CN105384163A - Method for preparing nitrogen-doped graphene with solvent heat - Google Patents
Method for preparing nitrogen-doped graphene with solvent heat Download PDFInfo
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- CN105384163A CN105384163A CN201510847676.9A CN201510847676A CN105384163A CN 105384163 A CN105384163 A CN 105384163A CN 201510847676 A CN201510847676 A CN 201510847676A CN 105384163 A CN105384163 A CN 105384163A
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Abstract
The invention relates to a method for preparing nitrogen-doped graphene with solvent heat. Under the protection of inert gas, nitrogen atoms are doped in a process of stripping off carbon tetrachloride from metallic potassium through heat treatment to obtain the nitrogen-doped graphene. The method comprises the following steps: adding a nitrogen-containing precursor, the carbon tetrachloride and the metallic potassium into a hydrothermal kettle under the protection of the inert gas, and sealing; carrying out heat treatment for 10 minutes to 12 hours at 160 DEG C to 240 DEG C. Compared with other preparation methods, the method is simple and feasible and can realize the preparation of the nitrogen-doped graphene in one step; the method has the advantages of low requirements on equipment, large yield and easiness in realizing industrialization. The prepared nitrogen-doped graphene has an excellent electro-catalysis oxygen reduction reaction performance and has a wide application prospect in the fields of fuel cells, metal-air cells and the like.
Description
Technical field
The present invention relates to nano-carbon material preparation field, refer to a kind of solvent thermal process preparing nitrogen-doped graphene especially.
Background technology
Graphene be a kind of by carbon atom with sp
2the carbon material with individual layer tow-dimensions atom structure that the monoatomic layer that hydridization connects is formed, there is unique physics and electrochemical properties, as: (K.S.Novoselov, the etal.Science2004 such as high-specific surface area, high conductivity, high mechanical strength, 306,666.).Therefore, Graphene continues the extensive concern being subject to scientific circles and industry member in recent years.
Theoretical and experimental study shows that N doping can affect the spin density of carbon atom around and charge distribution, the electronic structure of change Graphene and chemical property, thus activated carbon enable it have can be comparable with noble metal platinum-carbon-supported catalysts electrocatalysis characteristic (L.P.Zhang, etal.J.Phys.Chem.C115,11170.).Therefore, nitrogen-doped graphene, as nonmetallic catalyzer, its satisfactory stability in addition, has broad application prospects in fuel cell and metal-air battery.
At present, the synthetic method of the Graphene of N doping has: chemical Vapor deposition process, segregation growth method and post treatment method etc.But the technological line of these methods and synthesis device mostly relative complex, production cost are higher, are difficult to realize suitability for industrialized production.Such as, post treatment method needs to utilize the method such as mechanically peel or liquid phase stripping to prepare Graphene or graphene oxide in advance, then by its thermal treatment or utilize plasma body etc. to process in ammonia.
Summary of the invention
The object of the invention is to not enough and shortcomings such as solving prior art cost intensive, technique is loaded down with trivial details, productive rate is lower, a kind of simple, novel method preparing nitrogen-doped graphene powder is provided.This method adopts tetracol phenixin and potassium metal to be raw material, and by adding different nitrogen sources, a step obtains the Graphene of N doping in a mild condition.Follow-up annealing treatment comprehend further promote nitrogen-doped graphene to the electrocatalysis characteristic of oxygen reduction reaction, make its performance very close with commercial 20% platinum C catalyst.
A kind of nitrogen-doped graphene raw powder's production technology provided by the invention, makes nitrogen-atoms adulterate in potassium metal stripping tetracol phenixin formation Graphene process through Overheating Treatment, namely obtains described nitrogen-doped graphene under protection of inert gas;
Described method comprises: add in water heating kettle by nitrogenous precursor, tetracol phenixin and potassium metal under the protection of rare gas element, sealing; In 160 ~ 240 DEG C of thermal treatments 10 minutes ~ 12 hours.
The present invention utilizes the high activity of potassium metal, and (160 ~ 240 DEG C) can by CCl at a lower temperature
4peel off into Graphene, and the KCl generated is very easily water-soluble, product is easier to cleaning.
Preferably, the molar ratio of described nitrogenous precursor relative to tetracol phenixin 0.01 ~ 30% scope, preferably 1% ~ 10%, be more preferably 1% ~ 5%.
Again, preferably, the feed ratio of described tetracol phenixin and potassium metal can be 0.5 ~ 50mL:0.25 ~ 10g.
In the present invention, nitrogenous precursor can comprise: pyrroles, urea, trimeric cyanamide, cyanamide, dicyanamide, biuret, Trimustine, aniline, 1-ethyl-3-methyl-imidazoles cynoguanidine salt one or more.
Preferably, anneal is carried out in an inert atmosphere further through the nitrogenous graphene powder collected by thermal treatment reaction.Further anneal, can improve the quality of nitrogen-doped graphene further, can obtain the electrocatalysis characteristic suitable with commercialization 20% platinum carbon.
Again, preferably, described anneal temperature range is 400 ~ 1000 DEG C, and annealing time is 1 ~ 6 hour.
