CN106379882B - A kind of preparation method of multistage three-dimensional chain carbon nano net - Google Patents
A kind of preparation method of multistage three-dimensional chain carbon nano net Download PDFInfo
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- CN106379882B CN106379882B CN201610730016.7A CN201610730016A CN106379882B CN 106379882 B CN106379882 B CN 106379882B CN 201610730016 A CN201610730016 A CN 201610730016A CN 106379882 B CN106379882 B CN 106379882B
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Abstract
A kind of preparation method of multistage three-dimensional chain carbon nano net, it is 0.5 2.0mol/L that carbon source, which is first made, and urea concentration is 0.5 2.0mol/L, and iron salt concentration is 0.05 0.1mol/L, the mixed solution A of a concentration of 0.01 0.05mol/L of ethanedioic acid；By mixed solution, equably mixed solution B is made；By mixed solution B freezings, drying, under an argon atmosphere, after heating, multistage three-dimensional chain carbon nano net is obtained.For the present invention using glucide as carbon source, urea is nitrogen source, and molysite prepares chain carbon nano net super capacitor material for catalyst, and the low in raw material price of the method, method is simple, and reaction temperature is more mild, and energy consumption is relatively low.Product prepared by the present invention is in multistage three-dimensional net structure, and product morphology is uniform, and continuity is good, and specific surface area is larger, and is successional multilevel hierarchy, is conducive to the electric conductivity and adsorptivity that improve product.
Description
Technical field
The invention belongs to technical field of nano material, and in particular to a kind of preparation side of multistage three-dimensional chain carbon nano net
Method.
Background technology
Porous carbon materials may be used as the fields such as ultracapacitor, cell negative electrode material and sorbing material.Due to porous carbon
Material has a wide range of applications, and receives vast researcher concern always.The raw material for preparing porous carbon materials at present mainly has
High molecular polymer and biological carbon material.Carbon material prepared by high molecular polymer has structure uniform, and porosity is high, compares table
The advantages that area is big, and repeatability is high, but usual high molecular polymer is expensive, cost is higher.Biological carbon material comes
Source is extensive, cheap, is a kind of very potential raw material.The performance for improving carbon material at present mainly has following methods：
(1) elements such as nitrogen and sulphur are used to be doped.(2) preparing has carbon nano-structured carbon material, improves the specific surface area of product.
Therefore the performance of carbon material will be greatly improved by preparing the porous carbon materials of the N doping with high-specific surface area.Prepare nitrogen at present
The method of the carbon material of doping mainly has high temperature CVD method, and nitrating is carried out under ammonia atmosphere, and reaction temperature is higher, is 800 DEG C
More than, energy expenditure is also higher.Therefore a kind of low in raw material price is found, energy-efficient method is necessary.
Invention content
The present invention is directed to existing issue, and main purpose is to propose one kind using molysite as the multistage three-dimensional chain of catalyst preparation
The method of carbon nano net.For this method using carbohydrate as carbon source, urea is nitrogen source, and molysite is super to prepare chain carbon nano net for catalyst
Grade capacitor material.Specific surface area by the carbon material prepared by the method is larger, and synthesis temperature is relatively low.
To achieve the above object, technical scheme is as follows：
A kind of preparation method of multistage three-dimensional chain carbon nano net, includes the following steps：
1) carbohydrate carbon source, urea, molysite and ethanedioic acid are add to deionized water, are stirred evenly, carbon source, which is made, is
0.5-2.0mol/L, urea concentration 0.5-2.0mol/L, iron salt concentration 0.05-0.1mol/L, a concentration of 0.01- of ethanedioic acid
The mixed solution A of 0.05mol/L；
2) ultrasound 0.5-2h, is made equably mixed solution B under by the mixed solution A of above-mentioned preparation at 200~500W；
3) by mixed solution B freezings, drying, loose product C is obtained；
4) under an argon atmosphere by loose product C, at 100 DEG C, and 1h is kept the temperature, then heats to 500-800 DEG C, and keep the temperature
2-5h obtains multistage three-dimensional chain carbon nano net.
The present invention, which further improves, to be, carbohydrate carbon source is carboxymethyl cellulose, chitosan, sucrose or Portugal in step 1)
Grape sugar.
The present invention, which further improves, to be, molysite is ammonium ferric oxalate or ferric citrate amine in step 1).
The present invention, which further improves, to be, the time stirred in step 1) is 10-30min.
The present invention, which further improves, to be, freezing is specifically to freeze 2h at -30 DEG C in step 3).
