CN103691471A - Preparation method of nitrogen-doped graphene material - Google Patents
Preparation method of nitrogen-doped graphene material Download PDFInfo
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Abstract
The invention relates to a preparation method of a nitrogen-doped graphene material. The preparation method comprises the following steps: adding a micro-molecule fatty amine water solution into a water solution of graphite oxide dispersed by ultrasound, performing hydrothermal reaction for 36-72 hours, separating out precipitate, washing and drying to obtain the nitrogen-doped graphene material. The material containing nitrogen and carbon prepared by the preparation method is high in nitrogen content, and contains different nitrogen species such as secondary amine and pyridine nitrogen, so that the surface of the prepared material has alkali centers with different intensities, wherein the secondary amine is super base. In addition, the proportion and content of nitrogen species can be controlled by changing the species of micro-molecule amine, so that the effect of controlling the alkalinity and the alkali amount of a catalyst is achieved. The actual operation of the method is simple and feasible, and the preparation material does not contain any metal element, so the nitrogen-doped graphene material is a green environment-friendly catalyst. Good catalytic activity is shown in Michael addition reaction and ester exchange reaction, and the catalyst is in favor of separation and purification of products, so the catalyst has a potential industrial application value.
Description
Technical field
The present invention relates to a kind of preparation of nitrogenous material with carbon element, particularly a kind of preparation method of nitrogen-doped graphene material.
Background technology
Non-metallic catalyst is a kind of emerging green catalyst, has advantages of more efficient, environmental protection and economy in many Industrial Catalysis field.Material with carbon element is the important non-metallic catalyst of a class that development in recent years is got up, it does not add or any metallic element of load but directly with material with carbon element this as catalyst.Material with carbon element catalyst has shown the performance that is better than traditional metal catalyst in the reactions such as alkylated reaction, carbonylation, rearrangement reaction, cycloaddition reaction, has a high potential, and therefore becomes gradually the forward position direction of nonmetal catalytic field.
Graphene is the important material with carbon element of a class growing up in recent years, it be a kind of thickness only to have the two-dimensional nano material of 0.35nm and band gap width be zero, be therefore also a kind of semi-conducting material or the nonmetallic materials with certain metalline.Because it has unique electronic transport property, outstanding mechanical performance and high-specific surface area, Graphene has huge using value.Graphene is carried out to nitrogen doping treatment can its electronic structure of modulation, improve its physical and chemical performance, and nitrating can be adjusted Graphene performance effectively, makes it in more areas, have potential application.Therefore Graphene is carried out to the focus that nitrogen doping is current material with carbon element research.
Up to now, forefathers have explored the Graphene that several different methods is prepared nitrogen doping.The synthetic method of nitrating Graphene mainly comprises chemical vapour deposition technique, the pyrolysis of ammonia source, nitrogen plasma discharge method, arc discharge, ammonia electrothermal reaction method, solvent-thermal method and nitrogenous precursor transformation approach etc.Conventionally one-step synthesis, mainly take little molecule alkane and ammonia or hydrazine to adopt chemical vapour deposition technique preparation as raw material, can also take nitride and carbon tetrachloride under high-temperature and high-pressure conditions, to adopt solvent-thermal method preparation as raw material.The Graphene that chemical meteorology deposition method is produced is difficult to strip down from substrate, and the nitride that the latter uses has certain danger, and cannot the producing in enormous quantities of this two kinds of methods.Another kind method is post treatment method, mainly high-temperature process or with high energy ammonium ion bundle bombardment Graphene under ammonia atmosphere.The cost of these two kinds of methods is all very high, is difficult to large-scale production.
Chinese patent CN201210042207.6 discloses nitrogen-doped graphene of a kind of regular morphology and preparation method thereof.This nitrogen-doped graphene adopts chemical vapour deposition technique to be prepared, comprise the steps: metallic catalyst to be placed in reactor, in non-oxidizing atmosphere, heating makes described catalyzer temperature-elevating to 200～600 ℃, then to passing into carbon nitrogen source in described reactor, react, obtain nitrogen-doped graphene.The course of reaction of these class methods is more, operating condition is harsh.In addition, the nitrogen species of many preparation methods' nitrogen-doped graphene is relatively single and basicity is generally lower, and range of application is narrower.Therefore, how by a kind of method of cheap and simple, to prepare on a large scale the nitrogen-doped graphene that nitrogen containing species kind is many, basicity is high and remain a huge challenge.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of new nitrogen-doped graphene material, can overcome the defect of prior art.The present invention be take small molecule amine as nitrogenous source, adopts hydro-thermal method one-step synthesis to go out nitrogenous material with carbon element.Simple to operate, applicability is strong, can scale prepares that nitrogen content is high, the nitrogen-doped graphene material of nitrogen species abundant species.
