CN102120572A - Method for preparing nitrogen-doped graphene - Google Patents
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Abstract
The invention relates to a method for preparing nitrogen-doped graphene, in particular to a novel simple, convenient and scale method for preparing nitrogen-doped graphene at high temperature under the protection of inert gas by taking melamine as a nitrogen source. In the method, graphene oxide and the melamine are taken as raw materials, wherein the melamine is taken as the nitrogen source and the graphene oxide is taken as a carbon source; high temperature annealing is carried out in the atmosphere of inert gas, and the reduction of the graphene oxide and the nitrogen doping of graphene are realized; and by controlling reaction conditions such as temperature, time, the ratio of the raw materials and the like, graphene products with different nitrogen doping ratios can be prepared. The preparation method is simple and practicable; catalysts are not needed; the reaction process is easy to control; special requirements on equipment do not exist; the cost is low; and the method is easy to promote and use.
Description
Technical field
The present invention relates to a kind of preparation method of nitrogen-doped graphene, being specifically related to a kind of is easy, the mass-producing novel method that nitrogenous source high temperature under protection of inert gas prepares nitrogen-doped graphene with the trimeric cyanamide, belongs to material synthetic chemistry field.
Background technology
As a kind of energy gap is zero semi-conductor, and the important prerequisite that Graphene (Graphene) is applied to microelectronic device is that its band gap, carrier concentration etc. are adjustable, and chemical doping is the effective means that realizes this regulation and control.Therefore, the doping of Graphene has become the focus that the numerous subject researchists of physics, chemistry and materialogy pay close attention to, and the preparation doped graphene has very important significance to furtheing investigate its application in the nanoelectronics field.
The doping of Graphene is proposed by the physics research personnel at first.Up to now, set up the theoretical model of multiple doped graphene.Theoretical study results shows, in the lamella of Graphene, introduce as heteroatomss such as N, B, can effectively realize Graphene from the semi-metal of zero band gap to semi-conductive transformation, form n-type or the adulterated Graphene of p-type, thereby greatly expanded the application of Graphene in fields such as optics, electricity, magnetics.
Because the restriction of preparation method and experiment condition, the adulterated concrete technical scheme of Graphene do not have open always.2009, Liu Yun boundary research group reported first the preparation method of nitrogen-doped graphene, and studied nitrogen and mixed the influence of Graphene electric property.The author is by the chemical vapor deposition (CVD) method, as carbon source, ammonia is as nitrogenous source with methane gas, at the thick copper film of silicon base surface deposition 25 nm as catalyzer, under 800 ℃ high temperature, kept 10 minutes, and made which floor nitrogen-doped graphene of minority.So far, the preparation of doped graphene and performance study become the focus that people pay close attention to gradually.Many seminars attempt the prepared in various methods doped graphene one after another, the doped graphene of prior art mainly is that boron or nitrogen mix at present, for example adopts the method for electrothermal reaction, is nitrogenous source with the ammonia, nitrogen-atoms is replaced carbon atom in the Graphene lattice, the adulterated Graphene of preparation nitrogen; Perhaps be that starting raw material and ammonia are nitrogenous source, carry out high temperature annealing, realize the reduction of GO and the doping of nitrogen simultaneously, make nitrogen-doped graphene with the graphene oxide.In addition, use arc discharge method to prepare boron or nitrogen-doped graphene in addition.And only rest in the theoretical investigation about other atom doped Graphene, do not see disclosing of detailed technical scheme.So the doping of research Graphene is a meaningful and challenging subject.
To sum up, the preparation method of the nitrogen-doped graphene of prior art mainly is vapour deposition or arc discharge method.Because the professional and exacting terms of operation, these class methods and technology are difficult to promote the use of, for example use professional equipments such as high vacuum system, also need use the hydrogen of high risk, corrosive ammonia, highly toxic borine etc., its preparation condition harshness, cost height, dangerous big, be not suitable for large-scale application demand.
Summary of the invention
To use high toxicity and dangerous chemical reagent among the present nitrogen-doped graphene preparation method in order solving, to prepare problems such as difficulty is big, cost height, technical purpose of the present invention is to propose the novel method of a kind of low cost, scale operation nitrogen-doped graphene, it is simple and easy to do to make that this method possesses, and can prepare the advantage of the Graphene of high nitrogen doped ratio, and utilize the preparation-obtained product of this method can be widely used in the research in fields such as electron device, matrix material, sensing, bioanalysis.
