CN107265442A - A kind of nitrogen-doped graphene nanometer roll three-dimensional macro material and preparation method thereof - Google Patents
A kind of nitrogen-doped graphene nanometer roll three-dimensional macro material and preparation method thereof Download PDFInfo
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- CN107265442A CN107265442A CN201710525007.9A CN201710525007A CN107265442A CN 107265442 A CN107265442 A CN 107265442A CN 201710525007 A CN201710525007 A CN 201710525007A CN 107265442 A CN107265442 A CN 107265442A
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention provides a kind of preparation method of nitrogen-doped graphene nanometer roll three-dimensional macro material, comprise the following steps：A sealing carries out heating response after) graphene oxide solution is mixed with amide solvent, obtains hydrogel；B) hydrogel is placed in deionized water, displacement step A) in have neither part nor lot in the formamide of reaction, obtain the hydrogel after water displacement；C the quick-frozen rear freeze-drying of hydrogel after) water is replaced, obtains nitrogen-doped graphene nanometer roll three-dimensional macro material.
Description
Technical field
The invention belongs to technical field of graphene, and in particular to a kind of nitrogen-doped graphene nanometer roll three-dimensional macro material and
Its preparation method.
Background technology
Obtained three-dimensional macro material is assembled because of its high-specific surface area, stable loose structure and easily by graphene nano lamella
In characteristics such as functional modifications, had broad application prospects in fields such as energy storage, environmental protection, catalysis.Graphene three-dimensional macro material
The preparation method of material regulates and controls most important to its performance and application with internal structure.
The three-dimensional macro material that method is prepared " from bottom to top " is based on by graphene nano lamella, its internal graphene
Lamella still has serious face-to-face π-π and stacked, and its specific surface area is far below inside theoretical value, another aspect macroscopic body
Three-dimensional network access denial is to limit internal mass transfer process.It is a kind of to assemble three-dimensional macro material based on graphene nano volume for this
New material Constructed wetlands, graphene nano volume be by two-dimensional graphene nanoscale twins vertically helix-coil obtain have open
The one-dimensional tubular body of topological structure is put, the structural pipe wall of CNT seamless connection is different from.Graphene nano winds off the side put
π-the π that edge then avoids graphene sheet layer well with two ends are stacked, while can ensure that material is accessible in macroscopic body again
Transmission.But be the preparation that powder body material is rolled up on graphene nano in the prior art, have no technology and roll up graphene nano
It is assembled into three-dimensional macro material.
The content of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of nitrogen-doped graphene nanometer roll three-dimensional macro
Material and preparation method thereof, the nitrogen-doped graphene nanometer roll three-dimensional macro material that the present invention is provided has larger ratio surface
Product, and accessible transmission of the material in macroscopic material can be ensured.
The invention provides a kind of preparation method of nitrogen-doped graphene nanometer roll three-dimensional macro material, it is characterised in that
Comprise the following steps：
A sealing carries out heating response after) graphene oxide solution is mixed with amide solvent, obtains hydrogel；
B) hydrogel is placed in deionized water, displacement step A) in have neither part nor lot in the amide solvent of reaction, obtain
Hydrogel after water displacement；
C the quick-frozen rear freeze-drying of hydrogel after) water is replaced, obtains nitrogen-doped graphene nanometer roll three-dimensional macro
Material.
It is preferred that, the amide solvent is formamide, acetamide, acrylamide, Methacrylamide.
It is preferred that, the concentration of the graphene oxide solution is 2.5~10g/L.
It is preferred that, the volume ratio of the graphene oxide solution and formamide is 5：(0.8~1.2), preferably 5:1.
It is preferred that, the temperature of the heating response is 80~100 DEG C, and the time of the heating response is 10~18 hours.
It is preferred that, it is described quick-frozen for liquid nitrogen flash freezer.
Present invention also offers a kind of nitrogen-doped graphene nanometer roll three-dimensional macro prepared by above-mentioned preparation method
Material.
