CN105350113B - A kind of preparation method and products obtained therefrom of azotized carbon nano fiber - Google Patents
A kind of preparation method and products obtained therefrom of azotized carbon nano fiber Download PDFInfo
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- CN105350113B CN105350113B CN201510905371.9A CN201510905371A CN105350113B CN 105350113 B CN105350113 B CN 105350113B CN 201510905371 A CN201510905371 A CN 201510905371A CN 105350113 B CN105350113 B CN 105350113B
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Abstract
The invention discloses a kind of preparation method and products obtained therefrom of azotized carbon nano fiber, its preparation process is：Silica spheres are made in sol-gal process, and silica spheres are distributed in water, are modified with MPS, the SiO of modification2Then ball redisperse adds melamine and coated into water, the SiO of cladding2Ball is calcined, and melamine is decomposed completely, obtains nitrogenizing the silica spheres of carbon coating, the silica spheres for nitrogenizing carbon coating are performed etching with alkali, silica spheres is removed, obtains azotized carbon nano fiber.Preparation process of the present invention is simple, the nanofiber of gained has the advantages that dispersiveness is preferable, experimental repeatability is higher, is not easy to reunite, can be used as nano-noble metal particle load or by doping or it is compound improve its performance as needed, in order to be more widely applied in the field such as photocatalytic degradation organic matter and Photocatalyzed Hydrogen Production, bio-pharmaceutical load or cell imaging.
Description
Technical field
The present invention relates to a kind of preparation method and products obtained therefrom of azotized carbon nano fiber, belongs to semi-conducting material and prepares skill
Art field.
Background technology
Class graphitization carbonitride is considered as polymer stable at room temperature.It is that one kind is alternateed by carbon, nitrogen-atoms
Hexatomic ring is formed, is the organic semiconducting materials that formation is mutually closely connected by C-C keys between ring, layer and interlayer are Van der Waals
Power acts on, and this special chemical structure makes it the narrow bandgap semiconductor material that energy gap is 2.7eV.Class graphitization nitrogenizes
Carbon has Carrier recombination speed higher, has the advantages that chemical property is stable, easily prepares, and it is nontoxic, in visible-range
The features such as response, there is the research heat that outstanding Electronic Performance, mechanical strength and optical property etc. cause domestic and foreign scholars again
Tide.
At present, the method for preparing nano-graphite carbonitride is a lot, can generally be divided into：High temperature and high pressure synthesis, physics
Chemical vapour deposition technique, hydro-thermal method, high-temperature polymerization, template etc..Its high temperature direct polymerization method prepares carbonitride method
Simply, it is not high to equipment requirement, but the pattern of sample that this method obtains mostly is block carbonitride, and in the side such as photocatalysis
Face application is poor.And solvent heat rule has more strict requirements, the sample prepared under different temperatures, pressure to pressure and temp
Moral character can differ larger, and experiment condition is more harsh.At present, by means of template, by functional modification, carbonitride is calcined
The class graphitization carbonitride of the more various pattern of self assembly preparation turns into new study hotspot in journey.
The content of the invention
The invention provides a kind of preparation method and products obtained therefrom of azotized carbon nano fiber, this method technique is simple, institute
It is nanometer fibrous, good crystallinity to obtain carbonitride.
Concrete technical scheme of the present invention is as follows：
A kind of preparation method of azotized carbon nano fiber, comprises the following steps：
（1）Second alcohol and water is mixed, adds ammoniacal liquor, stir to obtain solution, then adds alkoxyl silicone into the solution
Alkane, alkoxy silane is hydrolyzed to silica, centrifugation, washing, obtain silica spheres；
（2）Silica spheres are distributed in water, used（3- mercaptopropyis）Trimethoxy silane（Abbreviation MPS）Repaiied
Decorations, are obtained（3- mercaptopropyis）The SiO of trimethoxy silane modification2Ball；
（3）Will（3- mercaptopropyis）The SiO of trimethoxy silane (MPS) modification2Ball is distributed in water, then adds trimerization
Cyanamide, centrifuged after stirring, obtain the SiO of melamine cladding2Ball；
（4）By step（3）Product calcined, melamine is decomposed completely, obtain nitrogenize carbon coating titanium dioxide
Silicon ball；
（5）The silica spheres for nitrogenizing carbon coating are performed etching in 5 ~ 10mol/L aqueous slkali, remove silica
Ball, obtain azotized carbon nano fiber.
