CN104986742B - One species bead chain shape graphitization azotized carbon nano material and preparation method thereof - Google Patents
One species bead chain shape graphitization azotized carbon nano material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to species bead chain shape graphitization azotized carbon nano material and preparation method thereof, belong to technical field of semiconductor material preparation.Azotized carbon nano material of the present invention is the class bead chain shape structure convexed to form by graphitization azotized carbon nano rod surface alignment class pearl, the diameter dimension of class pearl is 200 ~ 800 nm, 200~800nm of class pearl spacing, the nanorod diameter for connecting class pearl is 80~500nm, a length of 5~13.6 μm of chain.Its preparation method is：Melamine is dissolved into alcohol liquid, initial soln is obtained；Then salpeter solution is added, stirs and separates out precipitation, carbon nitride precursor solid powder is made, class bead chain shape graphitization azotized carbon nano material is then obtained by calcining.Preparation process is simple, and products obtained therefrom has surface smooth, size uniform, the advantages of dispersiveness is preferable, can be used as preparing the template of other materials, or is used as the carrier of noble metal nano particles.
Description
Technical field
The invention belongs to technical field of semiconductor material preparation, it is related to a species bead chain shape graphitization azotized carbon nano material
And preparation method thereof.
Background technology
Class graphitic nitralloy carbon is a kind of semi-conducting material compared with low energy gap (energy gap is 2.7eV), and with compared with
High Carrier recombination speed.Class graphitic nitralloy carbon has the advantages that heat endurance is good, chemical property stable, and without gold
Category, it is nontoxic, visible light-responded the features such as, make it a kind of novel photocatalyst, received significant attention in catalyst field, it is special
It is not its photoelectric property, light degradation organic dyestuff, catalysis organic reaction, photodissociation aquatic products hydrogen, makes it in electronics, optics, biology
It is widely used etc. many fields.
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 meteorology deposition method, chemical deposition, high-temperature polymerization, template etc..Although template can obtain different-shape
Sample, but this method complex process, morphology controllable are poor, and synthesis difficulty is higher.Wherein high-temperature polymerization refers under hot conditions
The a kind of direct of graphitization nitridation carbon polymer and easily method are prepared by presoma itself polycondensation, but this method is obtained
The pattern of the sample arrived mostly for bulk compared with thick-layer shape, hardly result in the sample of other patterns.In order to prepare not similar shape
The looks and higher pure phase graphitization azotized carbon nano material of crystallinity to high-temperature polymerization, it is necessary to be updated and innovated.
The content of the invention
The present invention prepares the weak point of graphitization nano carbonitride for high-temperature polymerization, and there is provided a species bead chain shape
Graphitization azotized carbon nano material, graphitization carbonitride pattern of the present invention is special, is class bead chain shape, good crystallinity, surface defect
It is few.Can be used as preparing the template of other materials, or as the carrier of noble metal nano particles, photocatalytic degradation organic matter, its
The application field such as the load of his nano particle and Photocatalyzed Hydrogen Production has broad application prospects, and can be also widely applied to biological medicament
Thing load etc..
Meanwhile, additionally provide the preparation method of above-mentioned class bead chain shape graphitization azotized carbon nano material, preparation method tool
There is the simple advantage of technique.
Concrete technical scheme of the present invention is as follows：
One species bead chain shape graphitization azotized carbon nano material, it is characterised in that：It is by graphitization azotized carbon nano rod table
The class bead chain shape structure that face class of permutation pearl is convexed to form, the diameter dimension of class pearl is between 200 ~ 800nm, class pearl
Away from 200~800nm, the nanorod diameter of connection class pearl is 80~500nm, a length of 5~13.6 μm of chain.
Its preparation method is：Melamine is dissolved into alcohol liquid, initial soln is obtained；Then salpeter solution is added, is stirred
And precipitation is separated out, carbon nitride precursor solid powder is made, then under inert gas shielding, class bead chain shape is obtained by calcining
Graphitization azotized carbon nano material.
The preparation method of above-mentioned class bead chain shape graphitization azotized carbon nano material, comprises the following steps：
（1）Melamine is added in alcohol liquid, stirring obtains uniform initial soln；
（2）To step（1）Initial soln in salpeter solution is added dropwise, stir, separate out precipitation；
（3）By step（2）Obtained precipitation is centrifuged, washed, drying, and obtains presoma solid powder；
（4）By step（3）Obtained presoma solid powder is heated to 380~450 DEG C, forged under inert gas shielding
Burning is decomposed completely to melamine, is cooled to room temperature, is obtained class bead chain shape graphitization azotized carbon nano material.