It is preferred that, specific surface area is 80~150m2/g。
Compared with prior art, the invention provides a kind of preparation side of nitrogen-doped graphene nanometer roll three-dimensional macro material
Method, comprises the following steps：A sealing carries out heating response after) graphene oxide solution is mixed with formamide, obtains hydrogel；
B) hydrogel is placed in deionized water, displacement step A) in have neither part nor lot in the formamide of reaction, obtain the water after water displacement
Gel；C the quick-frozen rear freeze-drying of hydrogel after) water is replaced, obtains nitrogen-doped graphene nanometer roll three-dimensional macro material.This
Invention realizes that graphene sheet layer nanometer assembles two processes with three-dimensional in rolls by one-step method, molten using polar molecule-amide-type
Agent realizes this double goal as driving reagent.During this, on the one hand amide solvent plays crosslinking agent and promotes three
Tie up the effect of assembling ,-C=O above and-NH2It can connect adjacent GO lamellas with GO lamellas formation hydrogen bond respectively；It is another
Amide groups in aspect, amide solvent belongs to short of electricity subbase group, and weak reducing agent makes a certain degree of weak reduction of GO lamellas,
This is that GO lamellas can form the necessary condition of volume in the case of freeze-drying in follow-up three-dimensional macro body；In addition, amide-type is molten
The compound of agent causes have a certain degree of N to adulterate on the graphene nano finally given volume three-dimensional macro material.Simultaneous oxidation stone
Black alkene concentration is also very crucial, and concentration is too low can not to form three-dimensional macro network structure, excessive concentration graphene oxide layer it
Between act on too strong, it is impossible to obtain a nanometer volume structure, inside will appear from serious lamella and stack phenomenon.Therefore, the present invention is provided
Nitrogen-doped graphene nanometer roll three-dimensional macro material has larger specific surface area, and can ensure material in macroscopic material
Accessible transmission.
As a result show, the specific surface area of nitrogen-doped graphene nanometer roll three-dimensional macro material that the present invention is provided for 80~
150m2/g。
Brief description of the drawings
Fig. 1 is the influence that different graphene oxide concentration on gel are molded；
Fig. 2 is gel situation of the graphene oxide (5g/L) under different crosslinking agents；
Fig. 3 is the SEM figures of N doped graphene nanometer roll three-dimensional macros material internal nanometer volume structure；
Fig. 4 is influence of the formamide addition to formation nanometer roll in macroscopic body；
Fig. 5 is the SEM figures of nitrogen-doped graphene three-dimensional macro material prepared by comparative example 5；
Fig. 6 is the swarming fitting of N element in XPS；
Fig. 7 is the nitrogen of N doped graphenes nanometer roll (N-GNSs-F) and pure zirconia graphene (GO-F) three-dimensional macro body
Adsorption-desorption curve；
Fig. 8 is N doped graphenes nanometer roll (N-GNSs-F) and pure zirconia graphene (GO-F) three-dimensional macro body to methylene
Base indigo plant (a, c) and the Adsorption effect of rhodamine B (b, d).
Embodiment
The invention provides a kind of preparation method of nitrogen-doped graphene nanometer roll three-dimensional macro material, including following step
Suddenly：
A sealing carries out heating response after) graphene oxide solution is mixed with amide solvent, obtains hydrogel；
B) hydrogel is placed in deionized water, displacement step A) in have neither part nor lot in the formamide of reaction, obtain water and put
Hydrogel after changing；
C the quick-frozen rear freeze-drying of hydrogel after) water is replaced, obtains nitrogen-doped graphene nanometer roll three-dimensional macro material
Material.
It is three-dimensional that the present invention carries out nitrogen-doped graphene nanometer roll using graphene oxide solution and amide solvent as raw material
The preparation of macroscopic material, wherein, the present invention realizes graphene sheet layer nanometer in rolls with three using amide solvent as driving reagent
Tie up the double goal of assembling.In the process, on the one hand amide solvent plays a part of crosslinking agent and promotes three-dimensional assembling, above
- C=O and-NH2It can connect adjacent GO lamellas with GO lamellas formation hydrogen bond respectively；On the other hand, in amide solvent
Amide groups belong to short of electricity subbase group, weak reducing agent makes a certain degree of weak reduction of GO lamellas, and this is follow-up three-dimensional macro body
Interior GO lamellas can form the necessary condition of volume in the case of freeze-drying；In addition, the compound of amide solvent causes final obtain
To graphene nano volume three-dimensional macro material on there is a certain degree of N to adulterate.