The step that the preparation method of a kind of nitrogen-doped graphene material provided by the invention comprises:
1) in the aqueous solution of the graphite oxide through ultrasonic dispersion, add the small aliphatic amine molecule aqueous solution, hydro-thermal reaction 36～72h.Wherein, the concentration of graphite oxide aqueous solution is 1-5g/L, and the molar concentration of the aqueous solution of small aliphatic amine molecule is 1～3mol/L.
2) isolate precipitated product, through washing, dry, obtain nitrogen-doped graphene material.
Described small aliphatic amine molecule is at least one in methylamine, dimethylamine, ethamine, diethylamine, propylamine or butylamine.Described small aliphatic amine molecule and the mass ratio of graphite oxide: 30-50: 1.5-2.5.
The step that the preparation method of a kind of nitrogen-doped graphene material provided by the invention comprises:
(1) in the mixed liquor of the concentrated sulfuric acid and phosphoric acid, add crystalline graphite powder and potassium permanganate, at 30-50 ℃, stir 6-24h, slowly add water and hydrogen peroxide reaction 20-30min, obtain the turbid liquid of graphite oxide.
(2) standing, graphite oxide difference water and ethanol decant 4-6 time, be dried, and obtains the graphite oxide of purifying.
(3) again graphite oxide is joined anhydrate in and slowly stir 20-30min, then ultrasonic dispersion, obtains the aqueous solution of graphite oxide.
(4) hydro-thermal method is prepared nitrogen-doped graphene: will in the aqueous solution of the aqueous solution of 1～3mol/L small aliphatic amine molecule and the graphene oxide of 1-5g/L, mix ultrasonic dispersion, then hydro-thermal reaction 36～72h at 60～120 ℃.
(5) separation, washes with water, dry, obtains described nitrogen-doped graphene material.
The concentrated sulfuric acid that step (1) is described and the volume ratio 7-8 of phosphoric acid: 1.The mass ratio of the concentrated sulfuric acid, crystalline graphite powder and potassium permanganate is: 400-450: 30-40: 80-100; The mass ratio of graphite powder, water and hydrogen peroxide is: 2-6: 200～400: 3-5;
Described dry of step (5) is 80～120 ℃ of vacuum drying 12-24h.
The power of described ultrasonic dispersion is 50-53KHz, and the time is 50-70min.
Compared with prior art, it is nitrogenous source that the present invention adopts small molecule amine fatty amine to the preparation method of a kind of nitrogen-doped graphene material provided by the invention, and at lower hydrothermal temperature, next step has synthesized nitrogen-doped graphene.The method cost is low, simple possible.In addition, nitrogen content is high, nitrogen species kind is many and be a kind of super base, therefore can large-scale production and have industrial application value.
Accompanying drawing explanation
Fig. 1 (a) and (b) be the TEM photo of the different enlargement ratios of embodiment 1 gained nitrogen-doped graphene.
Fig. 2 is Raman spectrogram (a) and the XPS spectrum figure (b) of the nitrogen-doped graphene of graphene oxide and embodiment 1～3 gained.
Fig. 3 is high-resolution C 1s XPS spectrum figure (a) and the high-resolution N 1s XPS spectrum figure (b) of the nitrogen-doped graphene of embodiment 1～3 gained.
Fig. 4 is the nitrogen-doped graphene of embodiment 1～4 gained catalytic activity figure to Michael addition reaction.(a) for differentiated yields, scheming over time, is (b) conversion ratio after different catalysts reaction 8h.
The specific embodiment
Below in conjunction with the specific embodiment and accompanying drawing, the present invention is done to further detailed, complete explanation.
(1) prepare graphite oxide: the SPA of the 240mL concentrated sulfuric acid and 30mL is joined in three-necked bottle, add wherein 6g graphite powder, then slowly add 18g potassium permanganate, after 50 ℃ of stirring 6-24h, add 400mL water.Now temperature acutely rises to 98 ℃, maintains 30min.The hydrogen peroxide that adds 3mL30%.
(2) purifying of graphite oxide: the turbid liquid of (1) gained is standing, decant then.First use deionized water decant four times, then use ethanol decant six times.80 ℃ of vacuum drying 24h can obtain graphite oxide.
(3) preparation of graphene oxide: take 10g graphite oxide and join in 1L deionized water and slowly stirring.Stir after 30min ultrasonic dispersion 30min.Obtained aqueous solution is the aqueous solution of graphene oxide.The pH value of the aqueous solution is between 4～5.
