CN104528703B - Preparation method of nitrogen/phosphorus-codoped graphene - Google Patents
Preparation method of nitrogen/phosphorus-codoped graphene Download PDFInfo
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Abstract
The invention discloses a preparation method of nitrogen/phosphorus-codoped graphene, which comprises the following steps: S100: proportionally and evenly mixing a phosphatic compound, a nitrogenous organic matter and a tricarbo compound, and drying and pulverizing or directly pulverizing, thereby obtaining precursor granules, wherein the mole ratio of N atoms in the nitrogenous organic matter to C atoms in the tricarbo compound is 10:1-100:1, and the mole ratio of N atoms in the nitrogenous organic matter to P atoms in the phosphatic compound is 10:1-1000:1; and S200. putting the precursor granules in a heating furnace, introducing a protective gas, keeping the temperature at 800-1300 DEG C for 0.5-5 hours, and cooling to obtain the nitrogen/phosphorus-codoped graphene. The method has the advantages of simple preparation process, accessible raw materials, low cost and high yield, and can easily implement large-scale production. The obtained graphene has the advantages of uniform distribution of N atoms and P atoms, adjustable doping content and favorable product quality, and has higher practical application value.
Description
Technical field
The present invention relates to technical field of material, more particularly to a kind of preparation method of nitrogen-phosphor codoping Graphene.
Background technology
Graphene is a kind of two-dimentional new carbon being made up of c atom hexatomic ring plane development.Good carrier moves
Shifting rate and extra specific surface area make Graphene become material star.However, pure Graphene is in use due to Van der Waals
The effect of power and coulomb electrostatic force is susceptible to the ability that interlayer is again fitted and lost storage electric charge.Research shows, by mixing
The miscellaneous free charge that can change, in the equally distributed situation in graphene sheet layer both sides, makes foreign atom periphery a range of certainly
Localization distribution is occurred by electronics, thus leading to graphene sheet layer that bending gauffer occurs.Gauffer graphene sheet layer can provide relatively
Strong support force, thus avoid graphene film interlayer stacking be combined, can also improve simultaneously overall porosity, mesoporous fraction thus
The impact application in fields such as energy storage, catalysis, environmental protection for the Graphene.
At present, the Graphene containing foreign atom is mainly prepared by chemical vapour deposition technique and ion implantation.
But, the requirement to equipment and technology for the above two method is harsh, preparation cost is high, is unfavorable for large-scale production.
Content of the invention
Based on the problems referred to above, the invention provides a kind of system preparing nitrogen-phosphor codoping Graphene simple, with low cost
Preparation Method.
For reaching above-mentioned purpose, the present invention adopts the following technical scheme that
A kind of preparation method of nitrogen-phosphor codoping Graphene, comprises the following steps:
S100: by phosphorus-containing compound, itrogenous organic substance and six carbon compounds according to certain ratio mix homogeneously, after being dried
Pulverize or directly pulverize, obtain granular precursor；
Wherein, in described itrogenous organic substance, n atom and the mol ratio of c atom in described six carbon compounds are 10:1～100:
1, in described itrogenous organic substance, n atom and the mol ratio of p atom in described phosphorus-containing compound are 10:1～1000:1；
S200: described granular precursor is placed in heating furnace, is passed through protective gas, be incubated at 800 DEG C～1300 DEG C
0.5h～5h, can get nitrogen-phosphor codoping Graphene after cooling.
Wherein in an embodiment, described itrogenous organic substance is one of carbamide, tripolycyanamide and dicyandiamide or many
Kind；
Described six carbon compounds are one or more of five Hydroxymethylfurfural, glucose, mannose and alginic acid；
Described phosphorus-containing compound is one of phosphoric acid and triphenylphosphine or two kinds.
Wherein in an embodiment, in s100, described phosphorus-containing compound, itrogenous organic substance and six carbon compounds pass through leaching
The mode mix homogeneously that stain, common dissolving or solid are co-mulled and made into.