In the present invention, the amide solvent is preferably formamide, acetamide, acrylamide, Methacrylamide, more
Preferably formamide.
The concentration of the graphene oxide solution is 2.5~10g/L, preferably 5.0g/L.
The graphene oxide solution and the volume ratio of amide solvent are 5：(0.8~1.2), preferably 5:1.
Sealing carries out heating response after graphene oxide solution and amide solvent are sufficiently mixed, and obtains hydrogel.Its
In, the temperature of the heating response is 80~100 DEG C, and the time of the heating response is 10~18 hours.
Obtain after hydrogel, the hydrogel be placed in deionized water, displacement step A) in have neither part nor lot in the acid amides of reaction
Class solvent, obtains the hydrogel after water displacement.In the present invention, the deionized water is excessive, to ensure in hydrogel not
The amide solvent displacement for participating in reaction is complete.
If under said ratio, not by the step for displacement with deionized water, unnecessary amide solvent is with molten
Agent is mutually present inside hydrogel, and its phase in version condition is different from water so that the sample volume after follow-up freeze-drying shrinks,
Inside is in GO lamella the stacked states.
Then, the quick-frozen rear freeze-drying of hydrogel after the water is replaced, obtains nitrogen-doped graphene nanometer roll three-dimensional
Macroscopic material.
In the present invention, it is described it is quick-frozen be preferably liquid nitrogen flash freezer, it is quick-frozen be make graphene sheet layer coiled one it is crucial because
Element.If chilling rate is excessively slow, the phenomenon that serious graphene oxide layer is stacked occurs, it is impossible to coiled.
Present invention also offers a kind of nitrogen-doped graphene nanometer roll three-dimensional for using above-mentioned preparation method to prepare is grand
Material is seen, the surface area of the nitrogen-doped graphene nanometer roll three-dimensional macro material is 80~150m2/g。
The present invention realizes that graphene sheet layer nanometer assembles two processes with three-dimensional in rolls by one-step method, utilizes polarity point
Son-formamide realizes this double goal as driving reagent.During this, on the one hand amide solvent plays crosslinking
Agent promotes the effect of three-dimensional assembling ,-C=O above and-NH2It can connect adjacent GO lamellas with GO lamellas formation hydrogen bond respectively
Connect；On the other hand, the amide groups in amide solvent belongs to short of electricity subbase group, and weak reducing agent makes GO lamellas a certain degree of
Weak reduction, this is that GO lamellas can form the necessary condition of volume in the case of freeze-drying in follow-up three-dimensional macro body；In addition, acyl
The compound of amine solvent causes have a certain degree of N to adulterate on the graphene nano finally given volume three-dimensional macro material.Simultaneously
Graphene oxide concentration is also very crucial, and concentration is too low can not to form three-dimensional macro network structure, excessive concentration graphene oxide
Acted between lamella too strong, it is impossible to obtain a nanometer volume structure, inside will appear from serious lamella and stack phenomenon.Therefore, it is of the invention
The nitrogen-doped graphene nanometer roll three-dimensional macro material of offer has larger specific surface area, and material can be ensured in macroscopic view
Accessible transmission in material.
As a result show, the specific surface area of nitrogen-doped graphene nanometer roll three-dimensional macro material that the present invention is provided for 80~
150m2/g。
For a further understanding of the present invention, the nitrogen-doped graphene nanometer roll three provided with reference to embodiment the present invention
Dimension macroscopic material and preparation method thereof is illustrated, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
1st, by 5g/L GO solution according to volume ratio 5:1 mixes with formamide and seals mixing, then heats 12h in 90 DEG C,
Form hydrogel.
Its gel forming photo is shown in that Fig. 1, Fig. 1 are 0.5 in the influence that different graphene oxide concentration on gel are molded, Fig. 1
Represent gel forming photo (comparative example 1) of the graphene oxide concentration as 0.5g/L, 1 to represent graphene oxide concentration be 1.0g/L
Gel forming photo, 2.5 represent gel forming photo (embodiment 2) of the graphene oxide concentration as 2.5g/L, and 5 represent oxidation
Graphene concentration is 5g/L gel forming photo (embodiment 1).