4) hydro-thermal method is prepared nitrogen-doped graphene: get the aqueous solution of 100mL graphene oxide, add wherein 24g n-propylamine, be diluted with water to 200mL.Seal and stir after 30min, more ultrasonic 1h.Above-mentioned solution is transferred in the stainless steel still with polytetrafluoro liner to 80 ℃ of hydrothermal treatment consists 72h.
(5) by black column solid crushing in still, add water decant three times.80 ℃ of vacuum drying 24h get final product to obtain the Graphene (being designated as PAGO) of nitrogen doping.
Fig. 1 is the TEM photo of the prepared nitrogen-doped graphene of the present embodiment.As seen from the figure: the size of prepared nitrogen-doped graphene is 5 μ m left and right, and there is a large amount of gauffers on surface, and these folds are the avtive spot of some reactions often.Right figure is some fold place enlarged drawings, and from then on figure can observe, and the thickness of nitrogen-doped graphene only has less than 2nm, i.e. the thickness of three to five layers of mono-layer graphite.Therefore prepared nitrogen-doped graphene is typical two-dimensional structure.
Fig. 2 is Raman spectrogram (left side) and the XPS spectrum figure (right side) of the nitrogen-doped graphene of graphene oxide and embodiment 1～3 gained.From Raman spectrogram: after hydrothermal treatment consists, D peak moves to high wave number, and the half-peak breadth at D peak diminishes, and this explanation nitrogen-atoms enters the skeleton of Graphene.From XPS spectrum figure: untreated graphene oxide only contains carbon and two kinds of elements of oxygen, and after hydrothermal treatment consists, has increased nitrogen element newly, and this also illustrates that nitrogen is doped in Graphene.The content of nitrogen is shown in Table 1.
Fig. 3 is and high-resolution C 1s XPS spectrum figure and the high-resolution N 1s XPS spectrum figure of the nitrogen-doped graphene of embodiment 1～3 gained.As seen from the figure, the content of carbon-oxygen bond obviously reduces and has new carbonnitrogen bond to form after hydrothermal treatment consists, illustrate in the process of hydrothermal treatment consists graphene oxide by partial reduction and nitrogen-doping in Graphene; The nitrogen being doped in Graphene exists with three kinds of forms: a kind of is pyridine nitrogen, and the second is amine, and the third is ammonium salt.
Embodiment 2
The present embodiment is from the different of embodiment 1: the ethamine that amine used is 70%, and the amount adding is 26g, the sample of gained is designated as EAGO.
All the other contents are with described in embodiment 1.
The Raman spectrum of gained nitrogen-doped graphene and XPS spectrum figure are as shown in Figure 2.
The high-resolution C 1s XPS spectrum figure of gained nitrogen-doped graphene and high-resolution N 1s XPS spectrum figure are as shown in Figure 3.
Embodiment 3
The present embodiment is from the different of embodiment 1: the methylamine that amine used is 30%, and the amount adding is 40g, the sample of gained is designated as MAGO.
All the other contents are with described in embodiment 1.
The Raman spectrum of gained nitrogen-doped graphene and XPS spectrum figure are as shown in Figure 2.
The high-resolution C 1s XPS spectrum figure of gained nitrogen-doped graphene and high-resolution N 1s XPS spectrum figure are as shown in Figure 3.
Embodiment 4
The present embodiment is from the different of embodiment 1: amine used is butylamine, and the amount adding is 29.7g, and the sample of gained is designated as BAGO.
All the other contents are with described in embodiment 1.
Embodiment 5
The measurement of the basicity of the nitrogen-doped graphene that investigation the present invention makes:
The basicity of nitrogen-doped graphene is recorded by the special indicator in Hami.The special indicator in Hami used is: aniline (pKa=27), triphenylmenthane (pKa=33), diphenyl-methane (pKa=35), isopropylbenzene (pKa=37), dimethylbenzene (pKa=39).
The nitrogenize Graphene of getting the special indicator in 3mL (or 1g) Hami and 0.1g embodiment 1～3 gained joins respectively in different vials, adds respectively the benzene of 5mL, and then sealing is preserved.After fortnight, observe change color situation.
Result is as shown in table 1, and Hami paricular value of three kinds of nitrogenize Graphenes is between 37 to 39, and the Graphene that these three kinds of nitrogenize are described is all solid super base.
Table 1
Embodiment 6
Investigate the catalytic activity of the prepared nitrogen-doped graphene of embodiment 1～3 to Knoevenagel condensation reaction:
6mmol benzaldehyde, 20mg catalyst and 9mmol malononitrile are joined respectively in the round-bottomed flask of 25mL, under 80 ℃ of argon shields, react 4h.Product is analyzed by gas-chromatography～GC-MS and gas chromatograph.