The present invention, which further improves, to be, dry in step 3) is specifically the dry 24- in vacuum freeze drier
48h。
The present invention, which further improves, to be, is kept the temperature in step 4) and is carried out in being placed in tube furnace.
The present invention, which further improves, to be, with the rate of 5-15 DEG C/min from room temperature to 100 DEG C in step 4).
The present invention, which further improves, to be, is warming up to the heating rate of 5-15 DEG C/min from 100 DEG C in step 4)
500-800℃。
Compared with prior art, the device have the advantages that：
1) for the present invention using glucide as carbon source, urea is nitrogen source, and molysite is super to prepare chain carbon nano net for catalyst
Grade capacitor material, the low in raw material price of the method, method is simple, and reaction temperature is more mild, and energy consumption is relatively low.
2) product prepared by the present invention is in multistage three-dimensional net structure, and product morphology is uniform, and continuity is good, compares table
Area is larger, and is successional multilevel hierarchy, is conducive to the electric conductivity and adsorptivity that improve product.
3) contain a small amount of iron simple substance in the product prepared by the present invention, the electric conductivity of product can be effectively improved, into
And improve the chemical property of product.
Description of the drawings
Fig. 1 is the XRD diagram of the present invention.
Fig. 2 is the low power SEM figures of the present invention.
Fig. 3 is the high power SEM figures of the present invention.
Fig. 4 is the transmission electron microscope picture of the present invention.
Specific implementation mode
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings
Embodiment 1
1) analytically pure urea, carboxymethyl cellulose, ammonium ferric oxalate and ethanedioic acid are add to deionized water, are stirred
It is a concentration of that a concentration of 0.5mol/L of carboxymethyl cellulose, urea concentration 0.8mol/L, ammonium ferric oxalate is made in 10min
The mixed solution A of 0.05mol/L and a concentration of 0.01mol/L of ethanedioic acid；
2) by the mixed solution A of above-mentioned preparation at 200W ultrasound 2h, equably mixed solution B is made；
3) mixed solution B is freezed into 2h at -30 DEG C, then the dry 40h in vacuum freeze drier, obtains loose production
Object C；
4) loose product C is placed in tube furnace, under an argon atmosphere, with the rate of 10 DEG C/min from room temperature extremely
100 DEG C, and 1h is kept the temperature, it then proceedes to be warming up to 600 DEG C with the heating rate of 15 DEG C/min, and keep the temperature 2h, obtains multistage three-dimensional
Chain carbon nano net.
Product is analyzed using Rigaku D/max2000PCX- x ray diffractometer xs, the XRD of products therefrom is shown in attached drawing 1, from figure
In it can be seen that product have apparent carbon peak at 25 ° or so.The S4800 Flied emissions Electronic Speculum that sample Rigaku is produced into
Row observation, as can be seen that product is in multistage three-dimensional net structure from Fig. 2 and Fig. 3, product morphology is uniform, and continuity is good.
The FEI Tecnai G2 F20 S-TWIN transmission electron microscopes that the sample is produced with U.S. FEI are observed, it can from Fig. 4
Go out, product is in the tulle structure similar to graphene.
Embodiment 2
1) analytically pure ferric citrate amine, urea, chitosan and ethanedioic acid are add to deionized water, stir 30min,
Be made chitosan concentration be 0.8mol/L, urea concentration 2.0mol/L, a concentration of 0.08mol/L of ferric citrate and ethanedioic acid
The mixed solution A of a concentration of 0.01mol/L；
2) by the mixed solution A of above-mentioned preparation at 500W ultrasound 2h, equably mixed solution B is made；
3) mixed solution B is freezed into 2h at -30 DEG C, then the dry 30h in vacuum freeze drier, obtains loose production
Object C；
4) loose product C is placed in tube furnace, under an argon atmosphere, with the rate of 10 DEG C/min from room temperature extremely
100 DEG C, and 1h is kept the temperature, it then proceedes to be warming up to 500 DEG C with the heating rate of 10 DEG C/min, and keep the temperature 5h, obtains multistage three-dimensional
Chain carbon nano net.
Embodiment 3
1) analytically pure urea, sucrose, ammonium ferric oxalate and ethanedioic acid are add to deionized water, stir 20min, system
Be 1mol/L at sucrose concentration, urea concentration 0.5mol/L, a concentration of 0.1mol/L of ammonium ferric oxalate and ethanedioic acid it is a concentration of
The mixed solution A of 0.05mol/L；
2) by the mixed solution A of above-mentioned preparation at 300W ultrasound 0.5h, equably mixed solution B is made；
3) mixed solution B is freezed into 2h at -30 DEG C, then drying for 24 hours, obtains loose production in vacuum freeze drier
Object C；
4) loose product C is placed in tube furnace, under an argon atmosphere, with the rate of 5 DEG C/min from room temperature to 100
DEG C, and 1h is kept the temperature, it then proceedes to be warming up to 800 DEG C with the heating rate of 10 DEG C/min, and keep the temperature 2h, obtains multistage three-dimensional chain
Carbon nano net.