Wherein in an embodiment, described phosphorus-containing compound be phosphoric acid when, described phosphorus-containing compound, itrogenous organic substance and
Six carbon compounds mix homogeneously in the following way:
Described itrogenous organic substance and mass concentration are the phosphate aqueous solution incipient impregnation of 1wt%～20wt%, then plus
Enter six carbon compounds, and stir.
Wherein in an embodiment, in s100, described drying condition is: 12h～24h is dried at 60 DEG C～100 DEG C.
Wherein in an embodiment, in s100, the granularity of described granular precursor is less than or equal to 20 mesh.
Wherein in an embodiment, in s200, the linear rate of flow of the described protective gas being passed through be 1cm/min～
10cm/min.
Wherein in an embodiment, in s200, the temperature controlled processes of described heating furnace are: with 1 DEG C/min～5 DEG C/
The speed of min, is continued to rise with the speed of 2 DEG C/min～10 DEG C/min after insulation 1h～5h to 600 DEG C～700 DEG C by room temperature
Temperature, to 800 DEG C～1300 DEG C, after insulation 0.5h～3h, is cooled to room temperature.
Wherein in an embodiment, in s200, the temperature controlled processes of described heating furnace are: with 1 DEG C/min～5 DEG C/
The speed of min after insulation 1h～5h, is cooled to room temperature by room temperature to 800 DEG C～1300 DEG C.
Wherein in an embodiment, described protective gas is one or more of nitrogen, argon and helium.
The method have the advantages that
The present invention can obtain nitrogen-phosphor codoping Graphene by disposable solid phase thermal cracking, compared with traditional method, this
The requirement to equipment and technology for the method for invention is relatively low, and preparation process is simple, and raw material is readily obtained, low cost, yield high it is easy to
Large-scale production, and preparation process is without the support of substrate, it is to avoid Graphene is difficult to detached problem with substrate；Meanwhile, profit
In the Graphene being obtained by the present invention, n atom and p atom are evenly distributed, and doping content is adjustable, good product quality, has
Higher actual application value.
Brief description
Fig. 1 is the Raman spectrogram of the nitrogen-phosphor codoping Graphene obtaining in the embodiment of the present invention 1；
Fig. 2 is the scanning electron microscope (SEM) photograph of the nitrogen-phosphor codoping Graphene obtaining in the embodiment of the present invention 1；
Fig. 3 is the transmission electron microscope picture of the nitrogen-phosphor codoping Graphene obtaining in the embodiment of the present invention 1；
Fig. 4 is the atomic force microscope characterization result of the nitrogen-phosphor codoping Graphene obtaining in the embodiment of the present invention 1, its
In, background is atomic force electromicroscopic photograph, and curve is the elevation carrection curve of Graphene；
Fig. 5 is the nitrogen physisorption result of the nitrogen-phosphor codoping Graphene obtaining in the embodiment of the present invention 1；
Fig. 6 is the x photoelectron spectroscopy figure of the nitrogen-phosphor codoping Graphene obtaining in the embodiment of the present invention 1.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that it is described herein concrete
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of preparation method of nitrogen-phosphor codoping Graphene, mixed by the Graphene that the method is prepared
Miscellaneous uniformly yield is high, and the physical and chemical performance of the product obtaining is stable, is not susceptible in use stack due to lamella
The compound and situation that leads to Graphene performance to be lost.
The preparation method of the present invention comprises the following steps:
S100, the preparation of granular precursor: by phosphorus-containing compound, itrogenous organic substance and six carbon compounds according to certain ratio
Example mix homogeneously, crushed after being dried or directly pulverizing, obtain granular precursor；Wherein, n atom and six carbonizations in itrogenous organic substance
In compound, the mol ratio of c atom is 10:1～100:1, the mol ratio of p atom in n atom and phosphorus-containing compound in itrogenous organic substance
For 10:1～1000:1.