As shown in Figure 1, the concentration of oxidation of precursor graphene is most important, and 2.5g/L is corresponding gel threshold value, to be reached
Three-dimensional macro body can be just built into the threshold value, if less than the threshold value (such as 0.5g/L and 1g/L), formamide can not also aid in it
It is cross-linked into stable gel.
Fig. 2 is gel situation of the graphene oxide (5g/L) under different crosslinking agents, in Fig. 2, and first photo is is not added with
Crosslinking agent is only the gel situation (comparative example 2) of graphene oxide solution, and second photo is hydrogel prepared by embodiment 1,
3rd photo is gel situation (comparative example 3) of the N,N-dimethylformamide as crosslinking agent.
As shown in Figure 2, DMF without the same assisted oxidation graphene of image of Buddha formamide 90 DEG C heat under
Stable hydrogel is formed, illustrates that formamide has its specific crosslinked action in graphene nano volume three-dimensional is constructed.
2nd, obtained hydrogel is immersed in large volume deionized water and replaces 48h, it is therefore intended that displaced in step 3 not
Participate in the formamide solvent of reaction.
Surface sweeping electronic microscope photos is carried out to the above-mentioned nitrogen-doped graphene nanometer roll three-dimensional macro material prepared, as a result seen
Fig. 3 and Fig. 4, Fig. 3 are the SEM of N doped graphene nanometer roll three-dimensional macros material internal nanometer volume structure prepared by embodiment 1
Figure.Fig. 4 is influence of the formamide addition to formation nanometer roll in macroscopic body.In Fig. 4, (a) is to be prepared by pure zirconia graphene
The SEM figures (comparative example 2) of obtained macroscopic body, (b) graphene oxide is with formamide with volume ratio 25:1 macroscopic view prepared
The SEM figures (comparative example 4) of body, (c) is N doped graphene nanometer roll three-dimensional macro material internal nanometer rolls prepared by embodiment 1
The SEM figures of structure.
As shown in Figure 4, influence of the formamide addition to forming nanometer roll is also very notable, as shown in figure 4, pure oxygen fossil
Black alkene and a small amount of formamide (volume ratio 25 of addition：1) the sample interior graphene oxide layer curling after cold do can not be caused,
Only reach a certain amount of (such as 5:1) it just can obtain the internal three-dimensional macro body in nanometer roll.
3rd, the hydrogel liquid nitrogen frozen after water displacement, and nitrogen-doped graphene nanometer roll three-dimensional is obtained by freeze-drying
Macroscopic material.
Wherein can freezing rate also very crucial to form nanometer roll in final macroscopic body, cold using the low speed of refrigerator
Freeze, then can not obtain a nanometer volume structure (comparative example 5).
Transmission electron microscope analysis is carried out to the above-mentioned nitrogen-doped graphene nanometer roll three-dimensional macro material prepared, as a result seen
Fig. 3, Fig. 3 are the SEM figures of N doped graphene nanometer roll three-dimensional macros material internal nanometer volume structure.
Fig. 6 is that the swarming of N element during N doped graphene nanometer roll three-dimensional macro materials XPS is tested is fitted, in Fig. 6, (a)
For N doped graphene nanometer roll three-dimensional macro bodies；(b) made annealing treatment for N doped graphenes nanometer roll three-dimensional macro body through 500 DEG C
(Fig. 6), it will be appreciated from fig. 6 that N element on nanometer roll with surface doping (formamide N, cross-linking) and body dopant (pyrroles N and
Pyridine N, impurity) two kinds of forms are present；The latter can still retain after the high temperature anneal, such as Fig. 6 b.
By specific area measuring, it is N doped graphenes nanometer roll (N-GNSs-F) and pure oxygen fossil as a result to see Fig. 7, Fig. 7
Nitrogen adsorption-desorption curve of black alkene (GO-F) three-dimensional macro body.The macroscopic view that assembling is obtained is rolled up by graphene nano as shown in Figure 7
Surface area per unit volume accumulates (92.1m2/ g, N-GNSs-F) it is graphene sheet layer assembling macroscopic body (59.8m2/ g, GO-F) nearly twice；
Graphene nano volume significantly avoids the aspectant π-π of lamella and stacked, so as to improve the specific surface area of macroscopic material.