In above-mentioned preparation method, unless otherwise instructed, carry out at room temperature.
Above-mentioned steps（1）In, when the concentration of ammoniacal liquor is 25wt%, ethanol, water, the volume of 25wt% ammoniacal liquor and alkoxy silane
Than for 10: 1: 0.3: 0.02~10: 1: 0.3:0.2.
Above-mentioned steps（1）In, the alkoxy silane is tetraethyl orthosilicate, methyl silicate, positive silicic acid propyl ester or positive silicon
Acid butyl ester.
Above-mentioned steps（1）In, after adding ammoniacal liquor, 30min is stirred, after adding alkoxy silane, stirs 5-8h.
Above-mentioned steps（2）In, with MPS to SiO2Ball is modified, and the effect of modification is to make SiO2Ball surface links sulfydryl,
Be advantageous to melamine to be coated on silica spheres, so that the carbonitride formed after calcining is coated to SiO2Ball surface is more held
Easily realize, if not modifying, be difficult to realize carbonitride coated Si O2Ball, it also is difficult to obtain azotized carbon nano fiber after then etching.
Above-mentioned steps（2）In, it is described（3- mercaptopropyis）Trimethyl oxosilane is liquid, and MPS and alkoxy silane
Volume ratio is： 8×10-3:1~50×10-3:1。
Above-mentioned steps（2）In, after silica spheres are distributed in water, add（3- mercaptopropyis）Trimethyl oxosilane, so
Stir 2 days afterwards, MPS is modified silica spheres.
Above-mentioned steps（3）In, the SiO that is modified with melamine MPS2Ball is coated, the SiO of MPS modifications2Ball and three
The mass ratio of poly cyanamid is 1：6~1：120.
In above-mentioned steps (3), after adding melamine, stirring reaction 10-12 hours.In the range of this time, ball and three
Poly cyanamid dispersiveness is more preferable, and what melamine can be more uniformly distributed coat.
In above-mentioned steps (4), after melamine cladding, the SiO after coating is handled by the way of calcining2Ball, make trimerization
Cyanamide is decomposed into carbonitride, and removes other organic principles（Such as MPS）, calcining heat is 550-650 DEG C.
In above-mentioned steps (4), calcine and carried out under inert gas shielding.
In above-mentioned steps (4), heating rate during calcining is in 1-5 DEG C/min.
In above-mentioned steps (4), calcination time 2-4h.
Above-mentioned steps（5）In, performed etching with the aqueous slkali that concentration is 5 ~ 10mol/L.The aqueous slkali is sodium hydroxide
Solution or potassium hydroxide solution.The etching, refer to the silica spheres for nitrogenizing carbon coating being put into aqueous slkali and stir one section
Time, silica is removed completely.After silica removes, remaining carbonitride can carry out self assembly, shape in aqueous slkali
Into nanofiber pattern.Alkaline concentration is too low to make etching insufficient, have a certain amount of silica spheres and be not etched away,
Alkaline concentration is too high to make the slow self assembly under this alkalescence condition of the carbonitride after etching be difficult to occur, and can not generate and receive
Rice fibrous morphology.
Above-mentioned steps（5）In, the dosage of aqueous slkali is excessive, and those skilled in the art can be according to public in the prior art
The dosage for the aqueous slkali used in etching opened is adjusted and selected.
Above-mentioned steps（5）In, etch period is generally 6 ~ 12h.
In above-mentioned preparation method, the azotized carbon nano fiber of final gained is also within the scope of the present invention.
Gained carbonitride is graphitization carbonitride, can also be referred to as graphite type carbon nitride, and the length of nanofiber is
200nm ~ 500nm, a diameter of 50-150 nm.
Further, gained azotized carbon nano fiber surface is relatively smooth, and preferably, fibre diameter is from one end to another for dispersiveness
One end becomes larger.