Step（1）In, the concentration that described melamine is dissolved in alcohol liquid is 0.16~0.40mol/L, preferably 0.16mol/
L。
Step（1）In, described alcohol liquid is second in ethylene glycol or the mixed liquor of ethylene glycol and glycerine, described mixed liquor
Glycol is 1 ~ 2 with glycerine volume ratio:1.
Step（2）In, described salpeter solution is the aqueous solution of nitric acid, and concentration is 0.1~0.5mol/L；
Step（2）In, described salpeter solution and the volume ratio of alcohol liquid are 1 ~ 3.6:1.
Step（2）In, it is 10~60 min to continue mixing time.
Step（3）In, described washing, detergent is followed successively by water and ethanol.
Step（4）In, described inert gas is nitrogen.
Step（4）In, described calcining, heating rate is 10 DEG C/min, and calcination time is 1~5h.
Reaction mechanism of the present invention is：By nitrate anion in salpeter solution and hydrogen ion self assembly, while making melamine matter
Then sonization, the presoma solid powder protonated polymerize through high-temperature calcination under inert gas shielding and then obtains product.
The amino of melamine is active reactive group, is added after nitric acid, easily carries out melamine protonation process, reduces melamine
Solubility in alcohol liquid.Calcination process, the melamine of protonation turns into stratiform along the polymerization of white precipitate nanofiber direction
Polymer, continues heating layered polymer and reaches that certain thickness is curled into rod, because layered polymer is in uneven thickness, therefore volume
Nanorod surfaces formation class bead chain shape pattern after song, in calcination temperature range, reaction temperature is higher, and what polymer was crimped gets over
Closely knit, crystallinity is better.
Class bead chain shape graphitization azotized carbon nano material of the present invention：Pattern is class bead chain shape, and crystallinity is high, there is less table
Planar defect, preparation process only carries out presoma processing without using template with nitric acid, and class bead chain shape can be synthesized by high temperature polymerization
Graphitization carbonitride, enriches the pattern of graphitization carbonitride, has wide application prospects in terms of the new material energy.The present invention is excellent
The product prepared in other templates, technique is simple, and cost is relatively low, and pattern is special, available for the template for preparing other materials, tool
There is preferable application prospect.
Brief description of the drawings
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates for the class bead chain shape graphitization carbonitride that the embodiment of the present invention 1 is synthesized；
Fig. 2 is ESEM (SEM) photo for the class bead chain shape graphitization carbonitride that the embodiment of the present invention 1 is synthesized；
Fig. 3 be the embodiment of the present invention it is 2-in-1 into class bead chain shape graphitization carbonitride ESEM (SEM) photo；
Fig. 4 is ESEM (SEM) photo for the class bead chain shape graphitization carbonitride that the embodiment of the present invention 3 is synthesized；
Fig. 5 is ESEM (SEM) photo for the class bead chain shape graphitization carbonitride that the embodiment of the present invention 9 is synthesized；
Fig. 6 is ESEM (SEM) photo for the class bead chain shape graphitization carbonitride that the embodiment of the present invention 10 is synthesized；
Fig. 7 is ESEM (SEM) photo for the graphitization carbonitride that comparative example 1 of the present invention is synthesized；
Fig. 8 be comparative example of the present invention it is 2-in-1 into graphitization carbonitride ESEM (SEM) photo；
Fig. 9 is ESEM (SEM) photo for the graphitization carbonitride that comparative example 5 of the present invention is synthesized.
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.
Embodiment 1
1.1 weigh 1.0g（0.0079mol）Melamine is added in 50mL ethylene glycol, stirs 30min, equal to obtaining
Even initial soln；
1.2 take 20 mL initial solns, and the concentration prepared is added dropwise for 0.3mol/L aqueous solution of nitric acid 24mL
In initial soln, 30min is persistently stirred, until precipitation is separated out completely；
1.3 above-mentioned precipitation is centrifuged after be washed with water after 2 times, then with ethanol centrifuge washing 2 times, dry, obtain
Presoma white solid powder；
1.4 are placed in presoma solid powder obtained above in tube furnace, nitrogen atmosphere protection under, according to 10 DEG C/
Min heating rates are warming up to 380 DEG C, and insulation 2h is calcined, and naturally cools to room temperature, that is, obtain the nitridation of class bead chain shape graphitization
Carbon sample（As shown in Figure 2）.
The architectural feature of gained class bead chain shape is：The diameter dimension of class pearl is 320 ~ 780nm.