It is preferred that as a kind of embodiment, itrogenous organic substance be one of carbamide, tripolycyanamide, dicyandiamide or
Multiple (including two kinds)；Six carbon compounds are the compound containing 6 c atoms, preferably five Hydroxymethylfurfural, glucose, sweet
One or more of the sugared alginic acid of dew (including two kinds)；Phosphorus-containing compound is phosphoric acid, triphenylphosphine or the mixture of the two.By
In phosphoric acid, there is pore-creating effect, by increasing capacitance it is possible to increase the specific surface area of the Graphene finally giving, therefore, phosphorus-containing compound is preferably phosphorus
Acid or the mixture of phosphoric acid and triphenylphosphine.
In the present invention, phosphorus-containing compound, itrogenous organic substance and six carbon compounds can be ground altogether by dipping, common dissolving or solid
The mode mix homogeneously of mill.For example, first itrogenous organic substance can be placed in dipping in the aqueous solution of phosphorus-containing compound, then add
Six carbon compounds, and stir；Also phosphorus-containing compound, itrogenous organic substance and six carbon compounds can be dissolved in a certain amount of water
In, and stir；Also phosphorus-containing compound, itrogenous organic substance and six carbon compounds directly can be mixed, then grind uniformly.
Further, when phosphorus-containing compound is for phosphoric acid, phosphorus-containing compound, itrogenous organic substance and six carbon compounds can pass through
Following manner mix homogeneously: by the itrogenous organic substance and mass concentration phosphate aqueous solution incipient impregnation for 1wt%～20wt%,
Add six carbon compounds, and stir.Incipient impregnation speed, mix homogeneously, it is suitable for commercial production；And at this
In the concentration range of phosphoric acid, be conducive to obtaining the more preferably excellent Graphene of performance.
By phosphorus-containing compound, itrogenous organic substance and six carbon compounds according to certain ratio mix homogeneously after, if mixture
In there is free moisture, then need to carry out drying operation, to remove the free moisture in mixture, the step then pulverized again
Suddenly, if there is not free moisture in mixture, can directly mixture be pulverized.It is preferred that drying condition is: 60 DEG C～
12h～24h is dried at 100 DEG C.Wherein, grinding mode is preferably mechanical activation comminution, such as mechanical lapping.It should be noted that it is nitrogenous
The blending process of Organic substance, phosphorus-containing compound and six carbon compounds and crushing process can be carried out simultaneously.
In the present invention, the granularity for the granular precursor obtaining after pulverizing is not particularly limited.In order to prepare performance
Excellent nitrogen-phosphor codoping Graphene, strengthens its physical and chemical stability, it is preferred that the granularity of granular precursor is less than or equal to 20
Mesh.
S200, solid phase heat scission reaction: the granular precursor obtaining in step s100 is placed in heating furnace, is passed through protection
Gas, is incubated 0.5h～5h at 800 DEG C～1300 DEG C, can get nitrogen-phosphor codoping Graphene after cooling.
It is preferred that the nitrogen-phosphor codoping Graphene that the present invention obtains has 2～3 layer graphene lamellas.
This step obtains required nitrogen-phosphor codoping Graphene by solid phase thermal cracking, and wherein, heating furnace is preferably built-in
Quartz ampoule or the tube furnace of alundum tube, to facilitate being passed through of protective gas, protective gas is preferably in nitrogen, argon and helium
One or more.The flow velocity of protective gas is unsuitable excessive, and its linear rate of flow is preferably 1cm/min～10cm/min.Under this speed,
Both can guarantee that yield and the purity of product, and the oxidation of product can have been prevented again, and then improve the physical and chemical performance of product.
In step s200, mode of heating can adopt a step heating mode, and temperature-gradient method mode may also be employed.In order to improve product
Amount of substance, firing rate is unsuitable too fast, it is preferred that when using a step heating mode, the temperature controlled processes of heating furnace are: with
The speed of 1 DEG C/min～5 DEG C/min after insulation 1h～5h, is cooled to room temperature by room temperature to 800 DEG C～1300 DEG C；When adopting
During with temperature-gradient method mode, the temperature controlled processes of heating furnace are: with the speed of 1 DEG C/min～5 DEG C/min by room temperature extremely
600 DEG C～700 DEG C, it is continuously heating to 800 DEG C～1300 DEG C with the speed of 2 DEG C/min～10 DEG C/min after insulation 1h～5h, protects
After warm 0.5h～3h, it is cooled to room temperature.