The carbonitride pattern of the present invention is nanofiber, and crystallinity is high, size uniform, good dispersion, is not easy to reunite, and is prepared
When use silica nanosphere as template, by being coated after the surface-functionalized modifications of MPS with melamine to template,
Cladding product can obtain graphitization carbonitride coated Si O through high temperature polymerization2The product of ball, the product are only fallen with etching alkaline solution
SiO2Ball can obtain graphitization azotized carbon nano fiber, is greatly enriched the pattern of graphitization carbonitride, can be used as nanometer
The load of noble metal granule or by doping or it is compound improve its performance as needed, in order to photocatalytic degradation organic matter with
And the field such as the load of Photocatalyzed Hydrogen Production, bio-pharmaceutical or cell imaging is more widely applied.Preparation method technique letter of the present invention
Single, experimental repeatability is higher, and cost is relatively low, and pattern is special, has preferable application prospect.
Brief description of the drawings
X-ray diffraction (XRD) collection of illustrative plates for the graphitization azotized carbon nano fiber that Fig. 1 embodiment of the present invention 1 synthesizes.
The ESEM for the intermediate product graphitization carbonitride coated silica ball that Fig. 2 embodiment of the present invention 1 synthesizes
(SEM) photo.
ESEM (SEM) photo for the graphitization azotized carbon nano fiber that Fig. 3 embodiment of the present invention 1 synthesizes.
Fig. 4 embodiment of the present invention it is 2-in-1 into graphitization azotized carbon nano fiber ESEM (SEM) photo.
ESEM (SEM) photo for the graphitization azotized carbon nano fiber that Fig. 5 embodiment of the present invention 3 synthesizes.
ESEM (SEM) photo for the graphitization azotized carbon nano fiber that Fig. 6 embodiment of the present invention 5 synthesizes.
Fig. 7 comparative examples of the present invention it is 2-in-1 into porous graphitization carbonitride ESEM (SEM) photo.
Embodiment
Below by embodiment, the present invention will be further elaborated, it should be appreciated that, the description below merely to
The present invention is explained, its content is not defined.
In following embodiments, the mass concentration of the ammoniacal liquor is 25%.
Embodiment 1
1.1 by 50mL ethanol and 5mL water wiring solution-formings, adds 1.5mL ammoniacal liquor, and homogeneous solution is obtained after stirring 30min；
1.2 add 0.4 mL tetraethyl orthosilicates (TEOS) in above-mentioned solution, stir 6 h, obtain silica and receive
Rice ball template product；
1.3 by product obtained above through centrifuging, wash, dry after, be distributed in 10 mL water, add 5 μ L（3- sulfydryls
Propyl group）Trimethyl oxosilane (MPS) solution, after stirring 2 days, through centrifuging, washing, obtain product；
1.4 take the product solid powder that 0.1g steps 1.3 obtain, and are distributed in 20mL water, add 1.5g melamines, stir
After mixing 12 h, through centrifuging, washing, dry, white solid powder is obtained；With 5 DEG C/min heating speed under inert gas shielding
Rate is heated to 550 DEG C, is incubated 4h, is decomposed completely to melamine, natural cooling, obtain graphitization carbonitride coated silica
Nanometer ball material；
1.5 products that will be obtained in step 1.4 after calcining perform etching in 7.5M sodium hydroxide solutions, and etch period is
12 h, then through centrifuge washing, drying, obtain nanometer fibrous carbonitride.
Fig. 1 is the X ray diffracting spectrum of sample, it can be seen that gained nanofiber azotized carbon nano fiber is
Pure phase graphite type carbon nitride.Fig. 2 is the stereoscan photograph of the sample before etching, and it can be seen from the figure that pattern is near-spherical, directly
Footpath size is 150 ~ 240 nm scopes.Fig. 3 is the stereoscan photograph of the sample after being etched, as can be seen from the figure Nanowire
Preferably, surface is relatively smooth, and every fiber becomes larger from one end to other end diameter, non-isodiametric cylinder for dimension dispersiveness
Shape, the length dimension of nanofiber is 200nm ~ 500nm, and diameter dimension is 50-150 nm.
Embodiment 2
Preparation method with embodiment 1, unlike：Silane reagent methyl silicate, in 7.5M sodium hydroxide solutions
Perform etching, mixing time 6h, it is substantially the same manner as Example 1 to obtain graphitization azotized carbon nano fiber morphology.Fig. 4 is to be carved
The stereoscan photograph of sample after erosion, as can be seen from the figure nanofiber length size is 200nm ~ 500nm, diameter dimension
For 50-150 nm.