As shown in Table 1, the nitrogen-doped graphene that the present invention makes is very high to the catalytic activity of Knoevenagel condensation reaction, and in 4h, conversion ratio just can reach and approach 100%, and the prepared catalyst of this explanation the present invention is a kind of base catalyst effectively.
Embodiment 7
Investigate the catalytic activity of the prepared nitrogen-doped graphene of embodiment 1～4 to ester exchange reaction:
0.2mol ethylene glycol, 0.2g catalyst are joined in round-bottomed flask, under 140 ℃ of argon shields, stir half an hour, then add 0.04mol methyl benzoate to continue to stir, every 2h, get a sample and analyze.Result is as shown in Fig. 4 (left figure).
0.2mol ethylene glycol, 0.2g catalyst are joined in round-bottomed flask, under 140 ℃ of argon shields, stir half an hour, then add 0.04mol methyl benzoate to continue to stir 8h.Product is analyzed by gas-chromatography～GC-MS and gas chromatograph, and result is as shown in Fig. 4 (right figure).
From Fig. 4 (left figure), the prepared catalyst conversion ratio after reaction 40h of embodiment 1～3 approaches 100%.Wherein the activity of embodiment 1 is higher than the activity of embodiment 2 and embodiment 3.From right figure, the prepared catalyst activity of embodiment 1 is the highest, the activity of the propylamine identical with nitrogenous thing amount is compared, and the activity of the catalyst that the present invention is made is higher, and the alkalescence of catalyst that this explanation is incorporated into Graphene gained by propylamine is stronger than simple propylamine.
The activity of embodiment 1～4 all will be higher than the magnesian activity of solid base, so the prepared catalyst of the present invention has certain commercial promise.
Claims (10)
1. a preparation method for nitrogen-doped graphene material, is characterized in that the step comprising:
1) in the aqueous solution of the graphite oxide through ultrasonic dispersion, add the small aliphatic amine molecule aqueous solution, hydro-thermal reaction 36～72h, wherein, the concentration of graphite oxide aqueous solution is 1-5g/L, the molar concentration of the aqueous solution of small aliphatic amine molecule is 1～3mol/L;
2) isolate precipitated product, through washing, dry, obtain nitrogen-doped graphene material.
2. preparation method according to claim 1, is characterized in that described small aliphatic amine molecule is at least one in methylamine, dimethylamine, ethamine, diethylamine, propylamine or butylamine.
3. preparation method according to claim 1, is characterized in that described small aliphatic amine molecule is methylamine, ethamine, n-propylamine or butylamine.
4. preparation method according to claim 1, is characterized in that described small aliphatic amine molecule and the mass ratio of graphite oxide: 30-50: 1.5-2.5.
5. a preparation method for nitrogen-doped graphene material, is characterized in that the step comprising:
(1) in the mixed liquor of the concentrated sulfuric acid and phosphoric acid, add crystalline graphite powder and potassium permanganate, at 30-50 ℃, stir 6-24h, slowly add water and hydrogen peroxide reaction 20-30min, obtain the turbid liquid of graphite oxide;
(2) standing, graphite oxide difference water and ethanol decant 4-6 time, be dried, and obtains the graphite oxide of purifying;
(3) again graphite oxide is joined anhydrate in and slowly stir 20-30min, then ultrasonic dispersion, obtains the aqueous solution of graphite oxide;
(4) hydro-thermal method is prepared nitrogen-doped graphene: will in the aqueous solution of the aqueous solution of 1～3mol/L small aliphatic amine molecule and the graphene oxide of 1-5g/L, mix ultrasonic dispersion, then hydro-thermal reaction 36～72h at 60～120 ℃;
(5) separation, washes with water, dry, obtains described nitrogen-doped graphene material.
6. preparation method according to claim 1, is characterized in that the concentrated sulfuric acid that step (1) is described and the volume ratio 7-8 of phosphoric acid: 1.
7. preparation method according to claim 1, is characterized in that the mass ratio of the concentrated sulfuric acid, crystalline graphite powder and potassium permanganate that step (1) is described is: 400-450: 30-40: 80-100.
8. preparation method according to claim 1, is characterized in that the mass ratio of step (1) graphite powder, water and hydrogen peroxide is: 2-6: 200～400: 3-5.
9. preparation method according to claim 1, is characterized in that described dry of step (5) is 80～120 ℃ of vacuum drying 12-24h.
10. preparation method according to claim 1, is characterized in that the power of described ultrasonic dispersion is 50-53KHz, and the time is 50-70min.
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| CN106006618A (en) * | 2016-05-26 | 2016-10-12 | 齐鲁工业大学 | Carbon alkyl chain modified graphene film as well as preparation method and application thereof |
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