In the present invention, the Main Function of itrogenous organic substance is to provide template, makes six carbon compounds planar polymerized and forms folder
Stratification compound, after temperature raises, itrogenous organic substance overwhelming majority volatilization or distillation escape, and leave the carbon skeleton of stratiform, thus being
The generation of Graphene provides the foundation；The effect of phosphorus-containing compound is to provide p source, when there is phosphoric acid in phosphorus-containing compound, by
The intermediate product producing in phosphoric acid and its pyrolysis process has the effect of pore-creating it is thus possible to improve Graphene specific surface
Long-pending.
It should be noted that in the nitrogen-phosphor codoping Graphene finally giving, the doping content of n atom and p atom can
By initial when each raw material ratio regulated and controled.
The preparation method of the nitrogen-phosphor codoping Graphene of the present invention, adopts and traditional diverse preparation of preparation method
Approach, the raw material that the method for the present invention uses is conventional industrial chemicals, and cost is relatively low；Meanwhile, the method for the present invention is to equipment
Relatively low with the requirement of technology, nitrogen-phosphor codoping Graphene can disposably be obtained by solid phase thermal cracking, simple to operate it is easy to rule
Modelling produces；In the Graphene that the method for the present invention obtains, n atom and p atom are evenly distributed, doping content is adjustable such that it is able to
Meet the application of Graphene different field；And the Graphene that the present invention obtains has hierarchical porous structure, there is preferably self-supporting
Performance, has the advantages that ultralight and superhigh specific surface area simultaneously, can resist in use and stack compound, have stable thing
Physicochemical performance and excellent service life；Additionally, the preparation process of the method is without the support of substrate, it is to avoid Graphene with
Substrate is difficult to detached problem.
For a better understanding of the present invention, below by specific embodiment to the nitrogen-phosphor codoping Graphene of the present invention
Preparation method is further described.Reaction raw materials in following examples are marketable material.
Embodiment 1
(1) add 80g dicyandiamide in beaker, then with the phosphoric acid incipient impregnation for 10wt% for the mass concentration after, then
Add 2g five Hydroxymethylfurfural, stir at 80 DEG C, put in baking oven and 12h is dried at 100 DEG C, grind after taking-up, obtain
It is less than or equal to the granular precursor of 20 mesh to granularity.Wherein, c atom in the n atom and five Hydroxymethylfurfural in dicyandiamide
Mol ratio is 40:1, and the mol ratio of the n atom in dicyandiamide and the p atom in phosphoric acid is 60:1.
(2) granular precursor obtaining step (1) is placed in the quartz boat in tube furnace, is passed through high pure nitrogen after sealing
As whole process protection gas, wherein, the linear rate of flow of nitrogen is 2cm/min；It is warming up to the speed of 2 DEG C/min after ventilation 1h
600 DEG C, it is incubated 2h, is then warming up to 1000 DEG C with the speed of 5 DEG C/min, be incubated 1h, naturally cool to room temperature, the product obtaining
It is nitrogen-phosphor codoping Graphene.