Fig. 1 is the X ray diffracting spectrum of sample, it can be seen that gained class bead chain shape carbonitride is graphite mould nitrogen
Change carbon.Fig. 2 is the stereoscan photograph of sample, and it can be seen from the figure that class bead chain shape carbonitride diameter dimension is 320 ~ 780nm models
Enclose, class bead chain shape thing spacing is 200 ~ 800nm；The nanorod diameter for connecting class pearl is 80 ~ 300nm；A length of 5 ~ 13.6 μ of chain
m。
Embodiment 2
Preparation method be the same as Example 1, unlike：After concentration is instilled for 0.5mol/L 14.4mL aqueous solution of nitric acid,
Mixing time is 10min；400 DEG C of calcining 1h.Gained class bead chain shape graphitization carbonitride pattern is as shown in figure 3, gained class pelletron
The architectural feature of shape is：The diameter dimension of class pearl is 300~500nm, 200~500nm of class pearl spacing；Connect class
The nanorod diameter of pearl is 80~250nm；A length of 5~the 12.5nm of chain.
Embodiment 3
Preparation method be the same as Example 1, unlike：After concentration is instilled for 0.5mol/L aqueous solution of nitric acid 14.4mL, stir
The time is mixed for 30min, 450 DEG C of calcining 1h.Gained class bead chain shape graphitization carbonitride pattern is as shown in figure 4, gained class bead chain shape
Architectural feature be：The diameter dimension of class pearl is 300~500nm, 200~500nm of class pearl spacing；Connect class pearl
The nanorod diameter of shape thing is 80~250nm；A length of 5~the 12.5nm of chain.
Embodiment 4
Preparation method be the same as Example 1, unlike：After the aqueous solution of nitric acid 24mL for instilling 0.3mol/L, mixing time is
60min.Gained class bead chain shape graphitization carbonitride pattern：The diameter dimension of class pearl is 320 ~ 780nm, class pearl spacing
200~800nm；The nanorod diameter for connecting class pearl is 80~300nm.
Embodiment 5
Preparation method be the same as Example 1, unlike：Take 1.0g melamines to be directly dissolved in 20mL ethylene glycol to stir, obtain
To uniform initial soln.Gained class bead chain shape graphitization carbonitride pattern：The diameter dimension of class pearl is 320 ~ 780nm, class
200~800nm of pearl spacing；The nanorod diameter for connecting class pearl is 80~300nm.
Embodiment 6
Preparation method be the same as Example 1, unlike：450 DEG C of calcining 3h.Gained class bead chain shape graphitization carbonitride pattern institute
Obtain class bead chain shape graphitization carbonitride pattern：The diameter dimension of class pearl be 400 ~ 800nm, class pearl spacing 500~
800nm；The nanorod diameter for connecting class pearl is 100~300nm.
Embodiment 7
Preparation method be the same as Example 1, unlike：0.5g melamines are added in 20mL ethylene glycol.Gained class pearl
Chain graphitization carbonitride pattern：The diameter dimension of class pearl is 300 ~ 800nm, 200~800nm of class pearl spacing；Even
The nanorod diameter for connecing class pearl is 80~300nm.
Embodiment 8
Preparation method be the same as Example 1, unlike：380 DEG C of calcining 5h.Gained class bead chain shape graphitization carbonitride pattern：
The diameter dimension of class pearl is 300 ~ 800nm, 500~800nm of class pearl spacing；The nanometer rods for connecting class pearl are straight
Footpath is 80~300nm.
Embodiment 9
Preparation method be the same as Example 1, unlike：It is 1 that melamine is dissolved in into volume ratio:1 ethylene glycol and glycerine
Class bead chain shape graphitization carbonitride is obtained in mixed alcohol liquid, after calcining, pattern is as shown in Figure 5：The diameter dimension of class pearl is
400 ~ 800nm, 500 ~ 800nm of class pearl spacing；The nanorod diameter for connecting teardrop shape thing is 80 ~ 500nm.
Embodiment 10
Preparation method be the same as Example 1, unlike：It is 2 that melamine is dissolved in into volume ratio:1 ethylene glycol and glycerine
Class bead chain shape graphitization carbonitride is obtained in mixed alcohol liquid, after calcining, pattern is as shown in Figure 6：The diameter dimension of class pearl is
400 ~ 800nm, 500 ~ 800nm of class pearl spacing；The nanorod diameter for connecting teardrop shape thing is 80 ~ 500nm.