Again, preferably, described noble gas component is nitrogen, argon gas, 5%H
2/ N
2gas or 5%H
2/ Ar gas.
Compared with other preparation method, the preparation that the present invention is simple, a step can realize nitrogen-doped graphene, and also equipment requirements is low, output large, is easy to industrialization.Nitrogen-doped graphene prepared by the present invention has the performance of excellent electrocatalytic oxidation reduction reaction, has broad application prospects in the field such as fuel cell, metal-air battery.
Accompanying drawing explanation
Fig. 1 illustrates the scanning electron microscope (SEM) photograph of nitrogen-doped graphene prepared by exemplary method of the present invention;
Fig. 2 illustrates the photoelectron spectrum figure of nitrogen element in nitrogen-doped graphene prepared by exemplary method of the present invention;
Fig. 3 illustrate nitrogen-doped graphene (G-A) prepared by exemplary method of the present invention, through further anneal nitrogen-doped graphene (NG-A) and 20%Pt/C to the electrocatalysis characteristic figure of oxygen reduction reaction.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the invention will be further described, provides detailed embodiment and concrete operating process, but should not limit the scope of the invention with this.
The present invention adopts tetracol phenixin and potassium metal to be raw material; by adding different nitrogen sources; under protection of inert gas, through Overheating Treatment, nitrogen-atoms carbon atom in potassium metal stripping tetracol phenixin is formed in Graphene process adulterate, a step can obtain the Graphene of N doping in a mild condition.Follow-up annealing treatment comprehend further promote nitrogen-doped graphene to the electrocatalysis characteristic of oxygen reduction reaction, make its performance very close with commercial 20% platinum C catalyst.
Particularly, a kind of nitrogen-doped graphene raw powder's production technology provided by the invention, carries out according to following steps:
1) in the glove box being full of rare gas element, nitrogenous precursor, tetracol phenixin and potassium metal added in water heating kettle, seal;
2) water heating kettle of sealing is put into baking oven for heating to certain temperature (160 ~ 240 DEG C), 10min ~ 24h, afterwards naturally cooling;
3) water heating kettle of cooling is opened in stink cupboard, by reaction gained powder successively with the mixed solvent of acetone and deionized water, ethanol and deionized water carry out cleaning, suction filtration;
4) powder after suction filtration is dry in vacuum drying oven;
5) be the electrocatalysis characteristic improving further prepared powder, by powder 400 ~ 1000 DEG C of annealing 1 ~ 6 hour in the tube furnace of protection of inert gas.
Compared with other preparation method, the preparation that the present invention is simple, a step can realize nitrogen-doped graphene, and also equipment requirements is low, output large, is easy to industrialization.Nitrogen-doped graphene prepared by the present invention has the performance of excellent electrocatalytic oxidation reduction reaction, has broad application prospects in the field such as fuel cell, metal-air battery.
Exemplify embodiment below further to describe the present invention in detail.Should understand equally; following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.The processing parameter etc. that following example is concrete is also only an example in OK range, and namely those skilled in the art can be done in suitable scope by explanation herein and select, and do not really want the concrete numerical value being defined in Examples below.
Embodiment 1
In the glove box of Ar gas shielded, 110 μ L pyrroles, 5mL tetracol phenixin and 1g potassium metal are loaded in 100mL water heating kettle, then seal;
Water heating kettle is taken out, puts into 200 DEG C of baking ovens, reacts 6 hours;
After water heating kettle naturally cooling, open in stink cupboard, prepared powder is poured in the mixed solvent that acetone and deionized water (volume ratio 1:1) are housed in advance, stir half an hour, then suction filtration; The powder of suction filtration is put into the mixed solvent that ethanol and deionized water (volume ratio 1:1) are housed in advance again and stir half an hour, then suction filtration; So repeatedly twice, the product that last suction filtration is obtained in 60 DEG C of vacuum drying ovens dry 12 hours;
Finally, gained nitrogen-doped graphene powder is collected;
In order to improve the electrocatalysis characteristic of nitrogen-doped graphene to oxygen reduction reaction, can by gained nitrogen-doped graphene in the tube furnace of Ar gas shielded 600 DEG C annealing 2 hours.
Fig. 1 is the stereoscan photograph that the present embodiment obtains, and has as can be seen from the figure successfully prepared the Graphene of tulle shape; Fig. 2 is the high resolution x-ray photoelectron energy spectrogram of N element in the azepine Graphene of the present embodiment acquisition.From in figure: the N in the azepine Graphene of gained exists with the form of pyridine nitrogen, pyrroles's nitrogen, greying nitrogen and oxynitride, the sufficient proof successful doping of nitrogen.Fig. 3 is the performance map of nitrogen-doped graphene when electrocatalytic oxidation reduction reaction of the present embodiment gained.As seen from the figure, this Graphene after annealing (NG-A) shows good electrocatalysis characteristic, and take-off potential is 65mV lower than business-like 20%Pt/C only, very close.But the large 1.84mAcm of its current density ratio 20%Pt/C
-2.