Referring to Fig. 1, it is the Raman spectrogram of the nitrogen-phosphor codoping Graphene that the present embodiment obtains, it can be seen that
1340cm-1、1580cm-1And 2680cm-1There are three characteristic peaks, respectively d, g and 2d peak in place, illustrates that the product obtaining is graphite
Alkene；The scanning electron microscope (SEM) photograph of the nitrogen-phosphor codoping Graphene that Fig. 2 obtains for the present embodiment, from the visible obvious gauffer graphene film of figure
Rotating fields；The transmission electron microscope picture of the nitrogen-phosphor codoping Graphene that Fig. 3 obtains for the present embodiment, as seen from the figure this Graphene have many
Pore property；The atomic force microscope characterization result of the nitrogen-phosphor codoping Graphene that Fig. 4 obtains for the present embodiment, elevation carrection shows
For 2～3 layer graphene lamellas；The nitrogen physisorption result of the nitrogen-phosphor codoping Graphene that Fig. 5 obtains for the present embodiment, its ratio
Surface area is up to 1960m2/ g, micropore and mesoporous abundant, and mesoporous pore size in 4nm about there is integrated distribution；Fig. 6 is this enforcement
The x photoelectron spectroscopy figure of the nitrogen-phosphor codoping Graphene that example obtains, result shows, nitrogen, P elements composition difference in this Graphene
For 5.07% (atomic ratio, similarly hereinafter), 0.99%, and oxygen content relatively low be 5.89%.
Embodiment 2
(1) add 80g dicyandiamide in beaker, then with the phosphoric acid incipient impregnation for 20wt% for the mass concentration after, then
Add 2g five Hydroxymethylfurfural, stir at 80 DEG C, put in baking oven and 12h is dried at 100 DEG C, grind after taking-up, obtain
It is less than or equal to the granular precursor of 20 mesh to granularity.Wherein, c atom in the n atom and five Hydroxymethylfurfural in dicyandiamide
Mol ratio is 40:1, and the mol ratio of the n atom in dicyandiamide and the p atom in phosphoric acid is 30:1.
(2) with embodiment 1.
Compared with Example 1, the concentration of the phosphoric acid in the raw material that the present embodiment is used there occurs change, and remaining prepares bar
Part does not all change, and with the rising of phosphoric acid concentration, the total pore volume of nitrogen-phosphor codoping Graphene finally giving and specific surface area are all
Become big.
Embodiment 3
(1) add 80g dicyandiamide in beaker, then with the phosphoric acid incipient impregnation for 1wt% for the mass concentration after, then plus
Enter 2g five Hydroxymethylfurfural, stir at 80 DEG C, put in baking oven and 12h is dried at 100 DEG C, grind after taking-up, obtain
Granularity is less than or equal to the granular precursor of 20 mesh.Wherein, the rubbing of the c atom in the n atom in dicyandiamide and five Hydroxymethylfurfural
Your ratio is 40:1, and the mol ratio of the n atom in dicyandiamide and the p atom in phosphoric acid is 600:1.
(2) with embodiment 1.
Compared with Example 1, the concentration of the phosphoric acid in the raw material that the present embodiment is used there occurs change, and remaining prepares bar
Part does not all change, with the reduction of phosphoric acid concentration, the micropore quantity of the nitrogen-phosphor codoping Graphene finally giving, total pore volume and ratio
Surface area all reduces.
Embodiment 4
(1) in beaker add 120g dicyandiamide, 1.5g five Hydroxymethylfurfural, the analytically pure strong phosphoric acid of 3.78ml and
600ml deionized water, stirs at 80 DEG C, and 16h is dried in the baking oven being subsequently placed in 80 DEG C, removes free moisture, takes out
After grind, obtain granularity be less than or equal to 20 mesh granular precursor.Wherein, in the n atom and five Hydroxymethylfurfural in dicyandiamide
C atom mol ratio be the mol ratio of p atom in 80:1, the n atom in dicyandiamide and strong phosphoric acid be 100:1.
(2) granular precursor obtaining step (1) is placed in the quartz boat in tube furnace, is passed through high-purity argon gas after sealing
As whole process protection gas, wherein, the linear rate of flow of argon is 5cm/min；It is warming up to the speed of 2 DEG C/min after ventilation 1h
1000 DEG C, it is incubated 2h, naturally cools to room temperature, the product obtaining is nitrogen-phosphor codoping Graphene.