Removal capacity of the N doped graphenes nanometer roll three-dimensional macro material to organic pollutants in water body is determined, is specially：Will
2mg adsorbents shake added to (dye strength is 100mg/L) in 20mL aqueous dye solutions, sealing after under 25 DEG C and 120rpm
24h is swung, the concentration of dye solution before and after absorption is determined with ultraviolet-visible spectrophotometer, it is N doping stones as a result to see Fig. 8, Fig. 8
Black alkene nanometer roll (N-GNSs-F) and pure zirconia graphene (GO-F) three-dimensional macro body to methylene blue (a, c) and rhodamine B (b,
D) Adsorption effect.
As shown in figure 8, assembling obtained three-dimensional macro body to dyes pollutant by N doped graphenes nanometer roll
Eliminating rate of absorption (methylene blue 96.8%, rhodamine B 94.6%) will be substantially better than the three-dimensional that pure zirconia graphene sheet layer is constructed
Macroscopic body (methylene blue 89.7%, rhodamine B 79.5%).
Comparative example 1
1st, by 0.5g/L GO solution with volume ratio 5:1 fully mixes with formamide.
2nd, 12h is heated in 90 DEG C, it is impossible to form gel.Its gel forming photo is shown in that Fig. 1, Fig. 1 are different graphene oxides
The influence of concentration on gel shaping.
Comparative example 2
1st, pure 5.0mg/mL GO solution is in the case of no addition crosslinking agent, and sealing heats 12h, nothing after 90 DEG C
Method formation gel.Its gel forming photo is shown in that Fig. 2, Fig. 2 are gel situation of the graphene oxide (5g/L) under different crosslinking agents.
Comparative example 3
1st, by 5.0g/L GO solution with volume ratio 5:1 fully mixes with N,N-dimethylformamide.
2nd, 12h is heated in 90 DEG C, it is impossible to form hydrogel.Its gel forming photo is shown in that Fig. 1, Fig. 1 are different graphite oxides
The influence of alkene concentration on gel shaping.
Comparative example 4
1st, by 5.0g/L GO solution with volume ratio 25:1 fully mixes with formamide.
2nd, 12h is heated in 90 DEG C, forms hydrogel.
3rd, obtained hydrogel is immersed in large volume deionized water and replaces 48h, it is therefore intended that displaced in step 2 not
Participate in the formamide solvent of reaction.
4th, the hydrogel liquid nitrogen frozen after water displacement, and graphene three-dimensional macro material is obtained by freeze-drying.It is right
It carries out electron-microscope scanning, and it is influence of the formamide addition to formation nanometer roll in macroscopic body as a result to see Fig. 4, Fig. 4.
Comparative example 5
1st, by 5.0g/L GO solution with volume ratio 5:1 fully mixes with formamide.
2nd, 12h is heated in 90 DEG C, forms hydrogel.Its gel forming photo is shown in that Fig. 1, Fig. 1 are that different graphene oxides are dense
Spend the influence to gel forming.
3rd, obtained hydrogel is immersed in large volume deionized water and replaces 48h, it is therefore intended that displaced in step 2 not
Participate in the formamide solvent of reaction.
4th, the hydrogel after water displacement, which is placed in -20 DEG C of refrigerator, freezes, and obtains N doping graphite by freeze-drying
Alkene three-dimensional macro material.
Electron-microscope scanning analysis is carried out to it, it is nitrogen-doped graphene three-dimensional macro prepared by comparative example 5 as a result to see Fig. 5, Fig. 5
The SEM figures of material.As shown in Figure 5, freezing rate can be also in rolls to graphene sheet layer in final macroscopic body one it is crucial because
Element, slow freezing is such as freezed with -20 DEG C of refrigerator, it is freeze-dried after obtain three-dimensional bulk inner as shown in figure 5, being by tight
The graphene oxide layer of weight, which is stacked, to be constituted, and the sample obtained with Fig. 1 through liquid nitrogen snap frozen is completely different；That is it is quick
Freezing is the necessary condition for promoting to be formed nanometer roll in macroscopic body.
Embodiment 2
1st, by 2.5g/L GO solution with volume ratio 5:1 fully mixes with formamide.