Embodiment 3
Preparation method with embodiment 1, unlike：Performed etching in 7.5M potassium hydroxide solutions, mixing time is
12h, Fig. 5 are the stereoscan photographs of the sample after being etched, as can be seen from the figure nanofiber length size be 200 nm ~
500 nm, diameter dimension are 50-150 nm.
Embodiment 4
Preparation method with embodiment 1, unlike：The silane volume of addition is 0.1mL, and the melamine of addition is
3.0g, products obtained therefrom pattern is similar with Fig. 1, and nanofiber length size is 200 nm ~ 500 nm, diameter dimension 50-110
nm。
Embodiment 5
5.1 by 50mL ethanol and 5mL water wiring solution-formings, adds 1.5mL ammoniacal liquor, and homogeneous solution is obtained after stirring 30min；；
5.2 add 1 mL butyl silicates in above-mentioned solution, stir 6 h, obtain the production of silica nanosphere template
Thing；
5.3 by product obtained above through centrifuging, wash, dry after, be distributed in 10 mL water, add 8 μ L（3- sulfydryls
Propyl group）Trimethyl oxosilane (MPS) solution, after stirring 3 days, through centrifuging, washing, obtain product；
5.4 take the product solid powder that 0.25g steps 5.3 obtain, and are distributed in 20mL water, add 1.5g melamines,
After stirring 10 h, through centrifuging, washing, dry, white solid powder is obtained；With 5 DEG C/min heating under inert gas shielding
Speed is heated to 600 DEG C, is incubated 2h, is decomposed completely to melamine, natural cooling, obtains graphitization nitridation carbon coating titanium dioxide
Silicon nanometer ball material；
5.5 products that will be obtained in step 5.4 after calcining perform etching in 5M sodium hydroxide solutions, etch period 12
H, then through centrifuge washing, drying, obtain nanometer fibrous carbonitride.
Fig. 6 is the stereoscan photograph of the sample after being etched, and as can be seen from the figure nanofiber length size is 200
The nm of nm ~ 500, diameter dimension is 80-150 nm.
Embodiment 6
Preparation method with embodiment 3, unlike：650 DEG C are heated under inert gas shielding, heating rate 1
DEG C/min, gained graphitization azotized carbon nano fiber morphology is same as Example 1, and azotized carbon nano fibre length size is 200
The nm of nm ~ 400, diameter dimension is 50-150 nm.
Embodiment 7
Preparation method with embodiment 1, unlike：Performed etching in 10M sodium hydroxide solutions, etch period 8h.
Gained graphitization azotized carbon nano fiber morphology is similar to Example 1, azotized carbon nano fibre length size be 200nm ~
500nm, diameter dimension are 50-150 nm.
Embodiment 8
Preparation method with embodiment 1, unlike：Silane reagent positive silicic acid propyl ester, enter in 10M sodium hydroxide solutions
Row etching, mixing time 10h.Gained graphitization azotized carbon nano fiber morphology is similar to Example 1, and graphitization carbonitride is received
Rice fibre length size is 200nm ~ 450nm, and diameter dimension is 50-150 nm.
Embodiment 9
9.1 by 50mL ethanol and 5mL water wiring solution-formings, adds 1.5mL ammoniacal liquor, and homogeneous solution is obtained after stirring 30min；
9.2 add 0.8 mL positive silicic acid propyl esters in above-mentioned solution, stir 6 h, obtain silica nanosphere template
Product；
9.3 by product obtained above through centrifuging, wash, dry after, be distributed in 10 mL water, add 10 μ L（3- sulfydryls
Propyl group）Trimethyl oxosilane (MPS) solution, after stirring 2 days, through centrifuging, washing, obtain product；
9.4 take the product solid powder that 0.2g steps 3.3 obtain, and are distributed in 20mL water, add 3g melamines, stirring
After 12 h, through centrifuging, washing, dry, white solid powder is obtained；With 5 DEG C/min heating rate under inert gas shielding
650 DEG C are heated to, 2h is incubated, is decomposed completely to melamine, natural cooling, obtain graphitization carbonitride coated silica and receive
Rice ball material；
9.5 products that will be obtained in step 3.4 after calcining perform etching in 5M potassium hydroxide solutions, etch period 12
H, then through centrifuge washing, drying, obtain nanometer fibrous carbonitride.