Embodiment 5
(1) 20g dicyandiamide, 2g five Hydroxymethylfurfural, the analytically pure strong phosphoric acid of 6.3ml and 500ml is added to go in beaker
Ionized water, stirs at 60 DEG C, and 24h is dried in the baking oven being subsequently placed in 60 DEG C, removes free moisture, grinds after taking-up,
Obtain the granular precursor that granularity is less than or equal to 20 mesh.Wherein, the c atom in the n atom and five Hydroxymethylfurfural in dicyandiamide
Mol ratio be the mol ratio of p atom in 10:1, the n atom in dicyandiamide and strong phosphoric acid be 10:1.
(2) granular precursor obtaining step (1) is placed in the quartz boat in tube furnace, is passed through high-purity argon gas after sealing
As whole process protection gas, wherein, the linear rate of flow of argon is 2cm/min；It is warming up to the speed of 1 DEG C/min after ventilation 0.5h
800 DEG C, it is incubated 5h, naturally cools to room temperature, the product obtaining is nitrogen-phosphor codoping Graphene.
Embodiment 6
(1) add 160g tripolycyanamide and 2.3g mannose in beaker, then add 0.55ml mass dense in beaker
Spend the phosphoric acid for 20wt%, and stir, be subsequently placed in ball milling 60min in ball mill, obtain granular precursor.Wherein, three
The mol ratio of the c atom in the n atom in poly cyanamid and mannose is 100:1, the p in the n atom in tripolycyanamide and phosphoric acid
The mol ratio of atom is 1000:1.
(2) granular precursor obtaining step (1) is placed in the quartz boat in tube furnace, is passed through high pure nitrogen after sealing
As whole process protection gas, wherein, the linear rate of flow of nitrogen is 5cm/min；With the speed liter of 1 DEG C/min after ventilation a period of time
Temperature, to 700 DEG C, is incubated 5h, is then warming up to 1300 DEG C with the speed of 10 DEG C/min, is incubated 0.5h, naturally cools to room temperature, obtain
The product arriving is nitrogen-phosphor codoping Graphene.
Embodiment 7
(1) add 160g tripolycyanamide and 2.3g glucose in beaker, then in beaker, add 2g triphenylphosphine, and
Stir, be subsequently placed in ball milling 30min in ball mill, obtain granular precursor.Wherein, the n atom in tripolycyanamide and Portugal
The mol ratio of the c atom in grape sugar is that the mol ratio of the p atom in 100:1, the n atom in tripolycyanamide and triphenylphosphine is
1000:1.
(2) granular precursor obtaining step (1) is placed in the quartz boat in tube furnace, is passed through high-purity helium after sealing
As whole process protection gas, wherein, the linear rate of flow of helium is 4cm/min；With the speed liter of 5 DEG C/min after ventilation a period of time
Temperature, to 650 DEG C, is incubated 1h, is then warming up to 800 DEG C with the speed of 10 DEG C/min, is incubated 3h, naturally cools to room temperature, obtain
Product is nitrogen-phosphor codoping Graphene.
Embodiment 8
(1) 160g dicyandiamide, 2.3g glucose, the analytically pure strong phosphoric acid of 0.5ml, 2g triphenylphosphine are added in beaker,
And stir, it is subsequently placed in ball milling 60min in ball mill, obtain granular precursor.Wherein, the n atom and five in dicyandiamide
The mol ratio of the c atom in Hydroxymethylfurfural is the p atom in 100:1, the n atom in dicyandiamide and strong phosphoric acid and triphenylphosphine
The mol ratio of summation is 500:1.
(2) granular precursor obtaining step (1) is placed in the quartz boat in tube furnace, is passed through high-purity argon gas after sealing
As whole process protection gas, wherein, the linear rate of flow of argon is 6cm/min；It is warming up to the speed of 4 DEG C/min after ventilation 1h
1300 DEG C, it is incubated 1h, naturally cools to room temperature, the product obtaining is nitrogen-phosphor codoping Graphene.