2nd, 12h is heated in 90 DEG C, forms hydrogel.Its gel forming photo is shown in that Fig. 1, Fig. 1 are that different graphene oxides are dense
Spend the influence to gel forming.
3rd, obtained hydrogel is immersed in large volume deionized water and replaces 48h, it is therefore intended that displaced in step 2 not
Participate in the formamide solvent of reaction.
4th, the hydrogel liquid nitrogen frozen after water displacement, and nitrogen-doped graphene nanometer roll three-dimensional is obtained by freeze-drying
Macroscopic material.
Specific area measuring is carried out to it, specific surface area is 75.3m2/g。
According to embodiment 1 provide method carry out organic pollutants in water body removal capacity determine, as a result for：To in water body
The eliminating rate of absorption (methylene blue 90.2%, rhodamine B 89.6%) of dyestuff contaminant.
Embodiment 3
1st, by 10g/L GO solution with volume ratio 5:1 fully mixes with formamide.
2nd, 12h is heated in 90 DEG C, forms hydrogel.
3rd, obtained hydrogel is immersed in large volume deionized water and replaces 48h, it is therefore intended that displaced in step 2 not
Participate in the formamide solvent of reaction.
4th, the hydrogel liquid nitrogen frozen after water displacement, and nitrogen-doped graphene nanometer roll three-dimensional is obtained by freeze-drying
Macroscopic material.
Specific area measuring is carried out to it, specific surface area is 81.5m2/g。
According to embodiment 1 provide method carry out organic pollutants in water body removal capacity determine, as a result for：To in water body
The eliminating rate of absorption (methylene blue 92.1%, rhodamine B 91.5%) of dyestuff contaminant.
Embodiment 4
1st, by 5g/L GO solution with volume ratio 5:0.8 fully mixes with formamide.
2nd, 12h is heated in 90 DEG C, forms hydrogel.
3rd, obtained hydrogel is immersed in large volume deionized water and replaces 48h, it is therefore intended that displaced in step 2 not
Participate in the formamide solvent of reaction.
4th, the hydrogel liquid nitrogen frozen after water displacement, and nitrogen-doped graphene nanometer roll three-dimensional is obtained by freeze-drying
Macroscopic material.
Specific area measuring is carried out to it, specific surface area is 88.3m2/g。
According to embodiment 1 provide method carry out organic pollutants in water body removal capacity determine, as a result for：To in water body
The eliminating rate of absorption (methylene blue 95.2%, rhodamine B 92.8%) of dyestuff contaminant.
Embodiment 5
1st, by 5g/L GO solution with volume ratio 5:1.2 fully mix with formamide.
2nd, 12h is heated in 90 DEG C, forms hydrogel.
3rd, obtained hydrogel is immersed in large volume deionized water and replaces 48h, it is therefore intended that displaced in step 2 not
Participate in the formamide solvent of reaction.
4th, the hydrogel liquid nitrogen frozen after water displacement, and nitrogen-doped graphene nanometer roll three-dimensional is obtained by freeze-drying
Macroscopic material.
Specific area measuring is carried out to it, specific surface area is 86.0m2/g。
According to embodiment 1 provide method carry out organic pollutants in water body removal capacity determine, as a result for：To in water body
The eliminating rate of absorption (methylene blue 93.6%, rhodamine B 92.3%) of dyestuff contaminant.
Embodiment 6
1st, by 2.5g/L GO solution with volume ratio 5:1 fully mixes with acetamide.
2nd, 12h is heated in 90 DEG C, forms hydrogel.
3rd, obtained hydrogel is immersed in large volume deionized water and replaces 48h, it is therefore intended that displaced in step 2 not
Participate in the formamide solvent of reaction.
4th, the hydrogel liquid nitrogen frozen after water displacement, and nitrogen-doped graphene nanometer roll three-dimensional is obtained by freeze-drying
Macroscopic material.
Specific area measuring is carried out to it, specific surface area is 75.3m2/g。
According to embodiment 1 provide method carry out organic pollutants in water body removal capacity determine, as a result for：To in water body
The eliminating rate of absorption (methylene blue 90.2%, rhodamine B 89.6%) of dyestuff contaminant.
Embodiment 7
1st, by 2.5g/L GO solution with volume ratio 5:1 fully mixes with acrylamide.