Gained graphitization azotized carbon nano fiber morphology is similar to Example 1, and azotized carbon nano fibre length size is
200nm ~ 400nm, diameter dimension are 50-150 nm.
Embodiment 10
10.1 by 50mL ethanol and 5mL water wiring solution-formings, adds 1.5mL ammoniacal liquor, and homogeneous solution is obtained after stirring 30min；
10.2 add 0.1 mL tetraethyl orthosilicates (TEOS) in above-mentioned solution, stir 6 h, obtain silica and receive
Rice ball template product；
10.3 by product obtained above through centrifuging, wash, dry after, be distributed in 10 mL water, add 7 μ L（3- sulfydryls
Propyl group）Trimethyl oxosilane (MPS) solution, after stirring 2 days, through centrifuging, washing, obtain product；
10.4 take the product solid powder that 0.05g steps 1.3 obtain, and are distributed in 20mL water, add 4g melamines, stir
After mixing 12 h, through centrifuging, washing, dry, white solid powder is obtained；With 5 DEG C/min heating speed under inert gas shielding
Rate is heated to 650 DEG C, is incubated 4h, is decomposed completely to melamine, natural cooling, obtain graphitization carbonitride coated silica
Nanometer ball material；
10.5 products that will be obtained in step 1.4 after calcining perform etching in 7.5M sodium hydroxide solutions, etch period
For 12 h, then through centrifuge washing, drying, obtain nanometer fibrous carbonitride.
Gained graphitization azotized carbon nano fiber morphology is similar to Example 1, and azotized carbon nano fibre length size is
200nm ~ 400nm, diameter dimension are 50-120 nm.
Embodiment 11
Preparation method with embodiment 10, unlike：Silane reagent 0.2mL positive silicic acid propyl esters, obtained silica
It is dispersed in water, takes the sample after 0.05gMPS modifications, adds the stirring of 6g melamines.Gained graphitization azotized carbon nano fiber
Pattern is similar to Example 1, and graphitization azotized carbon nano fibre length size is 200nm ~ 500nm, diameter dimension 65-140
nm。
Comparative example 1
Preparation method with embodiment 1, unlike：Concentration of sodium hydroxide solution is 1M, etch period 24h.Gained stone
Inkization carbonitride pattern is porous carbonitride, and is etched not exclusively, and more silica is not etched away, bore dia 110
nm~150 nm。
Comparative example 2
Preparation method with embodiment 1, unlike：Performed etching using 20M sodium hydroxide solutions, etch period 6h.
Fig. 7 is the stereoscan photograph of the sample after being etched, and as can be seen from the figure gained graphitization carbonitride pattern is porous
Sheet, do not crimp.
Comparative example 3
3.1 by 50mL ethanol and 5mL water wiring solution-formings, adds 1.5mL ammoniacal liquor, and homogeneous solution is obtained after stirring 30min；
3.2 add 0.4 mL tetraethyl orthosilicates (TEOS) in above-mentioned solution, stir 6 h, obtain silica and receive
Rice ball template product；
Product obtained above is centrifuged, washed, dried by 3.3, the solid powder for taking 0.1g to dry, is distributed in 20mL water
In water, 1.5g melamines are added, after stirring 12 h, through centrifuging, washing, dry, obtain white solid powder；By white solid
Powder is heated to 550 DEG C under inert gas shielding with 5 DEG C/min heating rate, is incubated 4h, divides completely to melamine
Solution, natural cooling.
3.4 products that will be obtained in step 3.3 after calcining perform etching in 7.5M sodium hydroxide solutions, and etch period is
12 h, then through centrifuge washing, drying, obtain product.
In the method, because being added without MPS, the product before being etched after calcining can not form the nitridation with class ball-type pattern
Carbon, so as to which the graphitization carbonitride pattern after etching is containing porose nitridation carbon plate, rather than nanofiber.