To achieve these goals, the present invention has adopted following technical scheme:
The preparation method of a kind of nitrogen-doped graphene (NG), it is characterized in that: raw material oxidation state Graphene (GO) and trimeric cyanamide (Melamine) mixed grinding are placed in the airtight rare gas element heating mix and react to carry out elevated temperature heat reduction and nitrogen, in airtight rare gas element, be cooled to room temperature at last, promptly get the nitrogen-doped graphene product.
Wherein, preparation method of the present invention can comprise raw material oxidation state preparation method of graphene, be about to natural graphite powder after Hummers ' method oxide treatment, wherein metal ion or other small molecules are removed in dialysis again, after vacuum-drying and grinding obtain oxidation state Graphene raw material.
Preparation method of the present invention also comprises the preparation method of raw material trimeric cyanamide, is about to the chemical pure trimeric cyanamide and handles through recrystallization, and vacuum-drying and grinding obtain the trimeric cyanamide raw material again.
The method that heats in the airtight rare gas element of the present invention is to feed the rare gas element heating in tube furnace.
Rare gas element of the present invention is argon gas or nitrogen.
Wherein, the purity of described rare gas element is 〉=99%.
Elevated temperature heat reduction of the present invention and nitrogen doping reaction conditions are: temperature of reaction is 700～1200 ℃, and the reaction times is 0.5～4 hour.
The mass ratio of raw material oxidation state Graphene of the present invention and trimeric cyanamide is: 1:50～2:1.
Beneficial effect of the present invention is:
The present invention can change experiment condition such as raw materials quality ratio grade according to the needs to the character of product, prepares the Graphene product of different nitrogen doping ratios; Utilize graphene oxide and trimeric cyanamide to prepare nitrogen-doped graphene through high temperature annealing, by the conditions such as ratio of regulation and control temperature of reaction, time and reactant, the control of nitrogen doping ratio in effective reduction of realization graphene oxide and the product;
Nitrogen-doped graphene of the present invention is to utilize trimeric cyanamide to be nitrogenous source, under hot conditions, contain on the oxidation state Graphene and carry out the nitrogen doping when oxygen functional group decomposes, in this technical scheme except that tube furnace of need, do not need other any specific equipment, so the preparation method is simple and easy to do, reaction process is easy to control, danger is little, cost is low, can produce in batches, and its technology of preparing is very easily promoted the use of.
Description of drawings
The X ray diffracting spectrum of Fig. 1 nitrogen-doped graphene (NG).
The atomic force microscope picture of Fig. 2 nitrogen-doped graphene (NG).
The scanning electron microscope picture of Fig. 3 nitrogen-doped graphene (NG).
The transmission electron microscope picture of Fig. 4 nitrogen-doped graphene (NG) and high-resolution-ration transmission electric-lens figure (illustration is selected area electron diffraction figure).
The Raman spectrogram of the different nitrogen doping ratio of Fig. 5 Graphene.
The x-ray photoelectron of nitrogen-doped graphene (NG) energy spectrogram under Fig. 6 differential responses condition: (a) differential responses temperature; (b) the differential responses time; (c) different graphene oxide and trimeric cyanamide mass ratio.
Fig. 7 nitrogen doping ratio is the N1s peak and the C1s peak of 10.1% Graphene.
Embodiment
1) preparation method of raw material trimeric cyanamide: trimeric cyanamide is carried out recrystallization, is solvent with water, filters the crystal vacuum-drying that obtains, and the product after mortar grinds stores for future use in moisture eliminator.
2) preparation method of raw material graphene oxide: (concrete operation method is referring to 1. Kovtyukhova, N. I. after preoxidation of improved Hummers ' method and oxidation for the analytical pure natural graphite powder; Ollivier, P. J.; Martin, B. R.; Mallouk, T. E.; Chizhik, S.A.; Buzaneva, E. V.; Gorchinskiy, A. D. Layer-by-Layer Assembly of Ultrathin Composite Films from Micron-Sized Graphite Oxide Sheets and Polycations.
Chem. Mater.1999,11,771～778; And 2. Hummers, W. S.; Offeman, R. E. Preparation of Graphitic Oxide
. J. Am. Chem. Soc.1958,80,1339～1339.), filter and washing, the residue sticky solid is put into dialysis tubing, and it is approaching neutral to the pH value to dialyse, and the products obtained therefrom drying is graphene oxide.