Embodiment 11
Preparation method be the same as Example 1, unlike：It is 1.5 that melamine is dissolved in into volume ratio:1 ethylene glycol and the third three
In alcohol mixed alcohol liquid, class bead chain shape graphitization carbonitride is obtained after calcining：The diameter dimension of class pearl is 300 ~ 800nm, class
500 ~ 800nm of pearl spacing；The nanorod diameter for connecting class pearl is 80 ~ 500nm.
Comparative example 1
12.1, which weigh 1.0g melamines, is added in 20mL ethylene glycol, stirring 30min to homogeneous solution；
12.2 the 0.3M sulfuric acid solutions prepared are added dropwise in above-mentioned solution, persistently stir 30min, until having precipitated
It is complete to separate out；
13.3 above-mentioned precipitation is centrifuged after with after water centrifuge washing 2 times, then with ethanol centrifuge washing 2 times, do
It is dry, obtain presoma solid powder；
13.4 are placed in presoma obtained above in tube furnace, according to 10 DEG C/min heating rates under nitrogen atmosphere protection
380 DEG C are warming up to, insulation 2h is calcined, and is naturally cooled to room temperature, is not generated bead chain shape graphitization carbonitride sample, pattern
Such as Fig. 7.
Comparative example 2
Preparation method be the same as Example 1, unlike：500 DEG C of calcining 2h, do not generate bead chain shape graphitization carbonitride sample
Product, pattern such as Fig. 8.
Comparative example 3
Preparation method be the same as Example 1, unlike：365 DEG C of calcining 2h, do not generate bead chain shape graphitization carbonitride sample
Product.
Comparative example 4
Preparation method be the same as Example 1, unlike：Programming rate is 5 DEG C/min, does not generate the nitridation of bead chain shape graphitization
Carbon sample.
Comparative example 5
Preparation method be the same as Example 1, unlike：Alcohol liquid is ethylene glycol and glycerine, and its volume ratio is 1:2, do not have
Generate bead chain shape graphitization carbonitride sample, pattern such as Fig. 9.
Comparative example 6
Preparation method be the same as Example 1, unlike：Sample calcines 2h in atmosphere, does not obtain class bead chain shape graphitization
Carbonitride sample.
Claims (3)
1. the preparation method of a species bead chain shape graphitization azotized carbon nano material, it is characterised in that comprise the following steps：
（1）Melamine is added in alcohol liquid, stirring obtains uniform initial soln；
（2）To step（1）Initial soln in salpeter solution is added dropwise, stir, separate out precipitation；
（3）By step（2）Obtained precipitation is centrifuged, is washed with water and ethanol, dried successively, obtains presoma solid powder
End；
（4）By step（3）Obtained presoma solid powder is heated to 380~450 DEG C, is fired under inert gas shielding
Melamine is decomposed completely, is cooled to room temperature, obtains class bead chain shape graphitization azotized carbon nano material；
Step（1）In, the concentration that described melamine is dissolved in alcohol is 0.16~0.40mol/L；Described alcohol liquid is ethylene glycol
With the mixed liquor of glycerine, ethylene glycol and glycerine volume ratio are 1~2 in described mixed liquor:1；
Step（4）In, described inert gas is nitrogen；Described calcining, heating rate is 10 DEG C/min, and calcination time is 1
~5h；
The class bead chain shape graphitization azotized carbon nano material that the preparation method is prepared is by graphitization azotized carbon nano rod
The class bead chain shape structure that surface alignment class pearl is convexed to form, the diameter dimension of class pearl is 200~800nm, class pearl
Thing 200~800nm of spacing, the nanorod diameter of connection class pearl is 80~500nm, a length of 5~13.6 μm of chain.
2. preparation method according to claim 1, it is characterised in that：Step（2）In, described salpeter solution is nitric acid
The aqueous solution, concentration is 0.1~0.5mol/L；The volume ratio of described salpeter solution and alcohol liquid is 1~3.6:1.
3. preparation method according to claim 1, it is characterised in that：Step（2）In, it is 10~60 to continue mixing time
min。
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| CN102616757B (en) * | 2012-01-11 | 2013-10-30 | 南京大学昆山创新研究院 | Preparation method for self-assembly carbonitride nanotube and nanotube prepared by using same |
| CN103769213B (en) * | 2014-01-07 | 2016-06-01 | 河北科技大学 | The preparation method of a kind of phosphorus doping graphite phase carbon nitride visible light catalyst |
| CN104292236A (en) * | 2014-09-15 | 2015-01-21 | 浙江大学 | Preparation method of three-dimensional porous g-C3N4 material |
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