Claims (10)
- A kind of 1. preparation method of azotized carbon nano fiber, it is characterized in that comprising the following steps：（1）Second alcohol and water is mixed, adds ammoniacal liquor, stir to obtain solution, then adds alkoxy silane into the solution, makes Alkoxy silane is hydrolyzed to silica, centrifugation, washing, obtains silica spheres；（2）Silica spheres are distributed in water, used（3- mercaptopropyis）Trimethoxy silane is modified, and is obtained（3- sulfydryls Propyl group）The SiO of trimethoxy silane modification2Ball；（3）Will（3- mercaptopropyis）The SiO of trimethoxy silane modification2Ball is distributed in water, then adds melamine, stirring Centrifuged after uniformly, obtain the SiO of melamine cladding2Ball；（4）By step（3）Product calcined, melamine is decomposed completely, obtain nitrogenize carbon coating silica spheres；（5）The silica spheres for nitrogenizing carbon coating are performed etching in 5 ~ 10mol/L aqueous slkali, remove silica spheres, Obtain azotized carbon nano fiber；Step（5）In, aqueous slkali is sodium hydroxide solution or potassium hydroxide solution.
- 2. preparation method according to claim 1, it is characterized in that：Step（1）In, the alkoxy silane is positive silicic acid second Ester, methyl silicate, positive silicic acid propyl ester or butyl silicate.
- 3. preparation method according to claim 1, it is characterized in that：Step（1）In, when the concentration of ammoniacal liquor is 25wt%, second Alcohol, water, the volume ratio of 25wt% ammoniacal liquor and alkoxy silane are 10: 1: 0.3: 0.02~0.2.
- 4. preparation method according to claim 1, it is characterized in that：（3- mercaptopropyis）Trimethyl oxosilane and alkoxyl silicone The volume ratio of alkane is 8 × 10-3:1~50×10-3:1；Step（3）In,（3- mercaptopropyis）The SiO of trimethoxy silane modification2Ball Mass ratio with melamine is 1：6~1：120.
- 5. according to the preparation method described in claim 1,3 or 4, it is characterized in that：Step（2）In, silica spheres are distributed to water In after, add（3- mercaptopropyis）Trimethyl oxosilane simultaneously stirs 2 days；In step (3), after adding melamine, stirring reaction 10-12 hours.
- 6. preparation method according to claim 1, it is characterized in that：Step（4）In, calcining heat is 550-650 DEG C.
- 7. the preparation method according to claim 1 or 6, it is characterized in that：Step（4）In, calcine under inert gas shielding Carry out.
- 8. the preparation method according to claim 1 or 6, it is characterized in that：Step（4）In, calcination time 2-4h；Step （5）In, etch period is 6 ~ 12h.
- It is 9. fine according to azotized carbon nano made from the preparation method of the azotized carbon nano fiber any one of claim 1-8 Dimension, it is characterized in that：The length of the azotized carbon nano fiber is 200nm ~ 500nm, a diameter of 50-150 nm.
- 10. azotized carbon nano fiber according to claim 9, it is characterized in that：Gained azotized carbon nano fiber surface is smooth, Good dispersion, fibre diameter pass through change greatly.
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| CN106744744B (en) * | 2017-01-20 | 2019-07-30 | 济南大学 | A kind of preparation method and products therefrom of cobalt doped honeycomb graphite phase carbon nitride nano material |
| CN106744745B (en) * | 2017-01-20 | 2019-07-30 | 济南大学 | A kind of graphite phase carbon nitride nanotube and preparation method thereof of carbon doping |
| CN107442151A (en) * | 2017-06-13 | 2017-12-08 | 江苏理工学院 | A kind of C3N4Nano wire photochemical catalyst and preparation method thereof |
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| CN103011099A (en) * | 2012-12-12 | 2013-04-03 | 常州大学 | Spherical mesoporous carbon nitride material and preparation method thereof |
| CN105056239A (en) * | 2015-08-06 | 2015-11-18 | 暨南大学 | Composite material of functional mesoporous silica loaded drug and siRNA, preparation and application thereof in preparation of anticancer drugs |
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| CN103011099A (en) * | 2012-12-12 | 2013-04-03 | 常州大学 | Spherical mesoporous carbon nitride material and preparation method thereof |
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