Embodiment 9
(1) 120g carbamide, 1.2g glucose, the analytically pure strong phosphoric acid of 0.26ml and 700ml deionization are added in beaker
Water, stirs at 65 DEG C, and 16h is dried in the baking oven being subsequently placed in 100 DEG C, removes free moisture, grinds, obtain after taking-up
Granularity is less than or equal to the granular precursor of 20 mesh.Wherein, the mol ratio of the c atom in the n atom in carbamide and glucose is
The mol ratio of the p atom in 100:1, the n atom in carbamide and strong phosphoric acid is 1000:1.
(2) granular precursor obtaining step (1) is placed in the quartz boat in tube furnace, is passed through high-purity argon gas after sealing
As whole process protection gas, wherein, the linear rate of flow of argon is 7cm/min；It is warming up to the speed of 5 DEG C/min after ventilation 1h
700 DEG C, it is incubated 3h, is then warming up to 1200 DEG C with the speed of 4 DEG C/min, be incubated 1.5h, naturally cool to room temperature, the product obtaining
Thing is nitrogen-phosphor codoping Graphene.
Embodiment 10
(1) 60g carbamide, 6g alginic acid, the analytically pure phosphoric acid of 1.3ml and 300ml deionized water are added in beaker, in 65
Stir at DEG C, 16h in the baking oven being subsequently placed in 80 DEG C, is dried, remove free moisture, grind after taking-up, obtain granularity and be less than
Granular precursor equal to 20 mesh.Wherein, the mol ratio of the n atom in carbamide and the c atom in alginic acid is 10:1, in carbamide
N atom and phosphoric acid in the mol ratio of p atom be 100:1.
(2) granular precursor obtaining step (1) is placed in the quartz boat in tube furnace, is passed through high-purity argon gas after sealing
As whole process protection gas, wherein, the linear rate of flow of argon is 4cm/min；It is warming up to the speed of 5 DEG C/min after ventilation 0.5h
680 DEG C, it is incubated 2.5h, is then warming up to 1100 DEG C with the speed of 5 DEG C/min, be incubated 2h, naturally cool to room temperature, the product obtaining
Thing is nitrogen-phosphor codoping Graphene.
Embodiment described above only have expressed the several embodiments of the present invention, and its description is more concrete and detailed, but simultaneously
Therefore the restriction to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, some deformation can also be made and improve, these broadly fall into the guarantor of the present invention
Shield scope.Therefore, the protection domain of patent of the present invention should be defined by claims.
Claims (9)
1. a kind of preparation method of nitrogen-phosphor codoping Graphene is it is characterised in that comprise the following steps:
S100: by phosphorus-containing compound, itrogenous organic substance and six carbon compounds according to certain ratio mix homogeneously, crushed after being dried
Or directly pulverize, obtain granular precursor；
Wherein, in described itrogenous organic substance, n atom and the mol ratio of c atom in described six carbon compounds are 10:1～100:1, institute
Stating n atom and the mol ratio of p atom in described phosphorus-containing compound in itrogenous organic substance is 10:1～1000:1；
S200: described granular precursor is placed in heating furnace, is passed through protective gas, be incubated 0.5h at 800 DEG C～1300 DEG C
～5h, can get nitrogen-phosphor codoping Graphene after cooling,
Described itrogenous organic substance is one or more of carbamide, tripolycyanamide and dicyandiamide；
Described six carbon compounds are one or more of five Hydroxymethylfurfural, glucose, mannose and alginic acid；
Described phosphorus-containing compound is one of phosphoric acid and triphenylphosphine or two kinds.
2. the preparation method of nitrogen-phosphor codoping Graphene according to claim 1 is it is characterised in that in s100, described contains
Phosphorus compound, itrogenous organic substance and six carbon compounds mix homogeneously by way of dipping, altogether dissolving or solid are co-mulled and made into.
3. the preparation method of nitrogen-phosphor codoping Graphene according to claim 1 is it is characterised in that described phosphorus-containing compound
During for phosphoric acid, described phosphorus-containing compound, itrogenous organic substance and six carbon compounds mix homogeneously in the following way:
Described itrogenous organic substance and mass concentration are the phosphate aqueous solution incipient impregnation of 1wt%～20wt%, add six
Carbon compound, and stir.
