1) Simultaneously ultrasonic disperse 0.5 hour is dissolved in lower stirring for 0.5 hour;
(3) 10ml glacial acetic acid is added dropwise in the colloidal sol obtained under agitation to step (2), it is small continues stirring 0.5 When after ultrasonic disperse 0.5 hour, obtain sticky sepia graphene oxide colloidal sol;
(4) colloidal sol that step (3) obtains being transferred in hydrothermal reaction kettle, 130 DEG C of temperature control, reaction cools down after 12 hours, Obtain three-dimensional nitrogen-doped graphene gel;
(5) the three-dimensional nitrogen-doped graphene gel for being obtained step (4) with ethanol soak repeatedly, wash to pH be 7 after, adopt It is medium with ethanol, carries out the supercritical fluid drying using ethanol as fluid to it in autoclave, that is, three-dimensional N doping is made Graphene aerogel, such as No. 1 sample in Fig. 4.
As depicted in figs. 1 and 2, it is the SEM image of obtained three-dimensional nitrogen-doped graphene aeroge, it is seen that Graphenic surface forms substantial amounts of fold, and interlaced, rambling unordered accumulation forms three dimensional network between graphene layer Shape structure.
As shown in figure 3, scheme for the XPS of obtained three-dimensional nitrogen-doped graphene aeroge.3a is that XPS composes scanning entirely in figure Figure, it can be seen that nitrogen is successfully doped in graphene, and the content of nitrogen is 3.57at%;Fig. 3 b are N1sSpectrogram, Combination can correspond to pyridine type nitrogen and pyrroles's type nitrogen respectively positioned at 398.69eV and 400.17eV peak in figure.Fig. 3 c are C1sSpectrogram, Combination can correspond to sp respectively positioned at 284.76eV, 285.31eV, 286.31eV and 287.10eV peak in figure2C-C、sp2C-N、 sp3C-N and C-O.
Comparative example 1
The difference of this comparative example and embodiment 4 is, glacial acetic acid is not added with preparation process, and the three-dimensional without acetic acid is made Nitrogen-doped graphene aeroge, such as No. 2 samples in Fig. 4.
Comparative example 2
The difference of this comparative example and embodiment 4 is, urea is not added with preparation process, the three-dimensional for the nitrogen that obtains undoping Graphene aerogel, such as No. 3 samples in Fig. 4.
Comparative example 3
The difference of this comparative example and embodiment 4 is, trisodium citrate is not added with preparation process, and three-dimensional nitrogen is made and mixes Miscellaneous graphene aerogel, such as No. 4 samples in Fig. 4.
As shown in Figure 4, under the same reaction conditions, obtained graphene airsetting after trisodium citrate and glacial acetic acid is added Colloid product is larger.
As shown in figure 5, wherein Fig. 5 a are the N of graphene aerogel made from embodiment 42Adsorption and desorption isotherms and BJH holes Footpath scatter chart, Fig. 5 b are the N of graphene aerogel made from comparative example 12Adsorption and desorption isotherms and BJH pore size distribution curves Figure, Fig. 5 c are the N of graphene aerogel made from comparative example 22Adsorption and desorption isotherms and BJH pore size distribution curve figures, Fig. 5 d are The N of graphene aerogel made from comparative example 32Adsorption and desorption isotherms and BJH pore size distribution curve figures, as seen from the figure, embodiment 4 With comparative example 1~3 made from the specific surface area of graphene aerogel be respectively 358.09cm2g-1、176.09cm2g-1、 214.68cm2g-1、114.22cm2g-1, by N2Adsorption isotherm line chart understands occur sluggish time of absorption at relative pressure about 0.43 Line phenomenon, belong to IV type adsorption isotherms;From BJH pore size distribution curve figures can be seen that aperture be distributed in mostly absolutely 0-10nm it Between.
In above-described embodiment, supercritical fluid drying is carried out by medium of ethanol, the drying temperature and drying pressure are only Critical-temperature and the critical pressure of ethanol need to be higher than, the critical-temperature of ethanol and critical pressure are respectively 243.1 degrees Celsius And 6.3Mpa.