3) oxidation state Graphene and trimeric cyanamide are pressed mass ratio 1:5 mixed grinding, mixture is put into crucible and is placed on the middle heating region of tube furnace, feeds the argon gas deoxygenation of purity 〉=99%, after 30 minutes, is warming up to 800 ℃ by 5 ℃/min temperature rise rate, keeps 1 h; Slowly reduce to room temperature then, generate black product---nitrogen-doped graphene in crucible bottom.
The present embodiment preparation method is with embodiment 1, and wherein the mass ratio of oxidation state graphite and trimeric cyanamide transfers to 1:1,1:10,1:20 in the step 3, under the constant situation of other condition, obtains black product---nitrogen-doped graphene equally.
The present embodiment preparation method is with embodiment 1, and the temperature of reaction of step 3 is adjusted to 700 ℃, 900 ℃, 1000 ℃, 1200 ℃ respectively, under the constant situation of other condition, obtains black product---nitrogen-doped graphene equally.
Embodiment 4
The present embodiment preparation method is with embodiment 1, and the regulation and control reaction times was respectively 10 minutes, 30 minutes, 4 hours, carried out under the condition of nitrogen gas of purity 〉=99%, under the constant situation of other condition, obtained black product---nitrogen-doped graphene equally.
The method of the invention prepares nitrogen-doped graphene, is not limited to the foregoing description, and the percentage composition of the nitrogen of the nitrogen-doped graphene for preparing under its differential responses condition sees Table 1; And the sign of the nitrogen-doped graphene product for preparing according to the method for the invention is seen shown in the accompanying drawing 1～7.
The percentage composition of the nitrogen of the nitrogen-doped graphene for preparing under the table 1 differential responses condition
| ? | C1s(At.%) | N1s(At.%) | O1s(At.%) |
| Oxidation state Graphene-trimeric cyanamide-800 ℃-1h-2:1 | 89.62 | 5.69 | 4.69 |
| Oxidation state Graphene-trimeric cyanamide-800 ℃-1h-1:5 | 90.41 | 6.55 | 3.03 |
| Oxidation state Graphene-trimeric cyanamide-800 ℃-1h-1:10 | 89.38 | 7.63 | 2.98 |
| Oxidation state Graphene-trimeric cyanamide-800 ℃-2h-1:50 | 88.4 | 8.36 | 3.24 |
| Oxidation state Graphene-trimeric cyanamide-800 ℃-30min-1:5 | 89.84 | 7.09 | 3.07 |
| Oxidation state Graphene-trimeric cyanamide-700 ℃-4h-1:5 | 86.83 | 10.14 | 3.03 |
Claims (8)
1. the preparation method of a nitrogen-doped graphene, it is characterized in that: raw material oxidation state Graphene and trimeric cyanamide mixed grinding are placed in the airtight rare gas element heating mix and react to carry out elevated temperature heat reduction and nitrogen, in airtight rare gas element, be cooled to room temperature at last, promptly get the nitrogen-doped graphene product.
2. the preparation method of a kind of nitrogen-doped graphene according to claim 1, it is characterized in that described preparation method also comprises raw material oxidation state preparation method of graphene, be about to natural graphite powder after Hummers ' method oxide treatment, wherein metal ion or other small molecules are removed in dialysis again, after vacuum-drying and grinding obtain oxidation state Graphene raw material.
3. the preparation method of a kind of nitrogen-doped graphene according to claim 1, it is characterized in that described preparation method also comprises the preparation method of raw material trimeric cyanamide, be about to the chemical pure trimeric cyanamide and handle through recrystallization, vacuum-drying and grinding obtain the trimeric cyanamide raw material again.
4. the preparation method of a kind of nitrogen-doped graphene according to claim 1 is characterized in that the method that heats in the described airtight rare gas element is to feed the rare gas element heating in tube furnace.
5. according to the preparation method of claim 1 or 4 described a kind of nitrogen-doped graphenes, it is characterized in that described rare gas element is argon gas or nitrogen.
6. the preparation method of a kind of nitrogen-doped graphene according to claim 5, the purity that it is characterized in that described rare gas element is 〉=99%.
7. the preparation method of a kind of nitrogen-doped graphene according to claim 1 is characterized in that described elevated temperature heat reduction and nitrogen doping reaction conditions are: 700～1200 ℃ of temperature of reaction, 0.5～4 hour reaction times.
8. the preparation method of a kind of nitrogen-doped graphene according to claim 1 is characterized in that the mass ratio of described raw material oxidation state Graphene and trimeric cyanamide is: 1:50～2:1.
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