4. the preparation method of nitrogen-phosphor codoping Graphene according to claim 1 is it is characterised in that in s100, described dry
Dry condition is: 12h～24h is dried at 60 DEG C～100 DEG C.
5. the preparation method of nitrogen-phosphor codoping Graphene according to claim 1 is it is characterised in that in s100, described before
The granularity driving body granule is less than or equal to 20 mesh.
6. the preparation method of nitrogen-phosphor codoping Graphene according to claim 1 is it is characterised in that in s200, described logical
The linear rate of flow of the protective gas entering is 1cm/min～10cm/min.
7. the preparation method of nitrogen-phosphor codoping Graphene according to claim 1 is it is characterised in that in s200, described plus
The temperature controlled processes of hot stove are: with the speed of 1 DEG C/min～5 DEG C/min by room temperature to 600 DEG C～700 DEG C, be incubated 1h
It is continuously heating to 800 DEG C～1300 DEG C with the speed of 2 DEG C/min～10 DEG C/min after～5h, after insulation 0.5h～3h, be cooled to
Room temperature.
8. the preparation method of nitrogen-phosphor codoping Graphene according to claim 1 is it is characterised in that in s200, described plus
The temperature controlled processes of hot stove are: with the speed of 1 DEG C/min～5 DEG C/min by room temperature to 800 DEG C～1300 DEG C, be incubated 1h
After～5h, it is cooled to room temperature.
9. the preparation method of nitrogen-phosphor codoping Graphene according to claim 1 is it is characterised in that described protective gas is
One or more of nitrogen, argon and helium.
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| CN104817063B (en) * | 2015-05-07 | 2016-08-17 | 常州大学 | A kind of preparation method of two dimension nitrogen phosphorus doping Graphene |
| CN104817077B (en) * | 2015-05-07 | 2016-08-24 | 常州大学 | A kind of preparation method of nitrogen phosphorus doping graphene film |
| CN104843692A (en) * | 2015-05-07 | 2015-08-19 | 常州大学 | Preparation method of two-dimensional sulfur nitrogen doped graphene |
| CN105214699B (en) * | 2015-09-30 | 2017-12-19 | 南开大学 | A kind of preparation method of porous doped carbon high-dispersion load phosphatization cobalt material and the application in electrocatalytic hydrogen evolution |
| CN105562050B (en) * | 2015-12-15 | 2018-12-11 | 华南理工大学 | A kind of porous class graphene-structured doping carbon material and the preparation method and application thereof |
| TWI648423B (en) | 2016-03-08 | 2019-01-21 | 財團法人工業技術研究院 | Metal-doped graphene and growth method of the same |
| CN107221459A (en) * | 2017-05-27 | 2017-09-29 | 中国石油大学(北京) | A kind of nitrogen-phosphor codoping graphene and preparation method and application |
| CN108232116A (en) * | 2017-12-15 | 2018-06-29 | 江苏大学 | A kind of preparation method of nitrogen, phosphor codoping Graphene gel electrochemistry storage sodium electrode |
| TWI676193B (en) * | 2018-07-31 | 2019-11-01 | 國家中山科學研究院 | A supercapacitor of n-p doping holey graphene material in ionic liquid electrolyte and method for producing thereof |
| CN110591698B (en) * | 2019-09-18 | 2022-12-27 | 宁波大学 | Preparation method and application of cyclotriphosphazene doped graphene quantum dots |
| CN111377439B (en) * | 2020-05-20 | 2022-09-16 | 延安大学 | Preparation method of graphene doped with two-dimensional nitrogen and phosphorus |
| CN114864295A (en) * | 2022-01-28 | 2022-08-05 | 上海工程技术大学 | Nitrogen-phosphorus co-doped graphene composite material, capacitor cathode material and preparation method of capacitor cathode material |
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