Embodiment 4
1) analytically pure ferric citrate amine, urea, glucose and ethanedioic acid are add to deionized water, stir 15min,
Be made concentration of glucose be 1.5mol/L, urea concentration 1mol/L, a concentration of 0.07mol/L of ferric citrate and ethanedioic acid it is dense
Degree is the mixed solution A of 0.02mol/L；
2) by the mixed solution A of above-mentioned preparation at 400W ultrasound 1h, equably mixed solution B is made；
3) mixed solution B is freezed into 2h at -30 DEG C, then the dry 48h in vacuum freeze drier, obtains loose production
Object C；
4) loose product C is placed in tube furnace, under an argon atmosphere, with the rate of 15 DEG C/min from room temperature extremely
100 DEG C, and 1h is kept the temperature, it then proceedes to be warming up to 700 DEG C with the heating rate of 5 DEG C/min, and keep the temperature 3h, obtains multistage three-dimensional chain
Shape carbon nano net.
Embodiment 5
1) analytically pure ferric citrate amine, urea, chitosan and ethanedioic acid are add to deionized water, stir 25min,
Be made chitosan concentration be 2mol/L, urea concentration 1.5mol/L, a concentration of 0.06mol/L of ferric citrate and ethanedioic acid it is dense
Degree is the mixed solution A of 0.04mol/L；
2) by the mixed solution A of above-mentioned preparation at 500W ultrasound 1.5h, equably mixed solution B is made；
3) mixed solution B is freezed into 2h at -30 DEG C, then the dry 36h in vacuum freeze drier, obtains loose production
Object C；
4) loose product C is placed in tube furnace, under an argon atmosphere, with the rate of 8 DEG C/min from room temperature to 100
DEG C, and 1h is kept the temperature, it then proceedes to be warming up to 650 DEG C with the heating rate of 12 DEG C/min, and keep the temperature 4h, obtains multistage three-dimensional chain
Carbon nano net.
Claims (7)
1. a kind of preparation method of multistage three-dimensional chain carbon nano net, which is characterized in that include the following steps：
1) carbohydrate carbon source, urea, molysite and ethanedioic acid are add to deionized water, are stirred evenly, it is 0.5- that carbon source, which is made,
2.0mol/L, urea concentration 0.5-2.0mol/L, iron salt concentration 0.05-0.1mol/L, a concentration of 0.01- of ethanedioic acid
The mixed solution A of 0.05mol/L；Wherein, molysite is ammonium ferric oxalate or ferric citrate amine；
2) by the mixed solution A of above-mentioned preparation at 200~500W ultrasound 0.5-2h, equably mixed solution B is made；
3) by mixed solution B freezings, drying, loose product C is obtained；
4) under an argon atmosphere by loose product C, with the rate of 5-15 DEG C/min from room temperature to 100 DEG C, and 1h is kept the temperature, so
After be warming up to 500-800 DEG C, and keep the temperature 2-5h, obtain multistage three-dimensional chain carbon nano net.
2. a kind of preparation method of multistage three-dimensional chain carbon nano net according to claim 1, which is characterized in that step 1)
Middle carbohydrate carbon source is carboxymethyl cellulose, chitosan, sucrose or glucose.
3. a kind of preparation method of multistage three-dimensional chain carbon nano net according to claim 1, which is characterized in that step 1)
The time of middle stirring is 10-30min.
4. a kind of preparation method of multistage three-dimensional chain carbon nano net according to claim 1, which is characterized in that step 3)
Middle freezing is specifically to freeze 2h at -30 DEG C.
5. a kind of preparation method of multistage three-dimensional chain carbon nano net according to claim 1, which is characterized in that step 3)
Middle drying is specifically the dry 24-48h in vacuum freeze drier.
6. a kind of preparation method of multistage three-dimensional chain carbon nano net according to claim 1, which is characterized in that step 4)
Middle heat preservation carries out in being placed in tube furnace.
7. a kind of preparation method of multistage three-dimensional chain carbon nano net according to claim 1, which is characterized in that step 4)
In be warming up to 500-800 DEG C from 100 DEG C with the heating rate of 5-15 DEG C/min.
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