Claims (5)

1. a kind of preparation method of three-dimensional nitrogen-doped graphene aeroge, it is characterised in that comprise the following steps:
(1) using natural graphite powder as carbon source, graphene oxide is prepared using Hummer methods, take the graphene oxide for preparing by its 0.5~9mg/mL of concentration solution is formulated as, solvent is water and ethanol with volume ratio 0.5~5:The mixed solution of 1 composition, room temperature Lower magnetic agitation 0.5~2 hour, ultrasonic disperse obtain graphene oxide colloidal sol in 0.5~2 hour;
(2) urea and trisodium citrate, the urea, citric acid three are added in the graphene oxide colloidal sol obtained to step (1) The mass ratio of sodium and graphene oxide is 1~20:1~5:1, dissolving in 0.5~2 hour and ultrasonic disperse 0.5~2 are stirred at room temperature Hour;
(3) glacial acetic acid, the volume of the glacial acetic acid and colloidal sol are added dropwise in the colloidal sol obtained under agitation to step (2) Than for 0.25~1:1, continue ultrasonic disperse 0.5~2 hour after stirring 0.5~2 hour, obtain sticky sepia graphite oxide Alkene colloidal sol;
(4) colloidal sol that step (3) obtains is transferred in hydrothermal reaction kettle, 120~180 DEG C of temperature control, it is cold after reacting 8~12 hours But, three-dimensional nitrogen-doped graphene gel is obtained;
(5) the three-dimensional nitrogen-doped graphene gel for being obtained step (4) with ethanol soak repeatedly, wash to pH be 7 after, using second Alcohol is medium, carries out the supercritical fluid drying using ethanol as fluid to it in autoclave, that is, three-dimensional N doping graphite is made Alkene aeroge.
A kind of 2. preparation method of N doping three-dimensional grapheme aeroge according to claim 1, it is characterised in that:It is described The compound concentration of graphene oxide solution is 5mg/mL in step (1).
A kind of 3. preparation method of N doping three-dimensional grapheme aeroge according to claim 1, it is characterised in that:It is described The mass ratio of urea, trisodium citrate and graphene oxide is 2 in step (2):1:1.
A kind of 4. preparation method of N doping three-dimensional grapheme aeroge according to claim 1, it is characterised in that:It is described The volume ratio of glacial acetic acid and colloidal sol is 0.5 in step (3):1.
A kind of 5. preparation method of N doping three-dimensional grapheme aeroge according to claim 1, it is characterised in that:It is described Temperature in step (4) in hydrothermal reaction kettle is 130 DEG C.
CN201711035506.6A 2017-10-30 2017-10-30 A kind of preparation method of three-dimensional nitrogen-doped graphene aeroge Pending CN107697905A (en)

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CN111389438A (en) * 2020-02-24 2020-07-10 哈尔滨工业大学 Preparation method and application of nitrogen-doped three-dimensional graphene-loaded manganese dioxide catalyst
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CN108525615A (en) * 2018-03-12 2018-09-14 东北石油大学 A kind of preparation and its application of the Ni-based nitrogen-doped graphene aeroge of three-dimensional foam
CN108525615B (en) * 2018-03-12 2020-08-25 东北石油大学 Preparation and application of three-dimensional foam nickel-based nitrogen-doped graphene aerogel
CN109037678A (en) * 2018-06-15 2018-12-18 陕西科技大学 A kind of preparation method of nitrogen sulphur codope three-dimensional graphene foam electrode active material
CN111389438A (en) * 2020-02-24 2020-07-10 哈尔滨工业大学 Preparation method and application of nitrogen-doped three-dimensional graphene-loaded manganese dioxide catalyst
CN111389438B (en) * 2020-02-24 2023-03-10 哈尔滨工业大学 Preparation method and application of nitrogen-doped three-dimensional graphene-loaded manganese dioxide catalyst
CN113289657A (en) * 2021-05-21 2021-08-24 山西大学 Preparation method and application of nitrogen-doped graphene catalytic membrane
CN113289657B (en) * 2021-05-21 2022-12-30 山西大学 Preparation method and application of nitrogen-doped graphene catalytic membrane
CN113479872A (en) * 2021-07-19 2021-10-08 常州大学 Preparation method of nitrogen-doped three-dimensional porous graphene hydrogel electrode material, electrode and application thereof

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