Embodiment 2
In the glove box of Ar gas shielded, 0.12g urea, 10mL tetracol phenixin and 2g potassium metal are loaded in 100mL water heating kettle, then seal, water heating kettle is taken out, puts into 200 DEG C of baking ovens, reacts 6 hours;
After water heating kettle naturally cooling, open in stink cupboard, prepared powder is poured in the mixed solvent that acetone and deionized water (volume ratio 1:1) are housed in advance, stir half an hour, then suction filtration; The powder of suction filtration is put into the mixed solvent that ethanol and deionized water (volume ratio 1:1) are housed in advance again and stir half an hour, then suction filtration; So repeatedly twice, the product that last suction filtration is obtained in 60 DEG C of vacuum drying ovens dry 12 hours;
Finally, gained nitrogen-doped graphene powder is collected.
In order to improve the electrocatalysis characteristic of nitrogen-doped graphene to redox reaction, can by gained nitrogen-doped graphene in the tube furnace of Ar gas shielded 600 DEG C annealing 2 hours.
Embodiment 3
In the glove box of Ar gas shielded, 0.252g trimeric cyanamide, 5mL tetracol phenixin and 1.2g potassium metal are loaded in 100mL water heating kettle, then seal, water heating kettle is taken out, puts into 200 degree of baking ovens, reacts 6 hours;
After water heating kettle naturally cooling, open in stink cupboard, prepared powder is poured in the mixed solvent that acetone and deionized water (volume ratio 1:1) are housed in advance, stir half an hour, then suction filtration; The powder of suction filtration is put into the mixed solvent that ethanol and deionized water (volume ratio 1:1) are housed in advance again and stir half an hour, then suction filtration; So repeatedly twice, the product that last suction filtration is obtained in 60 DEG C of vacuum drying ovens dry 12 hours;
Finally, gained nitrogen-doped graphene powder is collected.
In order to improve the electrocatalysis characteristic of nitrogen-doped graphene to redox reaction, can by gained nitrogen-doped graphene in the tube furnace of Ar gas shielded 600 DEG C annealing 2 hours.
Claims (7)
1. solvent thermal prepares a method for nitrogen-doped graphene, it is characterized in that, through Overheating Treatment, nitrogen-atoms is adulterated in potassium metal stripping tetracol phenixin formation Graphene process, namely obtain described nitrogen-doped graphene under protection of inert gas; Described method comprises: add in water heating kettle by nitrogenous precursor, tetracol phenixin and potassium metal under the protection of rare gas element, sealing; In 160 ~ 240 DEG C of thermal treatments 10 minutes ~ 12 hours.
2. preparation method according to claim 1, is characterized in that, the molar ratio of described nitrogenous precursor relative to tetracol phenixin 0.01 ~ 30% scope, preferably 1% ~ 5%.
3. preparation method according to claim 1 and 2, is characterized in that, the feed ratio of described tetracol phenixin and potassium metal is 0.5 ~ 50mL:0.25 ~ 10g.
4. the preparation method according to any one of claim 1-3, it is characterized in that, nitrogenous precursor comprises: pyrroles, urea, trimeric cyanamide, cyanamide, dicyanamide, biuret, Trimustine, aniline, 1-ethyl-3-methyl-imidazoles cynoguanidine salt one or more.
5. the preparation method according to any one of claim 1-4, is characterized in that, carries out anneal in an inert atmosphere further through the nitrogenous graphene powder collected by thermal treatment reaction.
6. preparation method according to claim 5, is characterized in that, the temperature range of described anneal is 400 ~ 1000 DEG C, and annealing time is 1 ~ 6 hour.
7. the preparation method according to any one of claim 1-6, is characterized in that, described noble gas component is nitrogen, argon gas, 5%H
2/ N
2gas or 5%H
2/ Ar gas.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115626638A (en) * | 2022-09-30 | 2023-01-20 | 苏州大学 | Nitrogen-doped graphene and preparation method and application thereof |
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| CN102485647A (en) * | 2010-12-02 | 2012-06-06 | 中国科学院上海硅酸盐研究所 | Method for preparing boron doped graphene |
| CN102718206A (en) * | 2011-03-29 | 2012-10-10 | 中国科学院大连化学物理研究所 | A macroscopic quantity preparation method for a nitrogen-doped graphene |
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Patent Citations (3)
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| CN102485647A (en) * | 2010-12-02 | 2012-06-06 | 中国科学院上海硅酸盐研究所 | Method for preparing boron doped graphene |
| CN102718206A (en) * | 2011-03-29 | 2012-10-10 | 中国科学院大连化学物理研究所 | A macroscopic quantity preparation method for a nitrogen-doped graphene |
| CN102290477A (en) * | 2011-09-13 | 2011-12-21 | 青岛科技大学 | Photovoltaic cell based on graphene PN junction and preparation method thereof |
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| LILI XU ET AL;: "Graphene and N-doped Graphene Coated with SnO2 Nanoparticles as Supercapacitor Electrodes", 《ECS TRANSACTIONS》 * |
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| CN115626638A (en) * | 2022-09-30 | 2023-01-20 | 苏州大学 | Nitrogen-doped graphene and preparation method and application thereof |
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