2nd, 12h is heated in 90 DEG C, forms hydrogel.
3rd, obtained hydrogel is immersed in large volume deionized water and replaces 48h, it is therefore intended that displaced in step 2 not
Participate in the formamide solvent of reaction.
4th, the hydrogel liquid nitrogen frozen after water displacement, and nitrogen-doped graphene nanometer roll three-dimensional is obtained by freeze-drying
Macroscopic material.
Specific area measuring is carried out to it, specific surface area is 75.3m2/g。
According to embodiment 1 provide method carry out organic pollutants in water body removal capacity determine, as a result for：To in water body
The eliminating rate of absorption (methylene blue 90.2%, rhodamine B 89.6%) of dyestuff contaminant.
Embodiment 8
1st, by 2.5g/L GO solution with volume ratio 5:1 fully mixes with Methacrylamide.
2nd, 12h is heated in 90 DEG C, forms hydrogel.
3rd, obtained hydrogel is immersed in large volume deionized water and replaces 48h, it is therefore intended that displaced in step 2 not
Participate in the formamide solvent of reaction.
4th, the hydrogel liquid nitrogen frozen after water displacement, and nitrogen-doped graphene nanometer roll three-dimensional is obtained by freeze-drying
Macroscopic material.
Specific area measuring is carried out to it, specific surface area is 75.3m2/g。
According to embodiment 1 provide method carry out organic pollutants in water body removal capacity determine, as a result for：To in water body
The eliminating rate of absorption (methylene blue 90.2%, rhodamine B 89.6%) of dyestuff contaminant.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (8)
1. a kind of preparation method of nitrogen-doped graphene nanometer roll three-dimensional macro material, it is characterised in that comprise the following steps：
A sealing carries out heating response after) graphene oxide solution is mixed with amide solvent, obtains hydrogel；
B) hydrogel is placed in deionized water, displacement step A) in have neither part nor lot in the amide solvent of reaction, obtain water and put
Hydrogel after changing；
C the quick-frozen rear freeze-drying of hydrogel after) water is replaced, obtains nitrogen-doped graphene nanometer roll three-dimensional macro material
Material.
2. preparation method according to claim 1, it is characterised in that the amide solvent be selected from formamide, acetamide,
Acrylamide, Methacrylamide.
3. preparation method according to claim 1, it is characterised in that the concentration of the graphene oxide solution is 2.5~
10g/L.It is preferred that concentration be 5g/L.
4. preparation method according to claim 1, it is characterised in that the graphene oxide solution and amide solvent
Volume ratio is 5：(0.8~1.2).
5. preparation method according to claim 1, it is characterised in that the temperature of the heating response is 80~100 DEG C, institute
The time for stating heating response is 10~18 hours.
6. preparation method according to claim 1, it is characterised in that described quick-frozen for liquid nitrogen flash freezer.
7. the nitrogen-doped graphene nanometer roll three that a kind of preparation method as described in claim 1~6 any one is prepared
Tie up macroscopic material.
8. nitrogen-doped graphene nanometer roll three-dimensional macro material according to claim 7, it is characterised in that specific surface area is
80~150m2/g。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113998693A (en) * | 2021-10-22 | 2022-02-01 | 北京石墨烯技术研究院有限公司 | Preparation method of graphene nano-roll |
| CN114284635A (en) * | 2021-12-28 | 2022-04-05 | 厦门大学 | Diaphragm modification method for lithium metal negative electrode protection |
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2017
- 2017-06-30 CN CN201710525007.9A patent/CN107265442A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| DA YOUNG HWANG ET AL: "Inclusion and exclusion of self-assembled molecules inside graphene scrolls and control of their inner-tube diameter", 《RSC ADV.》 * |
| QILE FANG ET AL: "Nitrogen-Doped Graphene Nanoscroll Foam with High Diffusion Rate and Binding Affinity for Removal of Organic Pollutants", 《SMALL》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113998693A (en) * | 2021-10-22 | 2022-02-01 | 北京石墨烯技术研究院有限公司 | Preparation method of graphene nano-roll |
| CN114284635A (en) * | 2021-12-28 | 2022-04-05 | 厦门大学 | Diaphragm modification method for lithium metal negative electrode protection |
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